Selective catalytic reduction system and process for treating NOx emissions using a zinc or titanium promoted palladium-zirconium catalyst

DOEpatents

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-08-02

A process and system (18) for reducing NO.sub.x in a gas using hydrogen as a reducing agent is provided. The process comprises contacting the gas stream (29) with a catalyst system (38) comprising sulfated zirconia washcoat particles (41), palladium, a pre-sulfated zirconia binder (44), and a promoter (45) comprising at least one of titanium, zinc, or a mixture thereof. The presence of zinc or titanium increases the resistance of the catalyst system to a sulfur and water-containing gas stream.

Zinc sulfide liquefaction catalyst

DOEpatents

Garg, Diwakar

1984-01-01

A process for the liquefaction of carbonaceous material, such as coal, is set forth wherein coal is liquefied in a catalytic solvent refining reaction wherein an activated zinc sulfide catalyst is utilized which is activated by hydrogenation in a coal derived process solvent in the absence of coal.

Cationic Zn-Porphyrin Polymer Coated onto CNTs as a Cooperative Catalyst for the Synthesis of Cyclic Carbonates.

PubMed

Jayakumar, Sanjeevi; Li, He; Chen, Jian; Yang, Qihua

2018-01-24

The development of solid catalysts containing multiple active sites that work cooperatively is very attractive for biomimetic catalysis. Herein, we report the synthesis of bifunctional catalysts by supporting cationic porphyrin-based polymers on carbon nanotubes (CNTs) using the direct reaction of 5,10,15,20-tetrakis(4-pyridyl)porphyrin zinc(II), di(1H-imidazol-1-yl)methane, and 1,4-bis(bromomethyl)benzene in the presence of CNTs. The bifunctional catalysts could efficiently catalyze the cycloaddition reaction of epoxides and CO 2 under solvent-free conditions with porphyrin zinc(II) as the Lewis acid site and a bromine anion as a nucleophilic agent working in a cooperative way. Furthermore, a relative amount of porphyrin zinc(II) and quaternary ammonium bromide could be facilely adjusted for facilitating cooperative behavior. The bifunctional catalyst with a TOF up to 2602 h -1 is much more active than the corresponding homogeneous counterpart and is one of the most active heterogeneous catalysts ever reported under cocatalyst-free conditions. The high activity is mainly attributed to the enhanced cooperation effect of the bifunctional catalyst. With a wide substrate scope, the bifunctional catalyst could be stably recycled. This work demonstrates a new approach for the generation of a cooperative activation effect for solid catalysts.

Supported versus colloidal zinc oxide for advanced oxidation processes

NASA Astrophysics Data System (ADS)

Laxman, Karthik; Al Rashdi, Manal; Al Sabahi, Jamal; Al Abri, Mohammed; Dutta, Joydeep

2017-07-01

Photocatalysis is a green technology which typically utilizes either supported or colloidal catalysts for the mineralization of aqueous organic contaminants. Catalyst surface area and surface energy are the primary factors determining its efficiency, but correlation between the two is still unclear. This work explores their relation and hierarchy in a photocatalytic process involving both supported and colloidal catalysts. In order to do this the active surface areas of supported zinc oxide nanorods (ZnO NR's) and colloidal zinc oxide nanoparticles (having different surface energies) were equalized and their phenol oxidation mechanism and capacity was analyzed. It was observed that while surface energy had subtle effects on the oxidation rate of the catalysts, the degradation efficiency was primarily a function of the surface area; which makes it a better parameter for comparison when studying different catalyst forms of the same material. Thus we build a case for the use of supported catalysts, wherein their catalytic efficiency was tested to be unaltered over several days under both natural and artificial light, suggesting their viability for practical applications.

Electron-microprobe study of chromitites associated with alpine ultramafic complexes and some genetic implications

USGS Publications Warehouse

Bird, M.L.

1978-01-01

Electron-microprobe and petrographic studies of alpine chromite deposits from around the world demonstrate that they are bimodal with respect to the chromic oxide content of their chromite. The two modes occur at 54 ? 4 and 37 ? 3 weight per cent chromic oxide corresponding to chromite designated as high-chromium and high-aluminum chromite respectively. The high-chromium chromite occurs exclusively with highly magnesian olivine (Fo92-97) and some interstitial diopside. The high-aluminum chromite is associated with more ferrous olivine (Fo88-92), diopside, enstatite, and feldspar. The plot of the mole ratios Cr/(Cr+Al+Fe3+) vs. Mg/(Mg+Fe2+) usually presented for alpine chromite is shown to have a high-chromium, high-iron to low-chromium, low-iron trend contrary to that shown by stratiform chromite. This trend is characteristic of alpine type chromite and is termed the alpine trend. However, a trend similar to that for startiform chromite is discernable on the graph for the high-chromium chromite data. This latter trend is well-developed at Red Mountain, Seldovia, Alaska. Analysis of the iron-magnesium distribution coefficient, Kd=(Fe/Mg)ol/(Fe/Mg)ch, between olivine and chromite shows that Kd for the high-chromium chromite from all ultramafic complexes has essentially the same constant value of .05 while the distribution coefficient for the high-aluminum chromite varies with composition of the chromite. These distribution coefficients are also characteristic of alpine-type chromites. The constant value for Kd for the high-chromium chromite and associated high-magnesium olivine in all alpine complexes suggests that they all crystallized under similar physico-chemical conditions. The two types of massive chromite and their associations of silicate minerals suggest the possibility of two populations with different origins. Recrystallization textures associated with the high-aluminum chromite together with field relationships between the gabbro and the chromite pods, suggest that the high-aluminum chromite was formed by metamorphic recrystallization of the ultramafic rocks and adjacent gabbro.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-31

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Continuous fabrication of a MnS/Co nanofibrous air electrode for wide integration of rechargeable zinc-air batteries.

PubMed

Wang, Yang; Fu, Jing; Zhang, Yining; Li, Matthew; Hassan, Fathy Mohamed; Li, Guang; Chen, Zhongwei

2017-10-26

Exploring highly efficient bifunctional electrocatalysts toward the oxygen reduction and evolution reactions is essential for the realization of high-performance rechargeable zinc-air batteries. Herein, a novel nanofibrous bifunctional electrocatalyst film, consisting of metallic manganese sulfide and cobalt encapsulated by nitrogen-doped carbon nanofibers (CMS/NCNF), is prepared through a continuous electrospinning method followed by carbonization treatment. The CMS/NCNF bifunctional catalyst shows both comparable ORR and OER performances to those of commercial precious metal-based catalysts. Furthermore, the free-standing CMS/NCNF fibrous thin film is directly used as the air electrode in a solid-state zinc-air battery, which exhibits superior flexibility while retaining stable battery performance at different bending angles. This study provides a versatile design route for the rational design of free-standing bifunctional catalysts for direct use as the air electrode in rechargeable zinc-air batteries.

Occurrence and mineral chemistry of chromite and related silicates from the Hongshishan mafic-ultramafic complex, NW China with petrogenetic implications

NASA Astrophysics Data System (ADS)

Ruan, Banxiao; Yu, Yingmin; Lv, Xinbiao; Feng, Jing; Wei, Wei; Wu, Chunming; Wang, Heng

2017-10-01

The Hongshishan mafic-ultramafic complex is located in the western Beishan Terrane, NW China, and hosts an economic Ni-Cu deposit. Chromite as accessory mineral from the complex is divided into three types based on its occurrence and morphology. Quantitative electron probe microanalysis (EPMA) have been conducted on the different types of chromites. Type 1 chromite occurs as inclusions within silicate minerals and has relatively homogeneous composition. Type 2 chromite occurs among serpentine, as interstitial phase. Type 3 chromite is zoned and exhibits a sudden change in compositions from core to rim. Type 1 chromite occurs in olivine gabbro and troctolite showing homogeneous composition. This chromite is more likely primary. Interstitial type 2 and zoned type 3 chromite has compositional variation from core to rim and is more likely modified. Abundant inclusions of orthopyroxene, phlogopite and hornblende occur within type 2 and type 3 chromites. The parental melt of type 1 chromite has an estimated composition of 14.5 wt% MgO, 12.3 wt% Al2O3 and 1.9 wt% TiO2 and is characterized by high temperature, picritic affinity, hydrous nature and high Mg and Ti contents. Compositions of chromite and clinopyroxene are distinct from those of Alaskan-type complexes and imply that the subduction-related environment is not reasonable. Post orogenic extension and the early Permian mantle plume are responsible for the emplacement of mafic-ultramafic complexes in the Beishan Terrane. The cores of zoned chromites are classified as ferrous chromite and the rims as ferrian chromite. The formation of ferrian rim involves reaction of ferrous chromite, forsterite and magnetite to produce ferrian chromite and chlorite, or alternaively, the rim can be simply envisioned as the result of external addition of magnetite in solution to the already formed ferrous chromite.

Mineral resource of the month: Chromium

USGS Publications Warehouse

Schulte, Ruth

2018-01-01

Although chromium is a metal, it does not occur naturally in metallic form. Chromium can be found in many minerals, but the only economically significant chromium-bearing mineral is chromite. Chromite has been mined from four different deposit types: stratiform chromite, podiform chromite, placer chromite, and laterite deposits. Most of the world's resources, however, are located in stratiform chromite deposits, such as the Bushveld Complex in South Africa. The economic potential of chromite resources depends on the thickness and continuity of the deposit and on the grade of the ore. Many of the major stratiform chromite deposits also contain economic levels of platinum, paladium, rhodium, osmium, iridium, and ruthenium.

Method and apparatus for maintaining the pH in zinc-bromine battery systems

DOEpatents

Grimes, Patrick G.

1985-09-10

A method and apparatus for maintaining the pH level in a zinc-bromine battery features reacting decomposition hydrogen with bromine in the presence of a catalyst. The catalyst encourages the formation of hydrogen and bromine ions. The decomposition hydrogen is therefore consumed, alloying the pH of the system to remain substantially at a given value.

Catalysts for the production of hydrocarbons from carbon monoxide and water

DOEpatents

Sapienza, Richard S.; Slegeir, William A.; Goldberg, Robert I.

1987-04-07

A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: and for olefinic hydrocarbons: where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Synthesis of triazole-based and imidazole-based zinc catalysts

DOEpatents

Valdez, Carlos A.; Satcher, Jr., Joe H.; Aines, Roger D.; Baker, Sarah E.

2013-03-12

Various methods and structures of complexes and molecules are described herein related to a zinc-centered catalyst for removing carbon dioxide from atmospheric or aqueous environments. According to one embodiment, a method for creating a tris(triazolyl)pentaerythritol molecule includes contacting a pentaerythritol molecule with a propargyl halide molecule to create a trialkyne molecule, and contacting the trialkyne molecule with an azide molecule to create the tris(triazolyl)pentaerythritol molecule. In another embodiment, a method for creating a tris(imidazolyl)pentaerythritol molecule includes alkylating an imidazole 2-carbaldehyde molecule to create a monoalkylated aldehyde molecule, reducing the monoalkylated aldehyde molecule to create an alcohol molecule, converting the alcohol molecule to create an alkyl halide molecule using thionyl halide, and reacting the alkyl halide molecule with a pentaerythritol molecule to create a tris(imidazolyl)pentaerythritol molecule. In another embodiment, zinc is bound to the tris(triazolyl)pentaerythritol molecule to create a zinc-centered tris(triazolyl)pentaerythritol catalyst for removing carbon dioxide from atmospheric or aqueous environments.

Oxygenates vs. synthesis gas

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

Kamil Klier; Richard G. Herman; Alessandra Beretta

1999-04-01

Methanol synthesis from H{sub 2}/CO has been carried out at 7.6 MPa over zirconia-supported copper catalysts. Catalysts with nominal compositions of 10/90 mol% and 30/70 mol% Cu/ZrO{sub 2} were used in this study. Additionally, a 3 mol% cesium-doped 10/90 catalyst was prepared to study the effect of doping with heavy alkali, and this promoter greatly increased the methanol productivity. The effects of CO{sub 2} addition, water injection, reaction temperature, and H{sub 2}/C0 ratio have been investigated. Both CO{sub 2} addition to the synthesis gas and cesium doping of the catalyst promoted methanol synthesis, while inhibiting the synthesis of dimethyl ether.more » Injection of water, however, was found to slightly suppress methanol and dimethyl ether formation while being converted to CO{sub 2} via the water gas shift reaction over these catalysts. There was no clear correlation between copper surface area and catalyst activity. Surface analysis of the tested samples revealed that copper tended to migrate and enrich the catalyst surface. The concept of employing a double-bed reactor with a pronounced temperature gradient to enhance higher alcohol synthesis was explored, and it was found that utilization of a Cs-promoted Cu/ZnO/Cr{sub 2}O{sub 3} catalyst as a first lower temperature bed and a Cs-promoted ZnO/Cr{sub 2}O{sub 3} catalyst as a second high-temperature bed significantly promoted the productivity of 2-methyl-1-propanol (isobutanol) from H{sub 2}/CO synthesis gas mixtures. While the conversion of CO to C{sub 2+} oxygenates over the double-bed configuration was comparable to that observed over the single Cu-based catalyst, major changes in the product distribution occurred by the coupling to the zinc chromite catalyst; that is, the productivity of the C{sub 1}-C{sub 3} alcohols decreased dramatically, and 2-methyl branched alcohols were selectively formed. The desirable methanol/2-methyl oxygenate molar ratios close to 1 were obtained in the present double-bed system that provides the feedstock for the synthesis of high octane and high cetane ethers, where the isobutanol productivity was as high as 139 g/kg cat/hr. Higher alcohol synthesis has been investigated over a Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalyst at temperatures higher (up to 703K) than those previously utilized, and no sintering of the catalyst was observed during the short-term testing. However, the higher reaction temperatures led to lower CO conversion levels and lower yield of alcohols, especially of methanol, because of equilibrium limitations. With the double catalyst bed configuration, the effect of pressure in the range of 7.6--12.4 MPa on catalyst activity and selectivity was studied. The upper bed was composed of the copper-based catalyst at 598K, and the lower bed consisted of a copper-free Cs-ZnO/Cr{sub 2}O{sub 3} catalyst at a high temperature of 678K. High pressure was found to increase CO conversion to oxygenated products, although the increase in isobutanol productivity did not keep pace with that of methanol. It was also shown that the Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalyst could be utilized to advantage as the second-bed catalyst at 613--643K instead of the previously used copper-free Cs-ZnO/ Cr{sub 2}O{sub 3} catalyst at higher temperature, With double Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalysts, high space time yields of up to 202 g/kg cat/hr, with high selectivity to isobutanol, were achieved.« less

Methods and catalysts for making biodiesel from the transesterification and esterification of unrefined oils

DOEpatents

Yan, Shuli [Detroit, MI; Salley, Steven O [Grosse Pointe Park, MI; Ng, K Y. Simon [West Bloomfield, MI

2012-04-24

A method of forming a biodiesel product and a heterogeneous catalyst system used to form said product that has a high tolerance for the presence of water and free fatty acids (FFA) in the oil feedstock is disclosed. This catalyst system may simultaneously catalyze both the esterification of FAA and the transesterification of triglycerides present in the oil feedstock. The catalyst system according to one aspect of the present disclosure represents a class of zinc and lanthanum oxide heterogeneous catalysts that include different ratios of zinc oxide to lanthanum oxides (Zn:La ratio) ranging from about 10:0 to 0:10. The Zn:La ratio in the catalyst is believed to have an effect on the number and reactivity of Lewis acid and base sites, as well as the transesterification of glycerides, the esterification of fatty acids, and the hydrolysis of glycerides and biodiesel.

Co3O4/MnO2/Hierarchically Porous Carbon as Superior Bifunctional Electrodes for Liquid and All-Solid-State Rechargeable Zinc-Air Batteries.

PubMed

Li, Xuemei; Dong, Fang; Xu, Nengneng; Zhang, Tao; Li, Kaixi; Qiao, Jinli

2018-05-09

The design of efficient, durable, and affordable catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is very indispensable in liquid-type and flexible all-solid-state zinc-air batteries. Herein, we present a high-performance bifunctional catalyst with cobalt and manganese oxides supported on porous carbon (Co 3 O 4 /MnO 2 /PQ-7). The optimized Co 3 O 4 /MnO 2 /PQ-7 exhibited a comparable ORR performance with commercial Pt/C and a more superior OER performance than all of the other prepared catalysts, including commercial Pt/C. When applied to practical aqueous (6.0 M KOH) zinc-air batteries, the Co 3 O 4 /MnO 2 /porous carbon hybrid catalysts exhibited exceptional performance, such as a maximum discharge peak power density as high as 257 mW cm -2 and the most stable charge-discharge durability over 50 h with negligible deactivation to date. More importantly, a series of flexible all-solid-state zinc-air batteries can be fabricated by the Co 3 O 4 /MnO 2 /porous carbon with a layer-by-layer method. The optimal catalyst (Co 3 O 4 /MnO 2 /PQ-7) exhibited an excellent peak power density of 45 mW cm -2 . The discharge potentials almost remained unchanged for 6 h at 5 mA cm -2 and possessed a long cycle life (2.5 h@5 mA cm -2 ). These results make the optimized Co 3 O 4 /MnO 2 /PQ-7 a promising cathode candidate for both liquid-type and flexible all-solid-state zinc-air batteries.

Three dimensional metal/N-doped nanoplate carbon catalysts for oxygen reduction, the reason for using a layered nanoreactor.

PubMed

Yeganeh Ghotbi, Mohammad; Javanmard, Arash; Soleimani, Hassan

2018-02-21

A layered nanoreactor (zinc hydroxide gallate/nitrate nanohybrid) has been designed as a nano-vessel to confine the gallate/nitrate reaction inside zinc hydroxide layers for production of metal/nitrogen-doped carbon catalysts. Metals (Fe 2+ , Co 2+ and Ni 2+ ) doped and bare zinc hydroxide nitrates (ZHN) were synthesized as the α-phase hydroxide hosts. By an incomplete ion-exchange process, nitrate anions between the layers of the hosts were then partially replaced by the gallate anions to produce the layered nanoreactors. Under heat-treatment, the reaction between the remaining un-exchanged nitrate anions and the organic moiety inside the basal spacing of each nanohybrid plate resulted in obtaining highly porous 3D metal/nitrogen-doped carbon nanosheets. These catalysts were then used as extremely efficient electrocatalysts for catalyzing oxygen reduction reaction (ORR). This study is intended to show the way to get maximum electrocatalytic activity of the metal/N-doped carbon catalysts toward the ORR. This exceptionally high ORR performance originates from the increased available surface, the best pore size range and the uniform distribution of the active sites in the produced catalysts, all provided by the use of new idea of the layered nanoreactor.

Effect of Oxide Coating on Performance of Copper-Zinc Oxide-Based Catalyst for Methanol Synthesis via Hydrogenation of Carbon Dioxide.

PubMed

Umegaki, Tetsuo; Kojima, Yoshiyuki; Omata, Kohji

2015-11-16

The effect of oxide coating on the activity of a copper-zinc oxide-based catalyst for methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial catalyst was coated with various oxides by a sol-gel method. The influence of the types of promoters used in the sol-gel reaction was investigated. Temperature-programmed reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the catalysts prepared using L(+)-arginine. These observations indicated that the copper species were weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared using ammonia show higher CO₂ conversion than the catalysts prepared using L(+)-arginine. Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity at low temperatures. At high temperature the conversion over the silica-coated catalyst does not significantly change with reaction temperature, while the conversion over the zirconia-coated catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the durability depends on hydrophilicity of the oxides.

Effect of Oxide Coating on Performance of Copper-Zinc Oxide-Based Catalyst for Methanol Synthesis via Hydrogenation of Carbon Dioxide

PubMed Central

Umegaki, Tetsuo; Kojima, Yoshiyuki; Omata, Kohji

2015-01-01

The effect of oxide coating on the activity of a copper-zinc oxide–based catalyst for methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial catalyst was coated with various oxides by a sol-gel method. The influence of the types of promoters used in the sol-gel reaction was investigated. Temperature-programmed reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the catalysts prepared using L(+)-arginine. These observations indicated that the copper species were weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared using ammonia show higher CO2 conversion than the catalysts prepared using L(+)-arginine. Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity at low temperatures. At high temperature the conversion over the silica-coated catalyst does not significantly change with reaction temperature, while the conversion over the zirconia-coated catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the durability depends on hydrophilicity of the oxides. PMID:28793674

Podiform chromite deposits--database and grade and tonnage models

USGS Publications Warehouse

Mosier, Dan L.; Singer, Donald A.; Moring, Barry C.; Galloway, John P.

2012-01-01

Chromite ((Mg, Fe++)(Cr, Al, Fe+++)2O4) is the only source for the metallic element chromium, which is used in the metallurgical, chemical, and refractory industries. Podiform chromite deposits are small magmatic chromite bodies formed in the ultramafic section of an ophiolite complex in the oceanic crust. These deposits have been found in midoceanic ridge, off-ridge, and suprasubduction tectonic settings. Most podiform chromite deposits are found in dunite or peridotite near the contact of the cumulate and tectonite zones in ophiolites. We have identified 1,124 individual podiform chromite deposits, based on a 100-meter spatial rule, and have compiled them in a database. Of these, 619 deposits have been used to create three new grade and tonnage models for podiform chromite deposits. The major podiform chromite model has a median tonnage of 11,000 metric tons and a mean grade of 45 percent Cr2O3. The minor podiform chromite model has a median tonnage of 100 metric tons and a mean grade of 43 percent Cr2O3. The banded podiform chromite model has a median tonnage of 650 metric tons and a mean grade of 42 percent Cr2O3. Observed frequency distributions are also given for grades of rhodium, iridium, ruthenium, palladium, and platinum. In resource assessment applications, both major and minor podiform chromite models may be used for any ophiolite complex regardless of its tectonic setting or ophiolite zone. Expected sizes of undiscovered podiform chromite deposits, with respect to degree of deformation or ore-forming process, may determine which model is appropriate. The banded podiform chromite model may be applicable for ophiolites in both suprasubduction and midoceanic ridge settings.

Catalytic decomposition of methanol for onboard hydrogen generation

NASA Technical Reports Server (NTRS)

Brabbs, T.

1978-01-01

The steam reformation of an equimolar mixture of methanol and water on a copper chromite catalyst was studied at three furnace temperatures and at feed space velocities from 800 to 2600 per hour. The hydrogen space velocity could be related to the reactor temperature by the equation Sv = A exp (-omega T), where A and omega are constants determined for each value of alpha and T is temperature. At a methanol conversion of 0.87 and a reactor temperature of 589 K, the extrapolated value of the hydrogen space velocity was 9400 per hour. This velocity was used to estimate the size of an onboard hydrogen reactor for automotive applications. Such a reactor would need only about 0.8 liter of catalyst to produce 7630 STP liters (1.5 lb) of hydrogen per hour. This quantity of catalyst would fit into nine tubes 17.8 centimeters along and 2.54 centimeters in inside diameter, which is smaller than most mufflers. The reactor products would contain 12 to 13 percent more chemical energy than the incoming methanol and water.

Cytotoxic and clastogenic effects of soluble and insoluble compounds containing hexavalent and trivalent chromium.

PubMed Central

Levis, A. G.; Majone, F.

1981-01-01

Cr(III) and Cr(VI) compounds of varying solubilities have been tested in vitro for their ability to inhibit cell growth and nucleic acid and protein syntheses in BHK cells, to induce alterations in the mitotic cycle in HEp cells, and to increase the frequency of chromosomal aberrations and sister chromatid exchanges (SCE) in CHO cells. All Cr(VI) compounds, and particularly those containing soluble Cr(VI), such as potassium dichromate and zinc yellow, differentially inhibit macromolecular syntheses in BKH cells, that of DNA being always the most affected. Among Cr(III) compounds, which generally have very low cytotoxicity, chromite is particularly active, and inhibits cell growth and DNA synthesis even more than the poorly soluble Cr(VI) compounds. Preincubation in growth medium, with or without metabolizing cell cultures, solubilizes considerable amounts of Cr(VI) from zinc yellow and chromite, but significant amounts are also obtained from the most insoluble Cr(VI) pigments. When BHK cells are treated with such preincubated solutions, reduction of soluble Cr(VI) to Cr(III) by cell metabolites is seen with all Cr(VI) compounds, accompanied by decreased cytotoxicity. The same differences between Cr(VI) and Cr(III) compounds apply to the cytotoxic effects on mitosis of HEp cells and the clastogenic effects on CHO cells. The activity of chromite, the only Cr(III) pigment capable of significantly increasing the frequency of SCE, is due to contamination with soluble Cr(VI). In contrast to the very low cytotoxicity of Cr(III), much higher chromium levels are detected in the cells incubated with soluble Cr(III) than with the same concentrations of soluble Cr(VI). 50% and 75% of chromium accumulated in the cells during treatments with Cr(VI) and Cr(III) respectively remains firmly bound to the cells, even when they are incubated for up to 48 h in normal growth medium. Chromium accumulated in the cells after treatment with Cr(III) is most probably bound to the cell membrane, whereas some of the Cr(VI) is transported through the cell membrane and reduced in the cell nucleus. The results of the present investigation are in agreement with those obtained with the same Cr(VI) and Cr(III) compounds in mutagenicity assays in bacteria and carcinogenicity tests in rodents. A re-evaluation of the mechanisms of chromium carcinogenisis is proposed. PMID:7272188

Chromite deposits of the north-central Zambales Range, Luzon, Philippines

USGS Publications Warehouse

Rossman, D.L.

1970-01-01

Peridotite and gabbro form an intrusive complex which is exposed over an area about 35 km wide and 150 km long in the center of the Zambales Range of western Luzon. The Zambales Complex is remarkable for its total known resources, mined and still remaining, of about 15 million metric tons of chromite ore. Twenty percent of Free World production was obtained from this area between 1950 and the end of 1964; in 1960 production reached a high of 606,103 metric tons of refractory-grade ore, mostly from the Coto mine near Masinloc, and 128,426 metric tons of metallurgical ore from the Acoje mine. The United States imports 80 to 90 percent of its refractory-grade chromite from the Philippines, and its basic refractory technology has been designed upon the chemical and physical characteristics of Coto high-alumina chromite ore. Continuation of this pattern will depend upon discovery of additional ore reserves to replace those depleted by mining. The Zambales Ultramafic Complex is of the alpine type in which lenticular or podiform deposits of chromite lie in peridotite or dunite, mostly near Contacts with gabbroic rocks. Layered structures, foliation, and lineation commonly are well developed and transect boundaries between major rock units, including chromite deposits, at any angle. Accordingly, these structures cannot be used as guides in exploration and mining as they are used in stratiform complexes such as the Bushveld, where chromite layers extend for many miles. Probably 90 percent of the known deposits in the Zambales Complex are located in two belts in its northern part. One zone containing high-aluminua refractory-grade deposits extends northeast from the Coto mine and Chromite Reservation No. I along a peridotite contact with olivine gabbro, and another of high-chromium metallurgical grade chromite extends south through the Zambales and Acoje properties, and swings westward around the south side of Mount Lanai along a peridotite contact with norite. The textures of ores, association of chromite with dunite as gangue and as halos, and the transecting nature of the layering, foliation, and lineation in relation to chromite, are similar in all deposits regardless of composition of the chromite mineral itself. Textures in chromite ores, and structural relationships between chromite deposits and country rocks, show that layering and related foliation and lineation were formed or modified by flowage. Gabbro is believed to form the upper part of the Complex in general. Geophysical methods have been rather unsuccessful in finding chromite in the Zambales Complex. Gravity surveys, in order to be successful, must correct for all features influencing gravity except for the chromite itself. Too often the uncertainties in position of rock units and in knowledge of rock densities or position of hidden geologic features (dikes, zones of alteration) preclude the possibility of making adequate corrections. Magnetic surveys have failed to reveal any magnetic patterns attributable to the presence of chromite. Exploration for chromite should be guided by the knowledge that chromite occurs only in certain geologic environments. Thus because nearly all known chromite deposits in the Zambales Complex lie in peridotite near the gabbro contact, search for chromite should be concentrated there. Likewise it is evident from structural evidence presented here that there is little relation between layering and distribution of either major rock units or chromite deposits. Thus one is not justified in using the layered structure to predict either the position or attitude of major rock unit contacts, or presence or position of chromite deposits. In such a productive complex it is geologically certain that unknown deposits still remain undiscovered. The most promising areas for exploration are near known groups of large deposits like Acoje and Chromite Reservation No. 1. Underground drilling has been very successful in finding buried tabular

Catalysts for the production of hydrocarbons from carbon monoxide and water

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

Sapienza, Richard S.; Slegeir, William A.; Goldberg, Robert I.

1987-01-01

A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n+1).gtoreq.x.gtoreq.O and for olefinic hydrocarbons: 2n.gtoreq.x.gtoreq.O where n is the number of carbon atoms in the product and x ismore » the molar amount of water in the reaction mixture.« less

Chromite in komatiites: 3D morphologies with implications for crystallization mechanisms

NASA Astrophysics Data System (ADS)

Godel, Bélinda; Barnes, Stephen J.; Gürer, Derya; Austin, Peter; Fiorentini, Marco L.

2013-01-01

High-resolution X-ray computed tomography has been carried out on a suite of komatiite samples representing a range of volcanic facies, chromite contents and degrees of alteration and metamorphism, to reveal the wide range of sizes, shapes and degrees of clustering that chromite grains display as a function of cooling history. Dendrites are spectacularly skeletal chromite grains formed during very rapid crystallization of supercooled melt in spinifex zones close to flow tops. At slower cooling rates in the interiors of thick flows, chromite forms predominantly euhedral grains. Large clusters (up to a dozen of grains) are characteristic of liquidus chromite, whereas fine dustings of mostly individual ~20-μm grains form by in situ crystallization from trapped intercumulus liquid. Chromite in coarse-grained olivine cumulates from komatiitic dunite bodies occurs in two forms: as clusters or chains of euhedral crystals, developing into "chicken-wire" texture where chromite is present in supra-cotectic proportions; and as strongly dendritic, semi-poikilitic grains. These dendritic grains are likely to have formed by rapid crescumulate growth from magma that was close to its liquidus temperature but supersaturated with chromite. In some cases, this process seems to have been favoured by nucleation of chromite on the margins of sulphide liquid blebs. This texture is a good evidence for the predominantly cumulus origin of oikocrysts and in situ origin of heteradcumulate textures. Our 3D textural analysis confirms that the morphology of chromite crystals is a distinctive indicator of crystallization environment even in highly altered rocks.

Ruthenium in komatiitic chromite

NASA Astrophysics Data System (ADS)

Locmelis, Marek; Pearson, Norman J.; Barnes, Stephen J.; Fiorentini, Marco L.

2011-07-01

The distinction between Ru in solid solution and Ru-bearing inclusions is essential for the predictive modeling of platinum-group element (PGE) geochemistry in applications such as the lithogeochemical exploration for magmatic sulfide deposits in komatiites. This study investigates the role of chromite in the fractionation of Ru in ultramafic melts by analyzing chromite grains from sulfide-undersaturated komatiites and a komatiitic basalt from the Yilgarn Craton in Western Australia. In situ analysis using laser ablation ICP-MS yields uniform Ru concentrations in chromites both within-grain and on a sample scale, with concentrations between 220 and 540 ppb. All other platinum-group elements are below the detection limit of the laser ablation ICP-MS analysis. Carius tube digestion isotope dilution ICP-MS analysis of chromite concentrates confirms the accuracy of the in-situ method. Time resolved laser ablation ICP-MS analyses have identified the presence of sub-micron Ir-bearing inclusions in some chromite grains from the komatiitic basalt. However, Ru-bearing inclusions have not been recognized in the analyzed chromites and this combined with the in situ data suggests that Ru exists in solid solution in the crystal lattice of chromite. These results show that chromite can control the fractionation and concentration of Ru in ultramafic systems.

Chromite from the Blue Ridge province of North Carolina.

USGS Publications Warehouse

Lipin, B.R.

1984-01-01

Chromite is found as ubiquitous accessory grains and occasional segregations within dunite bodies. Results of analysis of chromite textures and chemistry and estimation of equilibration T of olivine-chromite pairs are cited as evidence that the dunites are metamorphic rocks rather than primary mantle peridotites. They are considered to be disrupted fragments of ophiolites that were emplaced before or during the peak of Ordovician metamorphism which was responsible for dehydration of serpentine-bearing rocks and alteration of chromite compositions and textures.-M.S.

21 CFR 184.1021 - Benzoic acid.

Code of Federal Regulations, 2011 CFR

2011-04-01

... manufactured by treating molten phthalic anhydride with steam in the presence of a zinc oxide catalyst, by the... air in the presence of a transition metal salt catalyst. (b) The ingredient meets the specifications...

21 CFR 184.1021 - Benzoic acid.

Code of Federal Regulations, 2012 CFR

2012-04-01

... manufactured by treating molten phthalic anhydride with steam in the presence of a zinc oxide catalyst, by the... air in the presence of a transition metal salt catalyst. (b) The ingredient meets the specifications...

21 CFR 184.1021 - Benzoic acid.

Code of Federal Regulations, 2013 CFR

2013-04-01

... manufactured by treating molten phthalic anhydride with steam in the presence of a zinc oxide catalyst, by the... air in the presence of a transition metal salt catalyst. (b) The ingredient meets the specifications...

21 CFR 184.1021 - Benzoic acid.

Code of Federal Regulations, 2010 CFR

2010-04-01

... manufactured by treating molten phthalic anhydride with steam in the presence of a zinc oxide catalyst, by the... air in the presence of a transition metal salt catalyst. (b) The ingredient meets the specifications...

Catalysts for the production of hydrocarbons from carbon monoxide and water

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; Goldberg, R.I.

1985-11-06

A method of converting low H/sub 2//CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200 to 350/sup 0/C in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinum, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n + 1) greater than or equal to x greater than or equal to O and for olefinic hydrocarbons: 2n greater than or equal to x greater than or equal to O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Effect of support size on the catalytic activity of metal-oxide-doped silica particles in the glycolysis of polyethylene terephthalate.

PubMed

Wi, Rinbok; Imran, Muhammad; Lee, Kyoung G; Yoon, Sun Hong; Cho, Bong Gyoo; Kim, Do Hyun

2011-07-01

Zinc oxide (ZnO) and cerium oxide (CeO2) nanoparticles were deposited on the surface of preformed silica spheres with diameters ranging from 60 to 750 nm. Ultrasonic irradiation was employed to promote the deposition of the metal oxide nanoparticles on the surface of silica. Silica-supported zinc oxide or cerium oxide was used as a catalyst in the glycolysis of polyethylene terephthalate, one of the key processes in the depolymerization of polyethylene terephthalate. The effect of the support size on the catalytic activity was studied in terms of monomer yield, and the monomer concentration was analyzed via high-performance liquid chromatography (HPLC). The morphologies and surface properties of the catalysts were characterized using a scanning electron microscope, a transmission electron microscope, and a BET surface area analyzer, while the monomer was characterized via HPLC and nuclear-magnetic-resonance spectroscopy. Both the zinc oxide and cerium oxide deposited on a smaller support showed better distribution and less aggregation. The high specific surface area of the smaller support catalysts provided a large number of active sites. The highest monomer yield was obtained with a catalyst of 60-nm silica support.

Alcohol synthesis from CO or CO.sub.2

DOEpatents

Hu, Jianli [Kennewick, WA; Dagle, Robert A [Richland, WA; Holladay, Jamelyn D [Kennewick, WA; Cao, Chunshe [Houston, TX; Wang, Yong [Richland, WA; White, James F [Richland, WA; Elliott, Douglas C [Richland, WA; Stevens, Don J [Richland, WA

2010-12-28

Methods for producing alcohols from CO or CO.sub.2 and H.sub.2 utilizing a palladium-zinc on alumina catalyst are described. Methods of synthesizing alcohols over various catalysts in microchannels are also described. Ethanol, higher alcohols, and other C.sub.2+ oxygenates can produced utilizing Rh--Mn or a Fisher-Tropsch catalyst.

X-ray tomography as a powerful method for zinc-air battery research

NASA Astrophysics Data System (ADS)

Franke-Lang, Robert; Arlt, Tobias; Manke, Ingo; Kowal, Julia

2017-12-01

X-ray tomography is used to investigate material redistribution and effects of electrochemical reactions in a zinc-air battery in-situ. For this, a special battery set-up is developed which meets tomographic and electrochemical requirements. The prepared batteries are discharged and some of them have partially been charged. To analyse the three-dimensional structure of the zinc and air electrode a tomographic measurement is made in charge and discharge condition without disassembling the battery. X-ray tomography gives the opportunity to detect and analyse three different effects within the cell operation: tracking the morphology and transformation of zinc and air electrode, monitoring electrolyte decomposition and movement, finding electrical misbehaviour by parasitic reactions. Therefore, it is possible to identify the loss of capacity and major problems of cyclability. The electrolyte strongly reacts with the pure zinc that leads to gassing and a loss of electrolyte. The loss prevents a charge carrier exchange between the anode and the cathode and reduces the theoretical capacity. One of the chemical reaction produces hydroxylated zinc, namely zincate. The most crucial problems with cyclability are affected by zincate movement into the catalyst layer. This assumption is confirmed by finding pure zinc areas within the catalyst layer.

A new class of Cu/ZnO catalysts derived from zincian georgeite precursors prepared by co-precipitation† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc04130b Click here for additional data file.

PubMed Central

Smith, Paul J.; Kondrat, Simon A.; Chater, Philip A.; Yeo, Benjamin R.; Shaw, Greg M.; Lu, Li; Bartley, Jonathan K.; Taylor, Stuart H.; Spencer, Michael S.; Kiely, Christopher J.; Kelly, Gordon J.; Park, Colin W.

2017-01-01

Zincian georgeite, an amorphous copper–zinc hydroxycarbonate, has been prepared by co-precipitation using acetate salts and ammonium carbonate. Incorporation of zinc into the georgeite phase and mild ageing conditions inhibits crystallisation into zincian malachite or aurichalcite. This zincian georgeite precursor was used to prepare a Cu/ZnO catalyst, which exhibits a superior performance to a zincian malachite derived catalyst for methanol synthesis and the low temperature water–gas shift (LTS) reaction. Furthermore, the enhanced LTS activity and stability in comparison to that of a commercial Cu/ZnO/Al2O3 catalyst, indicates that the addition of alumina as a stabiliser may not be required for the zincian georgeite derived Cu/ZnO catalyst. The enhanced performance is partly attributed to the exclusion of alkali metals from the synthesis procedure, which are known to act as catalyst poisons. The effect of residual sodium on the microstructural properties of the catalyst precursor was investigated further from preparations using sodium carbonate. PMID:28451351

Crystal-Chemical Correlations in Chromites from Kimberlitic and Non-Kimberlitic Sources.

NASA Astrophysics Data System (ADS)

Freckelton, C. N.; Flemming, R. L.

2009-05-01

This study explores the utility of micro X-ray diffraction (μXRD) as a tool for diamond exploration, as a compliment to current industry-standard techniques such as electron probe microanalysis (EPMA). Here we examine chromite. As one of the first phases to crystallize in mantle rocks, it is a useful indicator of upper mantle magmatic conditions in rocks that have been sampled by kimberlites. In addition, chromite does not alter easily from chemical and physical weathering processes. As such, chromite is a useful kimberlite indicator mineral in diamond exploration. We present correlations between crystal structure (unit cell) and chemical composition of chromite, (Fe,Mg)[Cr, Al]2O4, using correlated μXRD and EPMA data for 133 chromites from a three source locations: Two kimberlite sources and one non-kimberlitic source from an Archean granite/greenstone terrain. Quantitative analysis was performed using Electron Probe Microanalysis (EPMA) at Mineral Services, South Africa, prior to the loan of the samples. Randomly-oriented chromite grains, approximately 500 μm in diameter, were analyzed as previously mounted for EPMA. Micro X-ray-diffraction was performed using a Bruker D8-Discover Diffractometer, with θ-θ geometry, with CuKα radiation, operating at 40 kV and 40 mA, with nominal beam diameter of 500 μm. The data were collected in omega scan mode. Two dimensional General Area Detector Diffraction System (GADDS) images were collected for 20 minutes per image, and integrated to produce one-dimensional plots of intensity versus 2θ, for subsequent unit cell refinement using CELREF. Although all samples in this study were considered to be 'chromite', a plot of Cr/(Cr+Al) versus Fe2+/(Fe2++Mg) shows extensive substitution among four dominant members: chromite (FeCr2O4), magnesio-chromite (MgCr2O4), spinel (MgAl2O4), and hercynite (FeAl2O4), where Mg and Fe2+ substitute for one another on the tetrahedral site, and Cr and Al substitute for one another on the octahedral site. Our data are widely variable as compared to the field occupied by chromite inclusions in diamonds (high Cr and Mg (˜60 wt %) and very low Ti (˜0.40 wt %). Plots of the unit cell parameter, ao, versus composition demonstrate a decrease in unit cell size with increasing Al content (and corresponding decrease in Cr content), consistent with a smaller cation radius for Al versus Cr (Al=0.675 Å and Cr=0.905 Å). The trend in unit cell size is unlikely to be effected by Mg-Fe substitution because of the very small difference in their tetrahedral cation radii (Fe2+=0.835 Å and Mg=0.86 Å). Initial plots of composition versus unit cell parameter were clearly able to distinguish a difference between unit cell of kimberlitic chromites and non-kimberlitic chromites. The significantly higher Cr content in kimberlitic chromites (radius=0.905 Å), and correspondingly higher Al content in non-kimberlitic chromites (radius=0.675 Å), results in a striking bimodal distribution in unit cell parameter, ao, where kimberlitic chromites have a larger unit cell (> 8.3 Å) than non-kimberlitic chromites (< 8.3 Å). This preliminary data provides a useful starting point for screening minerals from naturally relevant chromite solid solutions using their corresponding unit cell parameters. Future work will examine which site substitutions (octahedral versus tetrahedral) are affecting the unit cell as well as the effect of cation order-disorder on unit cell parameters.

Compositional variations in the Mesoarchean chromites of the Nuggihalli schist belt, Western Dharwar Craton (India): potential parental melts and implications for tectonic setting

NASA Astrophysics Data System (ADS)

Mukherjee, Ria; Mondal, Sisir K.; Rosing, Minik T.; Frei, Robert

2010-12-01

The chromite deposits in the Archean Nuggihalli schist belt are part of a layered ultramafic-mafic sequence within the Western Dharwar Craton of the Indian shield. The 3.1-Ga ultramafic-mafic units occur as sill-like intrusions within the volcano-sedimentary sequences of the Nuggihalli greenstone belt that are surrounded by the tonalite-trondhjemite-granodiorite (TTG) suite of rocks. The entire succession is exposed in the Tagdur mining district. The succession has been divided into the lower and the upper ultramafic units, separated by a middle gabbro unit. The ultramafic units comprise of deformed massive chromitite bodies that are hosted within chromite-bearing serpentinites. The chromitite bodies occur in the form of pods and elongated lenses (~60-500 m by ~15 m). Detailed electron microprobe studies reveal intense compositional variability of the chromite grains in silicate-rich chromitite (~50% modal chromite) and serpentinite (~2% modal chromite) throughout the entire ultramafic sequence. However, the primary composition of chromite is preserved in the massive chromitites (~60-75% modal chromite) from the Byrapur and the Bhaktarhalli mining district of the Nuggihalli schist belt. These are characterized by high Cr-ratios (Cr/(Cr + Al) = 0.78-0.86) and moderate Mg-ratios (Mg/(Mg + Fe2+) = 0.38-0.58). The compositional variability occurs due to sub-solidus re-equilibration in the accessory chromite in the serpentinite (Mg-ratio = 0.01-0.38; Cr-ratio = 0.02-0.99) and in silicate-rich chromitite (Mg-ratio = 0.06-0.48; Cr-ratio = 0.60-0.99). In the massive chromitites, the sub-solidus re-equilibration for chromite is less or absent. However, the re-equilibration is prominent in the co-existing interstitial and included olivine (Fo96-98) and pyroxene grains (Mg-numbers = 97-99). Compositional variability on the scale of a single chromite grain occurs in the form of zoning, and it is common in the accessory chromite grains in serpentinite and in the altered grains in chromitite. In the zoned grains, the composition of the core is modified and the rim is ferritchromit. In general, ferritchromit occurs as irregular patches along the grain boundaries and fractures of the zoned grains. In this case, ferritchromit formation is not very extensive. This indicates a secondary low temperature hydrothermal origin of ferritchromit during serpentinization. In some occurrences, the ferritchromit rim is very well developed, and only a small relict core appears to remain in the chromite grain. However, complete alteration of the chromite grains to ferritchromit without any remnant core is also present. The regular, well-developed and continuous occurrence of ferritchromit rims around the chromite grain boundaries, the complete alteration of the chromite grains and the modification of the core composition indicate the alteration in the Nuggihalli schist belt to be intense, pervasive and affected by later low-grade metamorphism. The primary composition of chromite has been used to compute the nature of the parental melt. The parental melt calculations indicate derivation from a high-Mg komatiitic basalt that is similar to the composition of the komatiitic rocks reported from the greenstone sequences of the Western Dharwar Craton. Tectonic discrimination diagrams using the primary composition of chromites indicate a supra-subduction zone setting (SSZ) for the Archean chromitites of Nuggihalli and derivation from a boninitic magma. The composition of the komatiitic basalts resembles those of boninites that occur in subduction zones and back-arc rift settings. Formation of the massive chromitites in Nuggihalli may be due to magma mixing process involving hydrous high-Mg magmas or may be related to intrusions of chromite crystal laden magma; however, there is little scope to test these models because the host rocks are highly altered, serpentinized and deformed. The present configurations of the chromitite bodies are related to the multistage deformation processes that are common in Archean greenstone belts.

Chromite oxidation by manganese oxides in subseafloor basalts and the presence of putative fossilized microorganisms.

PubMed

Ivarsson, Magnus; Broman, Curt; Holm, Nils G

2011-06-03

Chromite is a mineral with low solubility and is thus resistant to dissolution. The exception is when manganese oxides are available, since they are the only known naturally occurring oxidants for chromite. In the presence of Mn(IV) oxides, Cr(III) will oxidise to Cr(VI), which is more soluble than Cr(III), and thus easier to be removed. Here we report of chromite phenocrysts that are replaced by rhodochrosite (Mn(II) carbonate) in subseafloor basalts from the Koko Seamount, Pacific Ocean, that were drilled and collected during the Ocean Drilling Program (ODP) Leg 197. The mineral succession chromite-rhodochrosite-saponite in the phenocrysts is interpreted as the result of chromite oxidation by manganese oxides. Putative fossilized microorganisms are abundant in the rhodochrosite and we suggest that the oxidation of chromite has been mediated by microbial activity. It has previously been shown in soils and in laboratory experiments that chromium oxidation is indirectly mediated by microbial formation of manganese oxides. Here we suggest a similar process in subseafloor basalts.

Chromite oxidation by manganese oxides in subseafloor basalts and the presence of putative fossilized microorganisms

PubMed Central

2011-01-01

Chromite is a mineral with low solubility and is thus resistant to dissolution. The exception is when manganese oxides are available, since they are the only known naturally occurring oxidants for chromite. In the presence of Mn(IV) oxides, Cr(III) will oxidise to Cr(VI), which is more soluble than Cr(III), and thus easier to be removed. Here we report of chromite phenocrysts that are replaced by rhodochrosite (Mn(II) carbonate) in subseafloor basalts from the Koko Seamount, Pacific Ocean, that were drilled and collected during the Ocean Drilling Program (ODP) Leg 197. The mineral succession chromite-rhodochrosite-saponite in the phenocrysts is interpreted as the result of chromite oxidation by manganese oxides. Putative fossilized microorganisms are abundant in the rhodochrosite and we suggest that the oxidation of chromite has been mediated by microbial activity. It has previously been shown in soils and in laboratory experiments that chromium oxidation is indirectly mediated by microbial formation of manganese oxides. Here we suggest a similar process in subseafloor basalts. PMID:21639896

Chromite Ore from the Transvaal Region of South Africa

EPA Pesticide Factsheets

In 2001, EPA finalized a rule to to delete both chromite ore mined in the Transvaal Region of South Africa and the unreacted ore component of the chromite ore processing residue (COPR) from TRI reporting requirements.

Aromatic hydrocarbon production via eucalyptus urophylla pyrolysis over several metal modified ZSM-5 catalysts – an analysis by py-GC/MS

USDA-ARS?s Scientific Manuscript database

Metal modified HZSM-5 catalysts were prepared by ion exchange of NH4ZSM-5 (SIO2/Al2O3 = 23) using gallium, molybdenum, nickel and zinc, and their combinations thereof. The prepared catalysts were used to evaluate catalytic pyrolysis for the conversion of Eucalyptus urophylla to fuels and chemicals, ...

Application of Fe-Ti oxide dissolution experiments to the petrogenesis of the Ekati Diamond Mine kimberlites, Northwest Territories, Canada

NASA Astrophysics Data System (ADS)

Kressall, R.; Fedortchouk, Y.; McCammon, C. A.

2015-12-01

Composition of kimberlites is ambiguous due to assimilation and fractional crystallization. We propose that the evolution history of minerals can be used to decipher the magmatic history of kimberlites. We use Fe-Ti oxides (chromite and ilmenite) from six kimberlites from the Ekati Diamond Mine and dissolution experiments to elucidate the petrogenesis of kimberlites. Experiments at 0.1 MPa and variable ƒO2s in a diopside-anorthite melt show that the dissolution rate of ilmenite is highly sensitive to ƒO2. No significant difference was observed in chromite. Zoning in chromite is related to the Fe-content and oxidation state of the melt. Experiments at 1 GPa explore the development of chromite surface resorption features in the system Ca-Mg-Si-H-C-O. Five kimberlites contain a low abundance of ilmenite, owing to a relatively high ƒO2, though ilmenite constituted 65% of oxide macocrysts in one kimberlite. Chromite compositions evolve from Mg-chromite to magnesio-ulvöspinel-magnetite (MUM) in all but one kimberlite where chromite evolves to a pleonaste composition perhaps as a result of rapid emplacement. The high abundance of MUM spinel and low abundance of ilmenite in the matrix could be related to the change in the stable Ti-phase with increasing ƒO2. Core compositions of macrocrysts vary for different mantle sources but rims converge to a composition slightly more oxidized and Mg-rich than chromite from depleted peridotite. Ilmenite commonly has rims composed of perovskite, titanite and MUM. We suggest a model where the kimberlite melt composition is controlled by the co-dissolution and co-precipitation of silicates (predominantly orthopyroxene and olivine) to explain chromite evolution in kimberlites. Resorption-related surface features on chromite macrocrysts show trigon protrusions-depressions on {111} faces and step-like features along the crystal edges resembling products of experiments in H2O fluid. We propose predominantly H2O magmatic fluid in Ekati kimberlites.

Catalysts for coal liquefaction processes

DOEpatents

Garg, Diwakar

1986-01-01

Improved catalysts for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprise a combination of zinc or copper, or a compound thereof, and a Group VI or non-ferrous Group VIII metal, or a compound thereof.

Catalysts for coal liquefaction processes

DOEpatents

Garg, D.

1986-10-14

Improved catalysts for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprise a combination of zinc or copper, or a compound thereof, and a Group VI or non-ferrous Group VIII metal, or a compound thereof.

The structure of and origin of nodular chromite from the Troodos ophiolite, Cyprus, revealed using high-resolution X-ray computed tomography and electron backscatter diffraction

NASA Astrophysics Data System (ADS)

Prichard, H. M.; Barnes, S. J.; Godel, B.; Reddy, S. M.; Vukmanovic, Z.; Halfpenny, A.; Neary, C. R.; Fisher, P. C.

2015-03-01

Nodular chromite is a characteristic feature of ophiolitic podiform chromitite and there has been much debate about how it forms. Nodular chromite from the Troodos ophiolite in Cyprus is unusual in that it contains skeletal crystals enclosed within the centres of the nodules and interstitial to them. 3D imaging and electron backscatter diffraction have shown that the skeletal crystals within the nodules are single crystals that are surrounded by a rim of polycrystalline chromite. 3D analysis reveals that the skeletal crystals are partially or completely formed cage or hopper structures elongated along the < 111 > axis. The rim is composed of a patchwork of chromite grains that are truncated on the outer edge of the rim. The skeletal crystals formed first from a magma supersaturated in chromite and silicate minerals crystallised from melt trapped between the chromite skeletal crystal blades as they grew. The formation of skeletal crystals was followed by a crystallisation event which formed a silicate-poor rim of chromite grains around the skeletal crystals. These crystals show a weak preferred orientation related to the orientation of the core skeletal crystal implying that they formed by nucleation and growth on this core, and did not form by random mechanical aggregation. Patches of equilibrium adcumulate textures within the rim attest to in situ development of such textures. The nodules were subsequently exposed to chromite undersaturated magma resulting in dissolution, recorded by truncated grain boundaries in the rim and a smooth outer surface to the nodule. None of these stages of formation require a turbulent magma. Lastly the nodules impinged on each other causing local deformation at points of contact.

Trace-element fingerprints of chromite, magnetite and sulfides from the 3.1 Ga ultramafic-mafic rocks of the Nuggihalli greenstone belt, Western Dharwar craton (India)

NASA Astrophysics Data System (ADS)

Mukherjee, Ria; Mondal, Sisir K.; González-Jiménez, José M.; Griffin, William L.; Pearson, Norman J.; O'Reilly, Suzanne Y.

2015-06-01

The 3.1 Ga Nuggihalli greenstone belt in the Western Dharwar craton is comprised of chromitite-bearing sill-like ultramafic-mafic rocks that are surrounded by metavolcanic schists (compositionally komatiitic to komatiitic basalts) and a suite of tonalite-trondhjemite-granodiorite gneissic rocks. The sill-like plutonic unit consists of a succession of serpentinite (after dunite)-peridotite-pyroxenite and gabbro with bands of titaniferous magnetite ore. The chromitite ore-bodies (length ≈30-500 m; width ≈2-15 m) are hosted by the serpentinite-peridotite unit. Unaltered chromites from massive chromitites (>80 % modal chromite) of the Byrapur and Bhaktarhalli chromite mines in the greenstone belt are characterized by high Cr# (100Cr/(Cr + Al)) of 78-86 and moderate Mg# (100 Mg/(Mg + Fe2+)) of 45-55. In situ trace-element analysis (LA-ICPMS) of unaltered chromites indicates that the parental magma of the chromitite ore-bodies was a komatiite lacking nickel-sulfide mineralization. In the Ga/Fe3+# versus Ti/Fe3+# diagram, the Byrapur chromites plot in the field of suprasubduction zone (SSZ) chromites while those from Bhaktarhalli lie in the MOR field. The above results corroborate our previous results based on major-element characteristics of the chromites, where the calculated parental melt of the Byrapur chromites was komatiitic to komatiitic basalt, and the Bhaktarhalli chromite was derived from Archean high-Mg basalt. The major-element chromite data hinted at the possibility of a SSZ environment existing in the Archean. Altered and compositionally zoned chromite grains in our study show a decrease in Ga, V, Co, Zn, Mn and enrichments of Ni and Ti in the ferritchromit rims. Trace-element heterogeneity in the altered chromites is attributed to serpentinization. The trace-element patterns of magnetite from the massive magnetite bands in the greenstone belt are similar to those from magmatic Fe-Ti-V-rich magnetite bands in layered intrusions, and magnetites from andesitic melts, suggesting that magnetite crystallized from an evolved gabbroic melt. Enrichments of Ni, Co, Te, As and Bi in disseminated millerite and niccolite occurring within chromitites, and in disseminated bravoite within magnetites, reflect element mobility during serpentinization. Monosulfide solid solution inclusions within pyroxenes (altered to actinolite) in pyroxenite, and interstitial pyrites and chalcopyrites in magnetite, retain primary characteristics except for Fe-enrichment in chalcopyrite, probably due to sub-solidus re-equilibration with magnetite. Disseminated sulfides are depleted in platinum-group elements (PGE) due to late sulfide saturation and the PGE-depleted nature of the mantle source of the sill-like ultramafic-mafic plutonic rocks in the Nuggihalli greenstone belt.

Zinc-assisted hydrodeoxygenation of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran.

PubMed

Saha, Basudeb; Bohn, Christine M; Abu-Omar, Mahdi M

2014-11-01

2,5-Dimethylfuran (DMF), a promising cellulosic biofuel candidate from biomass derived intermediates, has received significant attention because of its low oxygen content, high energy density, and high octane value. A bimetallic catalyst combination containing a Lewis-acidic Zn(II) and Pd/C components is effective for 5-hydroxymethylfurfural (HMF) hydrodeoxygenation (HDO) to DMF with high conversion (99%) and selectivity (85% DMF). Control experiments for evaluating the roles of zinc and palladium revealed that ZnCl2 alone did not catalyze the reaction, whereas Pd/C produced 60% less DMF than the combination of both metals. The presence of Lewis acidic component (Zn) was also found to be beneficial for HMF HDO with Ru/C catalyst, but the synergistic effect between the two metal components is more pronounced for the Pd/Zn system than the Ru/Zn. A comparative analysis of the Pd/Zn/C catalyst to previously reported catalytic systems show that the Pd/Zn system containing at least four times less precious metal than the reported catalysts gives comparable or better DMF yields. The catalyst shows excellent recyclability up to 4 cycles, followed by a deactivation, which could be due to coke formation on the catalyst surface. The effectiveness of this combined bimetallic catalyst has also been tested for one-pot conversion of fructose to DMF. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Messengers from the deep: Fossil wadsleyite-chromite microstructures from the Mantle Transition Zone.

PubMed

Satsukawa, Takako; Griffin, William L; Piazolo, Sandra; O'Reilly, Suzanne Y

2015-11-13

Investigations of the Mantle Transition Zone (MTZ; 410-660 km deep) by deformation experiments and geophysical methods suggest that the MTZ has distinct rheological properties, but their exact cause is still unclear due to the lack of natural samples. Here we present the first direct evidence for crystal-plastic deformation by dislocation creep in the MTZ using a chromitite from the Luobusa peridotite (E. Tibet). Chromite grains show exsolution of diopside and SiO2, suggesting previous equilibration in the MTZ. Electron backscattered diffraction (EBSD) analysis reveals that olivine grains co-existing with exsolved phases inside chromite grains and occurring on chromite grain boundaries have a single pronounced crystallographic preferred orientation (CPO). This suggests that olivine preserves the CPO of a high-pressure polymorph (wadsleyite) before the high-pressure polymorph of chromite began to invert and exsolve. Chromite also shows a significant CPO. Thus, the fine-grained high-pressure phases were deformed by dislocation creep in the MTZ. Grain growth in inverted chromite produced an equilibrated microstructure during exhumation to the surface, masking at first sight its MTZ deformation history. These unique observations provide a window into the deep Earth, and constraints for interpreting geophysical signals and their geodynamic implications in a geologically robust context.

Electroless-plated Ni pattern with catalyst printing on indium-gallium-zinc oxide surface

NASA Astrophysics Data System (ADS)

Onoue, Miki; Ogura, Shintaro; Kusaka, Yasuyuki; Fukuda, Nobuko; Yamamoto, Noritaka; Kojima, Keisuke; Chikama, Katsumi; Ushijima, Hirobumi

2017-05-01

Electroless plated metals have been used for wiring and electrodes in the manufacture of electronic devices. To obtain plated patterns, etching and photoresist are generally used. However, through catalyst patterning by printing, we can obtain metal patterns without etching and photoresists by electroless plating. Solution-processed indium-gallium-zinc oxide (IGZO) has received significant attention for showing high performance and ease of preparation in air atmosphere. In this study, we prepared an electroless plated pattern by catalyst printing as electrodes of IGZO TFT. There are few reports on the application of plated metal electrodes prepared by catalyst printing to the source and drain electrodes of IGZO TFT. The prepared IGZO TFT exhibits a typical current-voltage (I-V) curve. The plated electrodes caused many problems such as performance degradation. However, our result showed that the plated metal electrodes can drive IGZO TFT. In addition, we confirm plated metal growth into the catalyst layer by cross sectional scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM/EDS) of the plated Ni. We discuss the relevance of the measured work function (WF) of the electrode materials and the performance of IGZO TFT.

Mineral deposits of Central America, with a section on manganese deposits of Panama

USGS Publications Warehouse

Roberts, Ralph Jackson; Irving, Earl Montgomery; Simons, F.S.

1957-01-01

The mineral deposits of Central America were studied between 1942 and 1945, in cooperation with the United States Department of State and the Foreign Economic Administration. Emphasis was originally placed on the study of strategic-mineral deposits, especially of antimony, chromite, manganese, quartz, and mica, but deposits of other minerals that offered promise of significant future production were also studied. A brief appraisal of the base-metal deposits was made, and deposits of iron ore in Honduras and of lead and zinc ores in Guatemala were mapped. In addition, studies were made of the regional geology of some areas, data were collected from many sources, and a new map of the geology of Central America was compiled.

Platinum-bearing chromite layers are caused by pressure reduction during magma ascent.

PubMed

Latypov, Rais; Costin, Gelu; Chistyakova, Sofya; Hunt, Emma J; Mukherjee, Ria; Naldrett, Tony

2018-01-31

Platinum-bearing chromitites in mafic-ultramafic intrusions such as the Bushveld Complex are key repositories of strategically important metals for human society. Basaltic melts saturated in chromite alone are crucial to their generation, but the origin of such melts is controversial. One concept holds that they are produced by processes operating within the magma chamber, whereas another argues that melts entering the chamber were already saturated in chromite. Here we address the problem by examining the pressure-related changes in the topology of a Mg 2 SiO 4 -CaAl 2 Si 2 O 8 -SiO 2 -MgCr 2 O 4 quaternary system and by thermodynamic modelling of crystallisation sequences of basaltic melts at 1-10 kbar pressures. We show that basaltic melts located adjacent to a so-called chromite topological trough in deep-seated reservoirs become saturated in chromite alone upon their ascent towards the Earth's surface and subsequent cooling in shallow-level chambers. Large volumes of these chromite-only-saturated melts replenishing these chambers are responsible for monomineralic layers of massive chromitites with associated platinum-group elements.

Sediment-dispersed extraterrestrial chromite traces a major asteroid disruption event.

PubMed

Schmitz, Birger; Häggström, Therese; Tassinari, Mario

2003-05-09

Abundant extraterrestrial chromite grains from decomposed meteorites occur in middle Ordovician (480 million years ago) marine limestone over an area of approximately 250,000 square kilometers in southern Sweden. The chromite anomaly gives support for an increase of two orders of magnitude in the influx of meteorites to Earth during the mid-Ordovician, as previously indicated by fossil meteorites. Extraterrestrial chromite grains in mid-Ordovician limestone can be used to constrain in detail the temporal variations in flux of extraterrestrial matter after one of the largest asteroid disruption events in the asteroid belt in late solar-system history.

Compaction of Chromite Cumulates applying a Centrifuging Piston-Cylinder

NASA Astrophysics Data System (ADS)

Manoochehri, S.; Schmidt, M. W.

2012-12-01

Stratiform accumulations of chromite cumulates, such as the UG2 chromitite layer in the Bushveld Complex, is a common feature in most of the large layered mafic intrusions. The time scales and mechanics of gravitationally driven crystal settling and compaction and the feasibility of these processes for the formation of such cumulate layers is investigated through a series of high temperature (1280-1300 °C) centrifuge-assisted experiments at 100-2000 g, 0.4-0.6 GPa. A mixture of natural chromite, with defined grain sizes (means of 5 μm, 13 μm, and 52 μm), and a melt with a composition thought to represent the parental magma of the Bushveld Complex, was first chemically and texturally equilibrated at static conditions and then centrifuged. Centrifugation leads to a single cumulate layer formed at the gravitational bottom of the capsule. This layer was analysed for porosity, mean grain size, size distribution and also travelling distance of chromite crystals. The experimentally observed mechanical settling velocity of chromite grains in a suspension with ~ 24 vol% crystals is calculated to be about half (~ 0.53) of the Stokes settling velocity, consistent with a sedimentation exponent n of 2.35±0.3. The settling leads to a porosity of about 52 % in the chromite layer. Formation times of chromite orthocumulates with initial crystal content in the melt of 1 % and grain sizes of 2 mm are thus around 0.6 m/day. To achieve more compacted chromite piles, centrifugation times and acceleration were increased. Within each experiment the crystal content of the cumulate layer increases downward almost linearly at least in the lower 2/3 of the cumulate pile. Although porosity in the lowermost segment of the chromite layer decreases with increasing effective stress integrated over time, the absolute decrease is smaller than for experiments with olivine (from a previous study). Formation times of a ½ meter single chromite layer with 70 vol% chromite, is calculated to be around 20 years whereas this value is around 0.4 years for olivine cumulates. When considering a natural outcrop of a layered intrusion with multiple layers of about 50 meters height, adcumulate formation time decreases to a few months. With increasing the effective stress integrated over time, applied during centrifugation, crystal size distribution histograms move slightly toward larger grain sizes, but looking at mean grain sizes, a narrow range of changes can be observed. Classic crystal size distribution profiles corrected for real 3D sizes (CSDCorrectin program) of the chromite grains in different experiments illustrate a collection of parallel log-linear trends at larger grain sizes with a very slight overturn at small grain sizes. This is in close agreement with the idealized CSD plots of adcumulus growth.

A Lewis acid β-diiminato-zinc-complex as all-rounder for co- and terpolymerisation of various epoxides with carbon dioxide.

PubMed

Reiter, M; Vagin, S; Kronast, A; Jandl, C; Rieger, B

2017-03-01

A β-diiminato-zinc-N(SiMe 3 ) 2 complex ( 1 ) was synthesised and fully characterised, including an X-ray diffraction study. The activity of catalyst 1 towards the coupling reaction of CO 2 and various epoxides, including propylene oxide (PO), cyclohexene oxide (CHO), styrene oxide (SO), limonene oxide (LO), octene oxide (OO) and epichlorohydrin (ECH), was investigated. Terpolymerisation of CO 2 , PO and LO, as well as CO 2 , CHO and PO, was successfully realised, resulting in polymers with adjustable glass transition temperatures and transparencies. Reaction conditions such as temperature, pressure and catalyst concentration were varied to find the optimal reaction values, especially regarding LO/CO 2 . In situ IR experiments hinted that at 60 °C and a critical LO concentration, polymerisation and depolymerisation are in an equilibrium (ceiling effect). Pressurising catalyst 1 with carbon dioxide resulted in a dimeric catalyst ( 2 ) with a OSiMe 3 group as a new initiator. Homopolymerisation of different epoxides was carried out in order to explain the reactivity concerning copolymerisation reaction of CO 2 and epoxides.

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

NASA Astrophysics Data System (ADS)

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

2014-06-01

Ureilites are ultramafic achondrites thought to be residues of partial melting on a carbon-rich asteroid. They show a trend of FeO-variation (olivine Fo from ∼74 to 95) that suggests variation in oxidation state. Whether this variation was established during high-temperature igneous processing on the ureilite parent body (UPB), or preserved from nebular precursors, is a subject of debate. The behavior of chromium in ureilites offers a way to assess redox conditions during their formation and address this issue, independent of Fo. We conducted a petrographic and mineral compositional study of occurrences of chromite (Cr-rich spinel) in ureilites, aimed at determining the origin of the chromite in each occurrence and using primary occurrences to constrain models of ureilite petrogenesis. Chromite was studied in LEW 88774 (Fo 74.2), NWA 766 (Fo 76.7), NWA 3109 (Fo 76.3), HaH 064 (Fo 77.5), LAP 03587 (Fo 74.9), CMS 04048 (Fo 76.4), LAP 02382 (Fo 78.6) and EET 96328 (Fo 85.2). Chromite occurs in LEW 88774 (∼5 vol.%), NWA 766 (<1 vol.%), NWA 3109 (<1 vol.%) and HaH 064 (<1 vol.%) as subhedral to anhedral grains comparable in size (∼30 μm to 1 mm) and/or textural setting to the major silicates (olivine and pyroxenes[s]) in each rock, indicating that it is a primary phase. The most FeO-rich chromites in these sample (rare grain cores or chadocrysts in silicates) are the most primitive compositions preserved (fe# = 0.55-0.6; Cr# varying from 0.65 to 0.72 among samples). They record olivine-chromite equilibration temperatures of ∼1040-1050 °C, reflecting subsolidus Fe/Mg reequilibration during slow cooling from ∼1200 to 1300 °C. All other chromite in these samples is reduced. Three types of zones are observed. (1) Inclusion-free interior zones showing reduction of FeO (fe# ∼0.4 → 0.28); (2) Outer zones showing further reduction of FeO (fe# ∼0.28 → 0.15) and containing abundant laths of eskolaite-corundum (Cr2O3-Al2O3); (3) Outermost zones showing extreme reduction of both FeO (fe# <0.15) and Cr2O3 (Cr# as low as 0.2). The grains are surrounded by rims of Si-Al-rich glass, graphite, Fe, Cr-carbides ([Fe,Cr]3C and [Fe,Cr]7C3), Cr-rich sulfides (daubréelite and brezinaite) and Cr-rich symplectic bands on adjacent silicates. Chromite is inferred to have been reduced by graphite, forming eskolaite-corundum and carbides as byproducts, during impact excavation. This event involved initial elevation of T (to 1300-1400 °C), followed by rapid decompression and drop in T (to <700 °C) at 1-20 °C/h. The kinetics of reduction of chromite is consistent with this scenario. The reduction was facilitated by silicate melt surrounding the chromites, which was partly generated by shock-melting of pyroxenes. Symplectic bands, consisting of fine-scale intergrowths of Ca-pyroxene, chromite and glass, formed by reaction between the Cr-enriched melt and adjacent silicates. Early chromite also occurs in a melt inclusion in olivine in HaH 064 and in a metallic spherule in olivine in LAP 02382. LAP 03587 and CMS 04048 contain ⩽μm-sized chromite + pyroxene symplectic exsolutions in olivine, indicating high Cr valence in the primary olivine. EET 96328 contains a round grain of chromite that could be a late-crystallizing phase. Tiny chromite grains in melt inclusions in EET 96328 formed in late, closed-system reactions. For 7 of the 8 ureilites we conclude that the relatively oxidizing conditions evidenced by the presence of primary or early chromite pertain to the period of high-T igneous processing. The observation that such conditions are recorded almost exclusively in low-Fo samples supports the interpretation that the ureilite FeO-variation was established during igneous processing on the UPB.

Electroplating sludge derived zinc-ferrite catalyst for the efficient photo-Fenton degradation of dye.

PubMed

Cao, Zhenbang; Zhang, Jia; Zhou, Jizhi; Ruan, Xiuxiu; Chen, Dan; Liu, Jianyong; Liu, Qiang; Qian, Guangren

2017-05-15

A zinc-dominant ferrite catalyst for efficient degradation of organic dye was prepared by the calcination of electroplating sludge (ES). Characterizations indicated that zinc ferrite (ZnFe 2 O 4 ) coexisted with Fe 2 O 3 structure was the predominant phase in the calcined electroplating sludge (CES). CES displayed a high decolorization ratio (88.3%) of methylene blue (MB) in the presence of H 2 O 2 combined with UV irradiation. The high efficiency could be ascribed to the photocatalytic process induced by ZnFe 2 O 4 and the photo-Fenton dye degradation by ferrous content, and a small amount of Al and Mg in the sludge might also contribute to the catalysis. Moreover, the degradation capability of dye by CES was supported by the synthetic ZnFe 2 O 4 with different Zn to Fe molar ratio (n(Zn): n(Fe)), as 84.81%-86.83% of dye was removed with n(Zn): n(Fe) ranged from 1:0.5 to 1:3. All synthetic ferrite samples in the simulation achieved adjacent equilibrium decolorization ratio, the flexible proportioning of divalent metal ions (M 2+ ) to trivalent metal ions (M 3+ ) applied in the synthesis indicated that the catalyst has a high availability. Therefore, an efficacious catalyst for the degradation of dye can potentially be derived from heavy metal-containing ES, it's a novel approach for the reutilization of ES. Copyright © 2016 Elsevier Ltd. All rights reserved.

Novel preparation of highly photocatalytically active copper chromite nanostructured material via a simple hydrothermal route

PubMed Central

Beshkar, Farshad; Zinatloo-Ajabshir, Sahar; Bagheri, Samira; Salavati-Niasari, Masoud

2017-01-01

Highly photocatalytically active copper chromite nanostructured material were prepared via a novel simple hydrothermal reaction between [Cu(en)2(H2O)2]Cl2 and [Cr(en)3]Cl3.3H2O at low temperature, without adding any pH regulator or external capping agent. The as-synthesized nanostructured copper chromite was analyzed by transmission electron microscopy (TEM), UV–vis diffuse reflectance spectroscopy, energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy. Results of the morphological investigation of the as-synthesized products illustrate that the shape and size of the copper chromite depended on the surfactant sort, reaction duration and temperature. Moreover, the photocatalytic behavior of as-obtained copper chromite was evaluated by photodegradation of acid blue 92 (anionic dye) as water pollutant. PMID:28582420

Stratiform chromite deposit model

USGS Publications Warehouse

Schulte, Ruth F.; Taylor, Ryan D.; Piatak, Nadine M.; Seal, Robert R.

2010-01-01

Stratiform chromite deposits are of great economic importance, yet their origin and evolution remain highly debated. Layered igneous intrusions such as the Bushveld, Great Dyke, Kemi, and Stillwater Complexes, provide opportunities for studying magmatic differentiation processes and assimilation within the crust, as well as related ore-deposit formation. Chromite-rich seams within layered intrusions host the majority of the world's chromium reserves and may contain significant platinum-group-element (PGE) mineralization. This model of stratiform chromite deposits is part of an effort by the U.S. Geological Survey's Mineral Resources Program to update existing models and develop new descriptive mineral deposit models to supplement previously published models for use in mineral-resource and mineral-environmental assessments. The model focuses on features that may be common to all stratiform chromite deposits as a way to gain insight into the processes that gave rise to their emplacement and to the significant economic resources contained in them.

Electrical properties of lanthanum chromite based ceramics in hydrogen and oxidizing atmospheres at high temperatures

NASA Astrophysics Data System (ADS)

Schmidt, V. H.

1981-06-01

Several results regarding the effect of hydrogen on lanthanum chromite were determined. Thermally-activated diffusion of hydrogen through La(Mg)CrO3 was found with a high activation energy. It was found that its electrical conductivity drops drastically, especially at low temperature, after exposure to hydrogen at high temperature. Also, the curvature of most of the conductivity plots, as well as the inability to observe the Hall effect, lends support to the proposal by Karim and Aldred that the small-polaron model which predicts thermally activated mobility is applicable to doped lanthanum chromite. From differential thermal analysis, an apparent absorption of hydrogen near 3000 C was noticed. Upon cooling the lanthanum chromite in hydrogen and subsequently reheating it in air, desorption occurred near 1700 C. The immediate purpose of this study was to determine whether hydrogen has a deleterious effect on lanthanum chromite in solid oxide fuel cells.

Chromite alteration processes within Vourinos ophiolite

NASA Astrophysics Data System (ADS)

Grieco, Giovanni; Merlini, Anna

2012-09-01

The renewed interest in chromite ore deposits is directly related to the increase in Cr price ruled by international market trends. Chromite, an accessory mineral in peridotites, is considered to be a petrogenetic indicator because its composition reflects the degree of partial melting that the mantle experienced while producing the chromium spinel-bearing rock (Burkhard in Geochim Cosmochim Acta 57:1297-1306, 1993). However, the understanding of chromite alteration and metamorphic modification is still controversial (e.g. Evans and Frost in Geochim Cosmochim Acta 39:959-972, 1975; Burkhard in Geochim Cosmochim Acta 57:1297-1306, 1993; Oze et al. in Am J Sci 304:67-101, 2004). Metamorphic alteration leads to major changes in chromite chemistry and to the growth of secondary phases such as ferritchromite and chlorite. In this study, we investigate the Vourinos complex chromitites (from the mines of Rizo, Aetoraches, Xerolivado and Potamia) with respect to textural and chemical analyses in order to highlight the most important trend of alteration related to chromite transformation. The present study has been partially funded by the Aliakmon project in collaboration between the Public Power Corporation of Greece and Institute of Geology and Mineral Exploration of Kozani.

Effect of Ce2O3, La2O3 and ZnO additives on the oxygenates conversion into liquid hydrocarbons

NASA Astrophysics Data System (ADS)

Kachalov, V. V.; Lavrenov, V. A.; Lishchiner, I. I.; Malova, O. V.; Tarasov, A. L.; Zaichenko, V. M.

2018-01-01

A selective modifying effect of cerium, magnesium and zinc oxide additives on the activity and the selectivity of a pentasil group zeolite catalyst in the reaction of conversion of oxygenates (methanol and dimethyl ether) to liquid hydrocarbons was found. It was found that zinc oxide contributes to the stable operation of the zeolite catalyst in the conversion of oxygenates in the synthesis gas stream and leads to the production of gasolines with low durene content (not more than 6.1 wt%). The obtained results demonstrate the rationale for producing hydrocarbons from synthesis gas without the stage of oxygenate separation with their subsequent conversion to synthetic gasoline.

Chromian spinels in highly altered ultramafic rocks from the Sartohay ophiolitic mélange, Xinjiang, NW China

NASA Astrophysics Data System (ADS)

Qiu, Tian; Zhu, Yongfeng

2018-06-01

The Sartohay ophiolitic mélange is located in western Junggar (Xinjiang province, NW China), which is a major component of the core part of the Central Asian Orogenic Belt (CAOB). Chromian spinels in serpentinite, talc schist, carbonate-talc schist and listwaenite in Sartohay ophiolitic mélange retain primary compositions with Cr# of 0.39-0.65, Mg# = 0.48-0.67, and Fe3+# < 0.08. Chromian spinels in deformed listwaenite were initially transformed into Fe2+-rich chromite during shearing deformation followed by Fe3+-rich chromite at shallow levels. The Cr# and Fe3+# of Fe2+-rich chromite (Cr# = 0.59-0.86, Fe3+# = 0.01-0.12, Mg# = 0.35-0.61) and Fe3+-rich chromite (Cr# = 0.85-1.00, Fe3+# = 0.17-0.38, Mg# < 0.29) increase with decrease of Mg#. We propose a model to illustrate the evolution of chromian spinels in highly altered ultramafic rocks from the Sartohay ophiolitic mélange. Chromian spinels in serpentinite and talc schist were rimmed by Cr-magnetite, which was dissolved completely during transformation from serpentinite/talc schist to listwaenite. Chromian spinels were then transformed into Fe2+-rich chromite in shear zones, which characterized by high fluid/rock ratios. This Fe2+-rich chromite and/or chromian spinels could then be transformed into Fe3+-rich chromite in oxidizing conditions at shallow levels.

Palladium, platinum, rhodium, iridium and ruthenium in chromite- rich rocks from the Samail ophiolite, Oman.

USGS Publications Warehouse

Page, N.J.; Pallister, J.S.; Brown, M.A.; Smewing, J.D.; Haffty, J.

1982-01-01

30 samples of chromitite and chromite-rich rocks from two stratigraphic sections, 250 km apart, through the basal ultramafic member of the Samail ophiolite were spectrographically analysed for platinum-group elements (PGE) and for Co, Cu, Ni and V. These data are reported as are Cr/(Cr + Al), Mg/(Mg + Fe) and wt.% TiO2 for most samples. The chromitite occurs as pods or lenses in rocks of mantle origin or as discontinuous layers at the base of the overlying cumulus sequence. PGE abundances in both sections are similar, with average contents in chromite-rich rocks: Pd 8 ppb, Pt 14 ppb, Rh 6 ppb, Ir 48 ppb and Ru 135 ppb. The PGE data, combined with major-element and petrographic data on the chromitite, suggest: 1) relatively larger Ir and Ru contents and highest total PGE in the middle part of each section; 2) PGE concentrations and ratios do not correlate with coexisting silicate and chromite abundances or chromite compositions; 3) Pd/PGE, on average, increases upward in each section; 4) Samail PGE concentrations, particularly Rh, Pt and Pd, are lower than the average values for chromite-rich rocks in stratiform intrusions. 2) suggests that PGEs occur in discrete alloy or sulphide phases rather than in the major oxides or silicates, and 4) suggests that chromite-rich rocks from the oceanic upper mantle are depleted in PGE with respect to chondrites. L.C.C.

Internal structure of multiphase zinc-blende wurtzite gallium nitride nanowires.

PubMed

Jacobs, B W; Ayres, V M; Crimp, M A; McElroy, K

2008-10-08

In this paper, the internal structure of novel multiphase gallium nitride nanowires in which multiple zinc-blende and wurtzite crystalline domains grow simultaneously along the entire length of the nanowire is investigated. Orientation relationships within the multiphase nanowires are identified using high-resolution transmission electron microscopy of nanowire cross-sections fabricated with a focused ion beam system. A coherent interface between the zinc-blende and wurtzite phases is identified. A mechanism for catalyst-free vapor-solid multiphase nanowire nucleation and growth is proposed.

Chromium valences in ureilite olivine and implications for ureilite petrogenesis

NASA Astrophysics Data System (ADS)

Goodrich, C. A.; Sutton, S. R.; Wirick, S.; Jercinovic, M. J.

2013-12-01

Ureilites are a group of ultramafic achondrites commonly thought to be residues of partial melting on a carbon-rich asteroid. They show a large variation in FeO content (olivine Fo values ranging from ∼74 to 95) that cannot be due to igneous fractionation and suggests instead variation in oxidation state. The presence of chromite in only a few of the most ferroan (Fo 75-76) samples appears to support such a model. MicroXANES analyses were used in this study to determine the valence states of Cr (previously unknown) in olivine cores of 11 main group ureilites. The goal of this work was to use a method that is independent of Fo to determine the oxidation conditions under which ureilites formed, in order to evaluate whether the ureilite FeO-variation is correlated with oxidation state, and whether it is nebular or planetary in origin. Two of the analyzed samples, LEW 88774 (Fo 74.2) and NWA 766 (Fo 76.7) contain primary chromite; two others, LAP 03587 (Fo 74.4) and CMS 04048 (Fo 76.2) contain sub-micrometer-sized exsolutions of chromite + Ca-rich pyroxene in olivine; and one, EET 96328 (Fo 85.2) contains an unusual chromite grain of uncertain origin. No chromite has been observed in the remaining six samples (Fo 77.4-92.3). Chromium in olivine in all eleven samples was found to be dominated by the divalent species, with valences ranging from 2.10 ± 0.02 (1σ) to 2.46 ± 0.04. The non-chromite-bearing ureilites have the most reduced Cr, with a weighted mean valence of 2.12 ± 0.01, i.e., Cr2+/Cr3+ = 7.33. All low-Fo chromite-bearing ureilites have more oxidized Cr, with valences ranging from 2.22 ± 0.03 to 2.46 ± 0.04. EET 96328, whose chromite grain we interpret as a late-crystallizing phase, yielded a reduced Cr valence of 2.15 ± 0.07, similar to the non-chromite-bearing samples. Based on the measured Cr valences, magmatic (1200-1300 °C) oxygen fugacities (fO2) of the non-chromite-bearing samples were estimated to be in the range IW-1.9 to IW-2.8 (assuming basaltic melt composition), consistent with fO2 values obtained by assuming olivine-silica-iron metal (OSI) equilibrium. For the primary chromite-bearing-ureilites, the corresponding fO2 were estimated (again, assuming basaltic melt composition) to be ∼IW to IW+1.0, i.e., several orders of magnitude more oxidizing than the conditions estimated for the chromite-free ureilites. In terms of Fo and Cr valence properties, ureilites appear to form two groups rather than a single “Cr-valence (or fO2) vs. Fo” trend. The chromite-bearing ureilites show little variation in Fo (∼74-76) but significant variation in Cr valence, while the non-chromite-bearing ureilites show significant variation in Fo (∼77-95) and little variation in Cr valence. These groups are unrelated to petrologic type (i.e., olivine-pigeonite, olivine-orthopyroxene, or augite-bearing). The chromite-bearing ureilites also have lower contents of Cr in olivine than most non-chromite-bearing ureilites, consistent with predictions based on Cr olivine/melt partitioning in spinel saturated vs. non-spinel-saturated systems. Under the assumption that at magmatic temperatures graphite-gas equilibria controlled fO2 at all depths on the ureilite parent body, we conclude: (1) that ureilite precursor materials having the Fo and Cr valence properties now observed in ureilites are unlikely to have been preserved during planetary processing; and (2) that the Fo and Cr valence properties now observed in ureilites are consistent with having been established by high-temperature carbon redox control over a range of depths on a plausible-sized ureilite parent body. The apparent limit on ureilite Fo values around 74-76 suggests that the precursor material(s) had bulk mg# ⩾ that of LL chondrites.

XPS and STEM studies of Allende acid insoluble residues

NASA Technical Reports Server (NTRS)

Housley, R. M.; Clarke, D. R.

1980-01-01

Data on Allende acid residues obtained both before and after etching with hot HNO3 are presented. X-ray photoelectron spectra show predominantly carbonaceous material plus Fe-deficient chromite in both cases. The HNO3 oxidizes the carbonaceous material to some extent. The small chromites in these residues have a wide range of compositions somewhat paralleling those observed in larger Allende chromites and in Murchison chromites, especially in the high Al contents; however, they are deficient in divalent cations, which makes them metastable and indicates that they must have formed at relatively low temperatures. It is suggested that they formed by precipitation of Cr(3+) and Fe(3+) from olivine at low temperature or during rapid cooling.

Natural occurrence and synthesis of two new postspinel polymorphs of chromite.

PubMed

Chen, Ming; Shu, Jinfu; Mao, Ho-kwang; Xie, Xiande; Hemley, Russell J

2003-12-09

A high-pressure polymorph of chromite, the first natural sample with the calcium ferrite structure, has been discovered in the shock veins of the Suizhou meteorite. Synchrotron x-ray diffraction analyses reveal an orthorhombic CaFe2O4-type (CF) structure. The unit-cell parameters are a = 8.954(7) A, b = 2.986(2) A, c = 9.891(7) A, V = 264.5(4) A3 (Z = 4) with space group Pnma. The new phase has a density of 5.62 g/cm3, which is 9.4% denser than chromite-spinel. We performed laser-heated diamond anvil cell experiments to establish that chromite-spinel transforms to CF at 12.5 GPa and then to the recently discovered CaTi2O4-type (CT) structure above 20 GPa. With the ubiquitous presence of chromite, the CF and CT phases may be among the important index minerals for natural transition sequence and pressure and temperature conditions in mantle rocks, shock-metamorphosed terrestrial rocks, and meteorites.

Electrical properties of lanthanum chromite based ceramics in hydrogen and oxidizing atmospheres at high temperatures. Final report

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

Schmidt, V.H.

1981-06-01

Several results regarding the effect of hydrogen on lanthanum chromite were determined. Thermally-activated diffusion of hydrogen through La(Mg)CrO/sub 3/ was found with a high activation energy. It was found that its electrical conductivity drops drastically, especially at low temperature, after exposure to hydrogen at high temperature. Also, the curvature of most of the conductivity plots, as well as the inability to observe the Hall effect, lends support to the proposal by Karim and Aldred that the small-polaron model which predicts thermally activated mobility is applicable to doped lanthanum chromite. From differential thermal analysis an apparent absorption of hydrogen near 300/supmore » 0/C was noticed. Upon cooling the lanthanum chromite in hydrogen and subsequently reheating it in air, desorption occurred near 170/sup 0/C. The immediate purpose of this study was to determine whether hydrogen has a deleterious effect on lanthanum chromite in solid oxide fuel cells.« less

Single-Site Active Iron-Based Bifunctional Oxygen Catalyst for a Compressible and Rechargeable Zinc-Air Battery.

PubMed

Ma, Longtao; Chen, Shengmei; Pei, Zengxia; Huang, Yan; Liang, Guojin; Mo, Funian; Yang, Qi; Su, Jun; Gao, Yihua; Zapien, Juan Antonio; Zhi, Chunyi

2018-02-27

The exploitation of a high-efficient, low-cost, and stable non-noble-metal-based catalyst with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) simultaneously, as air electrode material for a rechargeable zinc-air battery is significantly crucial. Meanwhile, the compressible flexibility of a battery is the prerequisite of wearable or/and portable electronics. Herein, we present a strategy via single-site dispersion of an Fe-N x species on a two-dimensional (2D) highly graphitic porous nitrogen-doped carbon layer to implement superior catalytic activity toward ORR/OER (with a half-wave potential of 0.86 V for ORR and an overpotential of 390 mV at 10 mA·cm -2 for OER) in an alkaline medium. Furthermore, an elastic polyacrylamide hydrogel based electrolyte with the capability to retain great elasticity even under a highly corrosive alkaline environment is utilized to develop a solid-state compressible and rechargeable zinc-air battery. The creatively developed battery has a low charge-discharge voltage gap (0.78 V at 5 mA·cm -2 ) and large power density (118 mW·cm -2 ). It could be compressed up to 54% strain and bent up to 90° without charge/discharge performance and output power degradation. Our results reveal that single-site dispersion of catalytic active sites on a porous support for a bifunctional oxygen catalyst as cathode integrating a specially designed elastic electrolyte is a feasible strategy for fabricating efficient compressible and rechargeable zinc-air batteries, which could enlighten the design and development of other functional electronic devices.

SYNTHESIS, REACTIVITY, AND CATALYTIC BEHAVIOR OF IRON/ZINC-CONTAINING SPECIES INVOLVED IN OXIDATION OF HYDROCARBONS UNDER GIF-TYPE CONDITIONS. (R823377)

EPA Science Inventory

The present study explores the nature and reactivity of iron- and zinc-containing species
generated in hydrocarbon-oxidizing Gif(IV)-type solutions Fe catalyst/Zn/O-2 in pyridine/acetic acid
(10:1 v/v). The ultimate goal of this investigation is to unravel the role of metal...

Decolorization of brilliant green dye using immersed lamp sonophotocatalytic reactor

NASA Astrophysics Data System (ADS)

Gole, Vitthal L.; Priya, Astha; Danao, Sanjay P.

2017-12-01

The textile and dye industries require an enormous amount of water for processing and produce a large volume of wastewater. Generated wastewater had potential hazards and a threat to the aquatic biota. The present work investigates the decolorization of brilliant green dye using a combination of two advanced oxidation techniques viz sonocatalysis and photocatalysis (immersed lamp) known as sonophotocatalysis (3 L capacity). The efficiency of decolorization is further improved in the presence of various additives viz. copper oxide, zinc oxide, and sodium chloride. The maximum decolorization of brilliant green (BG) (94.8% in 120 min) obtained in the presence of zinc oxide. The total organic carbon of the treated samples was measured to monitor complete mineralization of BG. The sonophotocatalytic process (in the presence of zinc oxide) shows maximum mineralization. Synergic combination of two oxidation processes increased the production of oxidizing radicals. Continuous cleaning of catalyst surface (due to sonolysis effect) improves the activity of the catalyst for photolysis operation. The present work is highly useful for the development of a sonophotocatalytic process.

DEVELOPMENT OF IMPROVED TITANIUM ORGANIC COMPOUNDS FOR USE AS HYDRAULIC FLUIDS

DTIC Science & Technology

HYDRAULIC FLUIDS, *METALORGANIC COMPOUNDS, *TITANATES, *TITANIUM COMPOUNDS, ALKYL RADICALS, CATALYSTS , CHLORIDES, COMPLEX COMPOUNDS, FLUIDS, PHOSPHORIC ACIDS, PROPYL RADICALS, VISCOSITY, ZINC COMPOUNDS

Stratiform chromite deposit model: Chapter E in Mineral deposit models for resource assessment

USGS Publications Warehouse

Schulte, Ruth F.; Taylor, Ryan D.; Piatak, Nadine M.; Seal, Robert R.

2012-01-01

Most environmental concerns associated with the mining and processing of chromite ore focus on the solubility of chromium and its oxidation state. Although trivalent chromium (Cr3+) is an essential micronutrient for humans, hexavalent chromium (Cr6+) is highly toxic. Chromium-bearing solid phases that occur in the chromite ore-processing residue, for example, can effect the geochemical behavior and oxidation state of chromium in the environment.

Investigation on the light alkanes aromatization over Zn and Ga modified HZSM-5 catalysts in the presence of methane

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

Li, Qingyin; Zhang, Fengqi; Jarvis, Jack

The catalytic co-aromatization of methane and paraffin-rich raffinate oil was investigated along with hexane, heptane and octane as its model compounds over zinc and gallium modified ZSM-5 zeolite catalysts. The benzene, toluene and xylene (BTX) components derived from light alkane aromatization were highly promoted with the assistance of methane. The co-existence of Zn and Ga metal species has a positive effect on the formation of BTX components, whereas the individual metal loaded catalyst resulted in the production of heavy aromatics, suggesting that zinc and gallium have a synergistic effect on the formation of BTX under the methane environment. When concernedmore » with gaseous analysis, the introduced methane might interact with smaller intermediates and then transform into larger hydrocarbons. From the DRIFT observation, it was witnessed that the interaction between light alkane and methane occurred on the surface of the charged Zn-Ga/ZSM-5 catalyst. According to the comprehensive catalyst characterizations, the excellent catalytic performance may be closely associated with greatly dispersed metal species on the zeolite support, improved microporous characteristic, moderate Bronsted and increased Lewis acidic sites during the paraffin-rich liquid feedstock aromatization under methane environment. This research provides a promising pathway for the highly effective and profitable utilization of petrochemical resources and natural gas.« less

Investigation on the light alkanes aromatization over Zn and Ga modified HZSM-5 catalysts in the presence of methane

DOE PAGES

Li, Qingyin; Zhang, Fengqi; Jarvis, Jack; ...

2018-03-16

The catalytic co-aromatization of methane and paraffin-rich raffinate oil was investigated along with hexane, heptane and octane as its model compounds over zinc and gallium modified ZSM-5 zeolite catalysts. The benzene, toluene and xylene (BTX) components derived from light alkane aromatization were highly promoted with the assistance of methane. The co-existence of Zn and Ga metal species has a positive effect on the formation of BTX components, whereas the individual metal loaded catalyst resulted in the production of heavy aromatics, suggesting that zinc and gallium have a synergistic effect on the formation of BTX under the methane environment. When concernedmore » with gaseous analysis, the introduced methane might interact with smaller intermediates and then transform into larger hydrocarbons. From the DRIFT observation, it was witnessed that the interaction between light alkane and methane occurred on the surface of the charged Zn-Ga/ZSM-5 catalyst. According to the comprehensive catalyst characterizations, the excellent catalytic performance may be closely associated with greatly dispersed metal species on the zeolite support, improved microporous characteristic, moderate Bronsted and increased Lewis acidic sites during the paraffin-rich liquid feedstock aromatization under methane environment. This research provides a promising pathway for the highly effective and profitable utilization of petrochemical resources and natural gas.« less

Study on mechanisms of different sulfuric acid leaching technologies of chromite

NASA Astrophysics Data System (ADS)

Shi, Pei-yang; Liu, Cheng-jun; Zhao, Qing; Shi, Hao-nan

2017-09-01

The extraction of chromate from chromite via the sulfuric acid leaching process has strong potential for practical use because it is a simple and environmentally friendly process. This paper aims to study the sulfuric acid leaching process using chromite as a raw material via either microwave irradiation or in the presence of an oxidizing agent. The results show that the main phases in Pakistan chromite are ferrichromspinel, chrompicotite, hortonolite, and silicate embedded around the spinel phases. Compared with the process with an oxidizing agent, the process involving microwaves has a higher leaching efficiency. When the mass fraction of sulfuric acid was 80% and the leaching time was 20 min, the efficiency could exceed 85%. In addition, the mechanisms of these two technologies fundamentally differ. When the leaching was processed in the presence of an oxidizing agent, the silicate was leached first and then expanded. By contrast, in the case of leaching under microwave irradiation, the chromite was dissolved layer by layer and numerous cracks appeared at the particle surface because of thermal shock. In addition, the silicate phase shrunk instead of expanding.

Photocatalytic oxidation of organic dyes with visible-light-driven codoped TiO2 photocatalysts

NASA Astrophysics Data System (ADS)

Zhang, Dongfang; Zeng, Fanbin

2011-06-01

A novel copper (II) and zinc (II) codoped TiO2 photocatalyst was synthesized by a modified sol-gel method using titanium (IV) isopropoxide, Zn(NO3)2 · 6H2O and copper(Il) nitrate as precursors. The samples were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS) and photo-luminescence spectra (PL). The XRD results showed undoped and Zn, Cu-codoped TiO2 nanoparticles mainly including anatase phase and a tiny amount of Zn- and Cu-oxides exist in the mixed system, which is attributed to the decomposition of copper and zinc nitrates in the TiO2 gel to form CuO and ZnO and randomly dispersed on the TiO2 surface. On the basis of the optical characterization results, we found that the codoping of copper (II) and zinc (II) resulted a red shift of adsorption and lower recombination probability between electrons and holes, which were the reasons for high photocatalytic activity of Zn, Cu-codoped TiO2 nanoparticles under visible light (λ > 400 nm). The photocatalytic activity of samples was tested for degradation of methyl orange (MO) in solutions. The results indicated that the visible-light driven capability of the codoped catalyst were much higher than that of the pure TiO2 catalyst under visible irradiation. Because of the synergetic effect of copper (II) and zinc (II) element, the Zn, Cu-codoped TiO2 catalyst will show higher quantum yield and enhance absorption of visible light. In the end, a key mechanism was proposed in order to account for the enhanced activity.

Palladium-Catalyzed α-Arylation of Zinc Enolates of Esters: Reaction Conditions and Substrate Scope

PubMed Central

Hama, Takuo; Ge, Shaozhong; Hartwig, John F.

2013-01-01

The intermolecular α-arylation of esters by palladium-catalyzed coupling of aryl bromides with zinc enolates of esters is reported. Reactions of three different types of zinc enolates have been developed. α-Arylation of esters occurs in high yields with isolated Reformatsky reagents, with Reformatsky reagents generated from α-bromo esters and activated zinc, and with zinc enolates generated by quenching lithium enolates of esters with zinc chloride. The use of zinc enolates, instead of alkali metal enolates, greatly expands the scope of the arylation of esters. The reactions occur at room temperature or at 70 °C with bromoarenes containing cyano, nitro, ester, keto, fluoro, enolizable hydrogen, hydroxyl or amino functionality and with bromopyridines. The scope of esters encompasses acyclic acetates, propionates, and isobutyrates, α-alkoxyesters, and lactones. The arylation of zinc enolates of esters was conducted with catalysts bearing the hindered pentaphenylferrocenyl di-tert-butylphosphine (Q-phos) or the highly reactive dimeric Pd(I) complex {[P(t-Bu)3]PdBr}2. PMID:23931445

Platinum-group element abundance and distribution in chromite deposits of the Acoje Block, Zambales Ophiolite Complex, Philippines

USGS Publications Warehouse

Bacuta, G.C.; Kay, R.W.; Gibbs, A.K.; Lipin, B.R.

1990-01-01

Platinum-group elements (PGE) occur in ore-grade concentration in some of the chromite deposits related to the ultramafic section of the Acoje Block of the Zambales Ophiolite Complex. The deposits are of three types: Type 1 - associated with cumulate peridotites at the base of the crust; Type 2 - in dunite pods from the top 1 km of mantle harzburgite; and Type 3 - like Type 2, but in deeper levels of the harzburgite. Most of the deposites have chromite compositions that are high in Cr with Cr/(Cr + Al) (expressed as chromium index, Cr#) > 0.6; high-Al (Cr# Pd, thought to be characteristic of PGE-barren deposits) and positive slope (Ir < Pd, characteristic of PGE-rich deposits). Iridium, Ru and Os commonly occur as micron-size laurite (sulfide) inclusions in unfractured chromite. Laurite and native Os are also found as inclusions in interstitial sulfides. Platinum and Pd occur as alloy inclusions (and possibly as solid solution) in interstitial Ni-Cu sulfides and as tellurobismuthides in serpentine and altered sulfides. Variability of PGE distribution may be explained by alteration, crystal fractionation or partial melting processes. Alteration and metamorphism were ruled out, because PGE contents do not correlate with degree of serpentinization or the abundance and type (hydroxyl versus non-hydroxyl) of silicate inclusions in chromite. Preliminary Os isotopic data do not support crustal contamination as a source of the PGEs in the Acoje deposits. The anomalous PGE concentrations in Type 1 high-Cr chromite deposits are attributed to two stages of enrichment: an early enrichment of their mantle source from previous melting events and a later stage of sulfide segregation accompanying chromite crystallization. High-Al chromite deposits which crystallized from basalts derived from relatively low degrees of melting owe their low PGE content to partitioning of PGEs in sulfides and alloys that remain in the mantle. High-Cr deposits crystallized from melts that were previously enriched with PGEs during early melting events of their mantle source; Pt and Pd ore concentrations (ppm levels) are attained by segregation of magmatic sulfides. The Acoje deposits indicate that ophiolites are a potential economic source of the PGEs. ?? 1990.

Boundaries of intergrowths between mineral individuals: A zone of secondary mineral formation in aggregates

NASA Astrophysics Data System (ADS)

Brodskaya, R. L.; Bil'Skaya, I. V.; Lyakhnitskaya, V. D.; Markovsky, B. A.; Sidorov, E. G.

2007-12-01

Intergrowth boundaries between mineral individuals in dunite of the Gal’moenan massif in Koryakia was studied in terms of crystal morphology, crystal optics, and ontogenesis. The results obtained allowed us to trace the staged formation of olivine and chromite and four generations of these minerals. Micro-and nanotopography of boundary surfaces between intergrown mineral individuals of different generations was examined with optic, electron, and atomic force microscopes. The boundaries between mineral individuals of different generations are distinguished by their microsculpture for both olivine and chromite grains. Both minerals demonstrate a compositional trend toward refinement from older to younger generations. The decrease in the iron mole fraction in olivine and chromite is accompanied by the crystallization of magnetite along weakened zones in olivine of the first generation and as outer rims around the chromite grains of the second generation observable under optic and electronic microscopes. The subsequent refinement of chromite results in the release of PGE from its lattice, as established by atomic power microscopy. The newly formed PGM are localized at the boundaries between mineral individuals and, thus, mark a special stage in the ontogenetic evolution of mineral aggregates. Further recrystallization is expressed in the spatial redistribution of grain boundaries and the formation of monomineralic intergrowth boundaries, i.e., the glomerogranular structure of rock and substructures of PGM, chromite, and olivine grains as intermediate types of organization of the granular assemblies in the form of reticulate, chain, and cellular structures and substructures of aggregates.

Occupational health assessment of chromite toxicity among Indian miners

PubMed Central

Das, Alok Prasad; Singh, Shikha

2011-01-01

Elevated concentration of hexavalent chromium pollution and contamination has contributed a major health hazard affecting more than 2 lakh mine workers and inhabitants residing in the Sukinda chromite mine of Odisha, India. Despite people suffering from several forms of ill health, physical and mental deformities, constant exposure to toxic wastes and chronic diseases as a result of chromite mining, there is a tragic gap in the availability of 'scientific’ studies and data on the health hazards of mining in India. Occupational Safety and Health Administration, Odisha State Pollution Control Board and the Odisha Voluntary Health Association data were used to compile the possible occupational health hazards, hexavalent chromium exposure and diseases among Sukinda chromite mines workers. Studies were reviewed to determine the routes of exposure and possible mechanism of chromium induced carcinogenicity among the workers. Our studies suggest all forms of hexavalent chromium are regarded as carcinogenic to workers however the most important routes of occupational exposure to Cr (VI) are inhalation and dermal contact. This review article outlines the physical, chemical, biological and psychosocial occupational health hazards of chromite mining and associated metallurgical processes to monitor the mining environment as well as the miners exposed to these toxicants to foster a safe work environment. The authors anticipate that the outcome of this manuscript will have an impact on Indian chromite mining industry that will subsequently bring about improvements in work conditions, develop intervention experiments in occupational health and safety programs. PMID:21808494

Depolymerization of cellulose into high-value chemicals by using synergy of zinc chloride hydrate and sulfate ion promoted titania catalyst.

PubMed

Wei, Weiqi; Wu, Shubin

2017-10-01

Experiments for cellulose depolymerization by synergy of zinc chloride hydrate (ZnCl 2 ·RH 2 O) and sulfated titania catalyst (SO 4 2- /TiO 2 ) were investigated in this study. The results showed the introduction of sulfate into the TiO 2 significantly enhanced the catalyst acid amount, especially for Brønsted acid site, which is beneficial for subsequent cellulose depolymerization. ZnCl 2 ·RH 2 O hydrate, only a narrow composition range of water, specifically 3.0≤R≤4.0, can dissolve cellulose, which finally resulted the cellulose with low crystallinity and weak intrachain and interchain hydrogen bond network. Coupling of ZnCl 2 ·RH 2 O hydrate and SO 4 2- /TiO 2 catalyst as a mixed reaction system promoted cellulose depolymerization, and the products can be adjusted by the control of reaction conditions, the low temperature (80-100°C) seemed beneficial for glucose formation (maximal yield 50.5%), and the high temperature (120-140°C) favored to produce levulinic acid (maximal yield 43.1%). Besides, the addition of organic co-solvent making HMF as the main product (maximal yield 38.3%). Copyright © 2017 Elsevier Ltd. All rights reserved.

Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods

NASA Astrophysics Data System (ADS)

Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep

2016-07-01

For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide.

PubMed

Schäfer, Pascal M; Fuchs, Martin; Ohligschläger, Andreas; Rittinghaus, Ruth; McKeown, Paul; Akin, Enver; Schmidt, Maximilian; Hoffmann, Alexander; Liauw, Marcel A; Jones, Matthew D; Herres-Pawlis, Sonja

2017-09-22

New zinc guanidine complexes with N,O donor functionalities were prepared, characterized by X-Ray crystallography, and examined for their catalytic activity in the solvent-free ring-opening polymerization (ROP) of technical-grade rac-lactide at 150 °C. All complexes showed a high activity. The fastest complex [ZnCl 2 (DMEGasme)] (C1) produced colorless poly(lactide) (PLA) after 90 min with a conversion of 52 % and high molar masses (M w =69 100, polydispersity=1.4). The complexes were tested with different monomer-to-initiator ratios to determine the rate constant k p . Furthermore, a polymerization with the most active complex C1 was monitored by in situ Raman spectroscopy. Overall, conversion of up to 90 % can be obtained. End-group analysis was performed to clarify the mechanism. All four complexes combine robustness against impurities in the lactide with high polymerization rates, and they represent the fastest robust lactide ROP catalysts to date, opening new avenues to a sustainable ROP catalyst family for industrial use. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chromite and other mineral deposits in serpentine rocks of the Piedmont Upland, Maryland, Pennsylvania, and Delaware

USGS Publications Warehouse

Pearre, Nancy C.; Heyl, Allen V.

1960-01-01

The Piedmont Upland in Maryland, Pennsylvania, and Delaware is about 160 miles long and at the most 50 miles wide. Rocks that underlie the province are the Baltimore gneiss of Precambrian age and quartzite, gneiss, schist, marble, phyllite, and greenstone, which make up the Glenarm series of early Paleozoic (?) age. These are intruded by granitic, gabbroic, and ultramaflc igneous rocks. Most of the ultramaflc rocks, originally peridotite, pyroxenite, and dunite, have been partly or completely altered to serpentine and talc; they are all designated by the general term serpentine. The bodies of serpentine are commonly elongate and conformable with the enclosing rocks. Many have been extensively quarried for building, decorative, and crushed stone. In addition, chromite, titaniferous magnetite, rutile, talc and soapstone, amphibole asbestos, magnesite, sodium- rich feldspar (commercially known as soda spar), and corundum have been mined or prospected for in the serpentine. Both high-grade massive chromite and lower grade disseminated chromite occur in very irregular and unpredictable form in the serpentine, and placer deposits of chromite are in and near streams that drain areas underlain by serpentine. A group of unusual minerals, among them kammererite, are typical associates of high-grade massive chromite but are rare in lower grade deposits. Chromite was first discovered in the United States at Bare Hills, Md., around 1810. Between 1820 and 1850, additional deposits were discovered and mined in Maryland and Pennsylvania, including the largest deposit of massive chromite ever found in the United States the Wood deposit, in the State Line district. A second period of extensive chromite mining came during the late 1860's and early 1870's. Production figures are incomplete and conflicting. Estimates from the available data indicate that the aggregate production from 27 of 40 known mines before 1900 totaled between 250,000 and 280,000 tons of lode-chromite ore; information is lacking for the other 13. Placer deposits produced considerably more than 15,000 tons of chromite concentrates. Exploratory work in several of the mines and placer deposits during World War I produced about 1,500 long tons of chromite ore, 920 tons of which was sold.Most of the chromite from Maryland and Pennsylvania was used to manufacture chemical compounds, pigments, and dyes before metallurgical and refractory uses for chromite were developed. Available analyses of the ores indicate that they would satisfy modern requirements for chemical-grade chromite. With the exception of such deposits as the Line Pit and Red Pit mines, the chromite contains too much iron for the best metallurgical grade, but many would be satisfactory low-grade metallurgical chromite. Perhaps 30,000 to 50,000 tons of chromite concentrates that would range from 30 to 54 percent Cr2O3 could be obtained from placer deposits in the State Line and Soldiers Delight districts. A small tonnage of chromite remains in dumps at six of the old mines. Lode and placer deposits in the Philadelphia district, placers in Montgomery County, Md., and possible downward extensions of known ore bodies below the floors of high-grade mines now flooded have not been completely explored. Although other chromite deposits probably lie concealed at relatively shallow depths, no practical method of finding them has been developed.Small deposits of titaniferous iron ore in serpentine were mined for iron before 1900, but the titanium content troubled furnace operators. Ore bodies are similar in occurrence to chromite deposits; they are massive or disseminated and are found near the edges of serpentine intrusive rocks. The small size of the deposits and comparatively low titanium content limit their importance as a potential source of titanium. A single rutile deposit in Harford County, Md., has been prospected but not mined. Pockets in schistose chlorite rock, probably altered from pyroxenite, contain as much as 16 percent rutile and average 8 percent. Rutile-bearing rock has been proved to a depth of about 58 feet. Talc and soapstone deposits that have been worked in the State Line and Jarrettsville-Dublin districts are the result of steatitization of serpentine at its contact with intrusive sodium-rich pegmatites. Deposits in the Marriottsville and Philadelphia districts seem to be related to shear or crush zones in the serpentine, which served as channelways for steatitizing solutions. Massive soapstone was extensively used in the 19th century for furnace, fireplace, and stove linings and for washtubs and bathtubs. Every year from 1906 until 1960 talc and soapstone have been produced from one or more of the deposits in Maryland and Pennsylvania. Deposits near Dublin and Marriottsville, Md., have produced steadily for years and production continues. Lava-grade steatite from Dublin, Md., is manufactured into ceramic products for electrical and refractory purposes. Slip-fiber amphibole asbestos deposits were known in the area as early as 1837, but early production was limited. The product was used mostly for linings of safes, boiler covers, and paints. During World War I the demand for domestic asbestos for chemical filters led to further development of deposits in Maryland. Between 1916 and 1940 many small veins of good-quality tremolite and anthophyllite were mined, and the fiber was prepared for market at Woodlawn, Md. Only the upper parts of veins, softened by weathering, were usable. Because prospecting was reportedly fairly thorough and known deposits are said to be mined out, and because demand for amphibole asbestos is limited, the possibility of future asbestos production from the area seems small, except as a byproduct of talc quarrying. Magnesite from several mines in Pennsylvania and Maryland was much in demand between 1828 and 1871 for the manufacture of epsom salt. Exploratory work at the old Goat Hill mines in 1921 indicated that the product could not be profitably prepared for market at that time. Although reportedly high grade, the magnesite veins are thin and small in comparison with other domestic deposits.Sodium-rich feldspar and corundum deposits occur in pegmatites that are unusual because they characteristically contain little or no quartz and mica and because, insofar as known, they are confined to serpentine rocks. Many of the known deposits of sodium-rich feldspar commercial soda-spar are reportedly mined out. It is possible, however, that other commercial deposits will be found in the area. At various times from 1825 until about 1892 in Pennsylvania, corundum mined or found at the surface was used to meet a demand of the abrasives industry. The increased use of artificial abrasives has diminished the demand for natural corundum, and interest in the small, irregular Pennsylvania deposits is at present largely historical or mineralogical.

Synthesis and characterization of nickel and zinc ferrite nanocatalysts for decomposition of CO2 greenhouse effect gas.

PubMed

Lin, Kuen-Song; Adhikari, Abhijit Krishna; Wang, Chi-Yu; Hsu, Pei-Ju; Chan, Ho-Yang

2013-04-01

The decomposition of CO2 over oxygen deficient nickel ferrite nanoparticles (NFNs) and zinc ferrite nanoparticles (ZFNs) at 573 K was studied. The oxidation states with fine structure of Fe/Ni or Fe/Zn species were also measured in NFNs and ZFNs catalysts, respectively. Oxygen deficiency of catalysts was obtained by reduction in hydrogen. Decomposition of CO2 into carbon and oxygen has been carried out within few minutes when it comes into contact with oxygen deficient catalysts through incorporation of oxygen into ferrite nanoparticles. Oxygen and carbon rather than CO were produced in the decomposition process. The complete decomposition of CO2 was possible because of higher degree of oxygen deficiency andsurface-to-volume ratio of the catalysts. The pre-edge XANES spectra of Fe species in both catalysts exhibit an absorbance feature at 7114 eV for the 1s to 3d transition which is forbidden by the selection rule in case of perfect octahedral symmetry. The EXAFS data showed that the NFNs had two central Fe atoms coordinated by primarily Fe-O and Fe-Fe with bond distances of 1.871 and 3.051 angstroms, respectively. In case of ZFNs these values are 1.889 and 3.062 A, respectively. Methane gas was produced during the reactivation of NFNs by flowing hydrogen gas. Decomposition of CO2, moreover, recovery of valuable methane using heat energy of offgas produced from power generation plant or steel industry is an appealing alternative for energy recovery.

Chemistry of chromites from Arroio Grande Ophiolite (Dom Feliciano Belt, Brazil) and their possible connection with the Nama Group (Namibia)

NASA Astrophysics Data System (ADS)

Ramos, Rodrigo Chaves; Koester, Edinei; Porcher, Carla Cristine

2017-12-01

The present paper shows a mineral chemistry study in chromites found in serpentine-talc schists of the Arroio Grande Ophiolite, located in the southeastern Dom Feliciano Belt, near the Brazil/Uruguay border. Using electron microscope scanning and electron microprobe techniques, this study found a supra-subduction zone signature in the chromites, together with evidence of metasomatism. It corroborates previous hypothesis that suggested a supra-subduction zone origin for the protoliths of the Arroio Grande meta-igneous rocks and a metasomatic origin for the chromite-bearing magnesian schists. The studied chromites present high Cr# (0.65-0.77) and Fe2+# (0.88-0.95), low MgO (0.85-2.47 wt%) and TiO2 (0.01-0.19 wt%) and anomalous high concentration of ZnO (up to 1.97 wt%). The results were compared with chemical data from detrital chromites from the Schwarzrand and Fish River Subgroups of the Nama Group (Namibia), demonstrating that they are compositionally similar with those found in the latter. These chromites, in turn, are believed to have been derived from the oceanic Marmora Terrane (Gariep Belt) in the west (present-day coordinates). Taking into consideration that oceanic metamafites from both the latter and the Arroio Grande Ophiolite share common bulk-rock geochemical features (in this paper interpreted as fragments of the same paleo-ocean floor - the Marmora back-arc basin), it is possible to raise the hypothesis that detrital material derived from the studied ophiolite might also be found in Nama Group. It is reinforced by the fact that sediments (related to the Pelotas-Aiguá Batholith granitoids) derived from the easternmost Dom Feliciano Belt, i.e. the region where Arroio Grande Ophiolite is located, is found in both Schwarzrand and Fish River Subgroups. Thus, we suggest that Arroio Grande Ophiolite detrital sediments might also have contributed to the Nama Basin infilling during Late Ediacaran-Lower Cambrian.

Crystallization of high-Ca chromium garnet upon interaction of serpentine, chromite, and Ca-bearing hydrous fluid

NASA Astrophysics Data System (ADS)

Chepurov, A. A.; Turkin, A. I.; Pokhilenko, N. P.

2017-10-01

The results of experimental modeling of the conditions of crystallization of high-Ca chromium garnets in the system serpentine-chromite-Ca-Cr-bearing hydrous fluid at a pressure of 5 GPa and temperature of 1300°C are reported. The mineral association including quantitatively predominant high-Mg olivine and diopside-rich clinopyroxene, bright-green garnet, and newly formed chrome spinel was formed. Garnet mostly crystallized around primary chromite grains and was characterized by a high concentration of CaO and Cr2O3. According to the chemical composition, garnets obtained are close to the uvarovite-pyrope varieties, which enter the composition of relatively rare natural paragenesis of garnet wehrlite. The experimental data obtained clearly show that high-Ca chromium garnets are formed in the reaction of chromite-bearing peridotite and Ca-rich fluid at high P-T parameters.

Nitrogen, Fluorine, and Boron Ternary Doped Carbon Fibers as Cathode Electrocatalysts for Zinc-Air Batteries.

PubMed

Wang, Lei; Wang, Yueqing; Wu, Mingguang; Wei, Zengxi; Cui, Chunyu; Mao, Minglei; Zhang, Jintao; Han, Xiaopeng; Liu, Quanhui; Ma, Jianmin

2018-05-01

Zinc-air batteries with high-density energy are promising energy storage devices for the next generation of energy storage technologies. However, the battery performance is highly dependent on the efficiency of oxygen electrocatalyst in the air electrode. Herein, the N, F, and B ternary doped carbon fibers (TD-CFs) are prepared and exhibited higher catalytic properties via the efficient 4e - transfer mechanism for oxygen reduction in comparison with the single nitrogen doped CFs. More importantly, the primary and rechargeable Zn-air batteries using TD-CFs as air-cathode catalysts are constructed. When compared to batteries with Pt/C + RuO 2 and Vulcan XC-72 carbon black catalysts, the TD-CFs catalyzed batteries exhibit remarkable battery reversibility and stability over long charging/discharging cycles. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simple-Cubic Carbon Frameworks with Atomically Dispersed Iron Dopants toward High-Efficiency Oxygen Reduction.

PubMed

Wang, Biwei; Wang, Xinxia; Zou, Jinxiang; Yan, Yancui; Xie, Songhai; Hu, Guangzhi; Li, Yanguang; Dong, Angang

2017-03-08

Iron and nitrogen codoped carbons (Fe-N-C) have attracted increasingly greater attention as electrocatalysts for oxygen reduction reaction (ORR). Although challenging, the synthesis of Fe-N-C catalysts with highly dispersed and fully exposed active sites is of critical importance for improving the ORR activity. Here, we report a new type of graphitic Fe-N-C catalysts featuring numerous Fe single atoms anchored on a three-dimensional simple-cubic carbon framework. The Fe-N-C catalyst, derived from self-assembled Fe 3 O 4 nanocube superlattices, was prepared by in situ ligand carbonization followed by acid etching and ammonia activation. Benefiting from its homogeneously dispersed and fully accessible active sites, highly graphitic nature, and enhanced mass transport, our Fe-N-C catalyst outperformed Pt/C and many previously reported Fe-N-C catalysts for ORR. Furthermore, when used for constructing the cathode for zinc-air batteries, our Fe-N-C catalyst exhibited current and power densities comparable to those of the state-of-the-art Pt/C catalyst.

Bridging the Gap: From Model Surfaces to Nanoparticle Analogs for Selective Oxidation and Steam Reforming of Methanol and Selective Hydrogenation Catalysis

NASA Astrophysics Data System (ADS)

Boucher, Matthew B.

Most industrial catalysts are very complex, comprising of non-uniform materials with varying structures, impurities, and interaction between the active metal and supporting substrate. A large portion of the ongoing research in heterogeneous catalysis focuses on understanding structure-function relationships in catalytic materials. In parallel, there is a large area of surface science research focused on studying model catalytic systems for which structural parameters can be tuned and measured with high precision. It is commonly argued, however, that these systems are oversimplified, and that observations made in model systems do not translate to robust catalysts operating in practical environments; this discontinuity is often referred to as a "gap." The focus of this thesis is to explore the mutual benefits of surface science and catalysis, or "bridge the gap," by studying two catalytic systems in both ultra-high vacuum (UHV) and near ambient-environments. The first reaction is the catalytic steam reforming of methanol (SRM) to hydrogen and carbon dioxide. The SRM reaction is a promising route for on-demand hydrogen production. For this catalytic system, the central hypothesis in this thesis is that a balance between redox capability and weak binding of reaction intermediates is necessary for high SRM activity and selectivity to carbon dioxide. As such, a new catalyst for the SRM reaction is developed which incorporates very small amounts of gold (<1 atomic %) supported on zinc oxide nanoparticles with controlled crystal structures. The performance of these catalysts was studied in a fixed-bed micro-reactor system at ambient pressures, and their structure was characterized by high-resolution microscopic and spectroscopic techniques. Pre-existing oxygen defects in zinc oxide {0001} surfaces, and those created by a perturbation of the defect equilibrium by addition of gold, provide an anchoring site for highly dispersed gold species. By utilizing shape control of zinc oxide supports, it is found that highly dispersed gold, capable of low-temperature redox behavior is most prominent on zinc oxide {0001} surfaces and leads to high SRM activity and selectivity to carbon dioxide. Like other Group IB metal catalysts the SRM over gold-zinc oxide proceeds through the formation and weak binding of formaldehyde, and subsequent coupling with methoxy to produce methyl formate. Mechanistic clarification of this point was achieved by studying the interaction methanol-water mixtures with model catalyst surfaces. Model catalysts were studied in a UHV chamber where the base pressure was maintained at 10-10 mbar. High resolutions surface science techniques show that hydrogen-bonded networks of water are capable of deprotonating methanol to methoxy on low index surfaces in the absence of atomic oxygen. These UHV studies show that adsorbates, other than oxygen, are capable of activating methanol on Group IB metal surfaces. The second reaction involves the selective hydrogenation of alkynes to alkenes. Selective hydrogenations of carbon-carbon multiple bonds are important for a wide range of industrial processes. The governing hypothesis for this reaction system is that cooperation between a minority metal with a low barrier for hydrogen dissociation, and a less-reactive host metal capable of hydrogen uptake via spillover will lead to high alkene selectivity. A strategy for the preparation of such a catalyst is developed using model catalyst studied in a UHV chamber. The model catalyst features isolated palladium atoms in a copper(111) surface, termed single atom alloy (SAA). Individual, isolated palladium atoms act as sites for hydrogen uptake, dissociation, and spillover onto an otherwise inert copper(111) host. Weak binding offered by copper provides a surface where selective hydrogenation reactions can take place. Palladium-copper SAA model catalysts are highly selective to the partial hydrogenation of acetylene, whereas surfaces containing larger palladium ensembles facilitate complete hydrogenation and decomposition. Nanoparticle analogs of palladium-copper SAAs were prepared to investigate the feasibility of this strategy for practical application. Very small amounts of palladium (<0.2 atomic %) on the surface of copper nanoparticles are highly active and selective catalysts for the partial hydrogenation of phenylacetylene to styrene. The performance of these catalysts was studied in a liquid-phase, stirred-tank batch reactor under a hydrogen head pressure of approximately 7 bar. Palladium alloyed into the surface of otherwise inactive copper nanoparticles shows a marked improvement in selectivity when compared to monometallic palladium catalysts with the same metal loading. This effect is attributed hydrogen spillover onto the copper surface. In summary, the development of new, highly active and selective catalysts for the methanol steam reforming reaction and for the partial hydrogenation of alkynes to alkenes was accomplished by the use of state-of-the-art techniques in both surface science and heterogeneous catalysis. The implications of this work can be extended to a wide variety of catalytic systems.

Synthesis of 6-alkyluridines from 6-cyanouridine via zinc(II) chloride-catalyzed nucleophilic substitution with alkyl Grignard reagents.

PubMed

Shih, Yu-Chiao; Yang, Ya-Ying; Lin, Chun-Chi; Chien, Tun-Cheng

2013-04-19

6-Cyanouracil derivatives underwent a direct nucleophilic substitution reaction with alkyl Grignard reagents in the presence of zinc(II) chloride as a catalyst to form the corresponding 6-alkyluracils. This methodology is applicable to sugar-protected 6-cyanouridine and 6-cyano-2'-deoxyuridine without the protection at the N(3)-imide and provides a facile and general access to versatile 6-alkyluracil and 6-alkyluridine derivatives.

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

Dayton, David C; Kataria, Atish; Gupta, Rabhubir

The objective of the project is to develop and demonstrate a novel fluidized-bed process module called a Therminator to simultaneously destroy and/or remove tar, NH3 and H2S from raw syngas produced by a fluidized-bed biomass gasifier. The raw syngas contains as much as 10 g/m3 of tar, 4,000 ppmv of NH3 and 100 ppmv of H2S. The goal of the Therminator module would be to use promising regenerable catalysts developed for removing tar, ammonia, and H2S down to low levels (around 10 ppm). Tars are cracked to a non-condensable gas and coke that would deposit on the acid catalyst. Wemore » will deposit coke, much like a fluid catalytic cracker (FCC) in a petroleum refinery. The deposited coke fouls the catalyst, much like FCC, but the coke would be burned off in the regenerator and the regenerated catalyst would be returned to the cracker. The rapid circulation between the cracker and regenerator would ensure the availability of the required amount of regenerated catalyst to accomplish our goal. Also, by removing sulfur down to less than 10 ppmv, NH3 decomposition would also be possible in the cracker at 600-700°C. In the cracker, tar decomposes and lays down coke on the acid sites of the catalyst, NH3 is decomposed using a small amount of metal (e.g., nickel or iron) catalyst incorporated into the catalyst matrix, and H2S is removed by a small amount of a metal oxide (e.g. zinc oxide or zinc titanate) by the H2S-metal oxide reaction to form metal sulfide. After a tolerable decline in activity for these reactions, the catalyst particles (and additives) are transported to the regenerator where they are exposed to air to remove the coke and to regenerate the metal sulfide back to metal oxide. Sulfate formation is avoided by running the regeneration with slightly sub-stoichiometric quantity of oxygen. Following regeneration, the catalyst is transported back to the cracker and the cycling continues. Analogous to an FCC reactor system, rapid cycling will allow the use of very active cracking catalysts that lose activity due to coking within the order of several seconds.« less

Hydrocarbon polymeric binder for advanced solid propellant

NASA Technical Reports Server (NTRS)

Potts, J. E. (Editor)

1972-01-01

A series of DEAB initiated isoprene polymerizations were run in the 5-gallon stirred autoclave reactor. Polymerization run parameters such as initiator concentration and feed rate were correlated with the molecular weight to provide a basis for molecular weight control in future runs. Synthetic methods were developed for the preparation of n-1,3-alkadienes. By these methods, 1,3-nonadiene was polymerized using DEAB initiator to give an ester-telechelic polynonadiene. This was subsequently hydrogenated with copper chromite catalyst to give a hydroxyl terminated saturated liquid hydrocarbon prepolymer having greatly improved viscosity characteristics and a Tg 18 degrees lower than that of the hydrogenated polyisoprenes. The hydroxyl-telechelic saturated polymers prepared by the hydrogenolysis of ester-telechelic polyisoprene were reached with diisocyanates under conditions favoring linear chain extension gel permeation chromatography was used to monitor this condensation polymerization. Fractions having molecular weights above one million were produced.

Cresol Izomerization in the Presence of Acid Catalysts

NASA Astrophysics Data System (ADS)

Tarasov, A. L.; Dunaev, S. F.; Kustov, L. M.

2018-02-01

It is shown for toluene oxidation with nitrous oxide that modifying HZSM-5 zeolite with zinc oxide nanoparticles considerably improves the selectivity and yield of cresols. It is found that a 2% ZnO/HZSM-5 composite catalyst also exhibits enhanced and stable activity at high temperatures. For the o-cresol isomerization reaction, this modification of HZSM-5 zeolite greatly reduces the contribution from disproportionation and cracking reactions proceeding with formation of phenol, C6-C9 aromatic hydrocarbons, and xylenols. The regularities of their formation in the presence of the studied catalysts are determined using the results from thermodynamic calculations for the equilibrium concentrations of cresol isomers.

AZO nanorods thin films by sputtering method

NASA Astrophysics Data System (ADS)

Rosli, A. B.; Shariffudin, S. S.; Awang, Z.; Herman, S. H.

2018-05-01

Al-doped zinc oxide (AZO) nanorods thin film were deposited on Au catalyst using RF sputtering at 300 °C. The 15 nm thickness Au catalyst were deposited on glass substrates by sputtering method followed by annealing for 15 min at 500 °C to form Au nanostructures on the glass substrate. The AZO thin films were then deposited on Au catalyst at different RF power ranging from 50 - 200 W. The morphology of AZO was characterized using Field Emission Scanning Electron Microscopy while X-ray Diffraction was used to examine crystallinity of AZO thin films. From this work, the AZO nanorods was found grow at 200 W RF power.

Catalytic properties of new anode materials for solid oxide fuel cells operated under methane at intermediary temperature

NASA Astrophysics Data System (ADS)

Sauvet, A.-L.; Fouletier, J.

The recent trend in solid oxide fuel cell concerns the use of natural gas as fuel. Steam reforming of methane is a well-established process for producing hydrogen directly at the anode side. In order to develop new anode materials, the catalytic activities of several oxides for the steam reforming of methane were characterized by gas chromatography. We studied the catalytic activity as a function of steam/carbon ratios r. The methane and the steam content were varied between 5 and 30% and between 1.5 and 3.5%, respectively, corresponding to r-values between 0.07 and 0.7. Catalyst (ruthenium and vanadium)-doped lanthanum chromites substituted with strontium, gadolinium-doped ceria (Ce 0.9Gd 0.1O 2) referred as to CeGdO 2, praseodymium oxide, molybdenum oxide and copper oxide were tested. The working temperature was fixed at 850°C, except for 5% ruthenium-doped La 1- xSr xCrO 3 where the temperature was varied between 700 and 850°C. Two types of behavior were observed as a function of the activity of the catalyst. The higher steam reforming efficiency was observed with 5% of ruthenium above 750°C.

Dissolution Behavior of Mg from Magnesia-Chromite Refractory into Al-killed Molten Steel

NASA Astrophysics Data System (ADS)

Liu, Chunyang; Yagi, Motoki; Gao, Xu; Kim, Sun-Joong; Huang, Fuxiang; Ueda, Shigeru; Kitamura, Shin-ya

2018-06-01

Magnesia-chromite refractory materials are widely employed in steel production, and are considered a potential MgO source for the generation of MgO·Al2O3 spinel inclusions in steel melts. In this study, a square magnesia-chromite refractory rod was immersed into molten steel of various compositions held in an Al2O3 crucibles. As the immersion time was extended, Mg and Cr gradually dissolved from the magnesia-chromite refractory, and the Mg and Cr contents of the steel melts increased. However, it was found that the inclusions in the steel melts remained as almost pure Al2O3 because the Mg content of the steel melts was low, approximately 1 ppm. On the surface of the magnesia-chromite refractory, an MgO·Al2O3 spinel layer with a variable composition was formed, and the thickness of the MgO·Al2O3 spinel layer increased with the immersion time and the Al content of the steel melts. At the rod interface, the formed layer consisted of MgO-saturated MgO·Al2O3 spinel. The MgO content decreased along the thickness direction of the layer, and at the steel melts interface, the formed layer consisted of Al2O3-saturated MgO·Al2O3 spinel. Therefore, the low content of Mg in steel melts and the unchanged inclusions were because of the equilibrium between Al2O3-saturated MgO·Al2O3 layer and Al2O3. In addition, the effects of the Al and Cr contents of the steel melts on the dissolution of Mg from the magnesia-chromite refractory are insignificant.

Reduction of Chromite in Liquid Fe-Cr-C-Si Alloys

NASA Astrophysics Data System (ADS)

Demir, Orhan; Eric, R. Hurman

1994-08-01

The kinetics and the mechanism of the reduction of chromite in Fe-Cr-C-Si alloys were studied in the temperature range of 1534 °C to 1702 °C under an inert argon atmosphere. The rotating cylinder technique was used. The melt consisted of 10 and 20 wt Pct chromium, the carbon content varied from 2.8 wt Pct to saturation, and the silicon content varied from 0 to 2 wt Pct. The rotational speed of the chromite cylinder ranged from 100 to 1000 rpm. The initial chromium to iron ratios of the melts varied between 0.11 and 0.26. In Fe-C melts, the effect of rotational speed on the reduction of chromite was very limited. Carbon saturation (5.4 wt Pct) of the alloy caused the reduction to increase 1.5 times over the reduction observed in the unsaturated (4.87 wt Pct) alloy at a given rotational speed. The addition of chromium to the carbon-saturated Fe-C alloy increased the reduction rate. The addition of silicon to the liquid phase increased the reduction rate drastically. The reduction of chromite in Fe-Cr-C melts is hindered because of the formation of, approximately, a 1.5-mm-thick M7C3-type carbide layer around the chromite cylinders. This carbide layer did not form when silicon was present in the melt. It was found that the reduction rate is controlled by the liquid-state mass transfer of oxygen. The calculated apparent activation energies for diffusion were 102.9 and 92.9 kJ/mol of oxygen in the Si-O and C-O systems, respectively.

Simple and novel electrochemical sensor for the determination of tetracycline based on iron/zinc cations-exchanged montmorillonite catalyst.

PubMed

Gan, Tian; Shi, Zhaoxia; Sun, Junyong; Liu, Yanming

2014-04-01

A simple and novel electrochemical sensor for the determination of tetracycline (TC), a kind of antibiotic that may induce residue in the food chain, was developed by the modification of iron/zinc cation-exchanged montmorillonite (Fe/Zn-MMT) catalyst on glassy carbon electrode (GCE). The morphology and the structure of the Fe/Zn-MMT nanomaterial were characterized by scanning electron microscopy and X-ray diffraction, respectively. The results of electrochemical experiments demonstrated that the sensor exhibited excellent electrocatalytic activity to the oxidation of TC in the presence of sodium dodecyl sulfate. The sensor displayed a wide linear range from 0.30 to 52.0 μM and a low detection limit of 0.10 μM by using the derivative differential pulse voltammetry. Moreover, the electrochemical sensor was applied to the detection of TC in feedstuff and meat samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Nitrogen-doped micropore-dominant carbon derived from waste pine cone as a promising metal-free electrocatalyst for aqueous zinc/air batteries

NASA Astrophysics Data System (ADS)

Lei, Xiaoke; Wang, Mengran; Lai, Yanqing; Hu, Langtao; Wang, Hao; Fang, Zhao; Li, Jie; Fang, Jing

2017-10-01

The exploitation for highly effective and low-cost metal-free catalysts with facile and environmental friendly method for oxygen reduction reaction is still a great challenge. To find an effective method for catalyst synthesis, in this manuscript, waste biomass pine cone is employed as raw material and nitrogen-doped micropore-dominant carbon material with excellent ORR catalytic activity is successfully synthesized. The as-prepared N-doped micropore-dominant carbon possesses a high surface area of 1556 m2 g-1. In addition, this carbon electrocatalyst loaded electrode exhibits a high discharge voltage 1.07 V at the current density of 50 mA cm-2, which can be ascribed to the rich micropores and high content of pyridinic N of the prepared carbon, indicative of great potential in the application of zinc/air batteries.

Metal Catalyst for Low-Temperature Growth of Controlled Zinc Oxide Nanowires on Arbitrary Substrates

PubMed Central

Kim, Baek Hyun; Kwon, Jae W.

2014-01-01

Zinc oxide nanowires generated by hydrothermal method present superior physical and chemical characteristics. Quality control of the growth has been very challenging and controlled growth is only achievable under very limited conditions using homogeneous seed layers with high temperature processes. Here we show the controlled ZnO nanowire growth on various organic and inorganic materials without the requirement of a homogeneous seed layer and a high temperature process. We also report the discovery of an important role of the electronegativity in the nanowire growth on arbitrary substrates. Using heterogeneous metal oxide interlayers with low-temperature hydrothermal methods, we demonstrate well-controlled ZnO nanowire arrays and single nanowires on flat or curved surfaces. A metal catalyst and heterogeneous metal oxide interlayers are found to determine lattice-match with ZnO and to largely influence the controlled alignment. These findings will contribute to the development of novel nanodevices using controlled nanowires. PMID:24625584

Nanostructured Perovskite LaCo1-xMnxO3 as Bifunctional Catalysts for Rechargeable Metal-Air Batteries

NASA Astrophysics Data System (ADS)

Ge, Xiaoming; Li, Bing; Wuu, Delvin; Sumboja, Afriyanti; An, Tao; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

2015-09-01

Bifunctional catalyst that is active for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the most important components of rechargeable metal-air batteries. Nanostructured perovskite bifunctional catalysts comprising La, Co and Mn(LaCo1-xMnxO3, LCMO) are synthesized by hydrothermal methods. The morphology, structure and electrochemical activity of the perovskite bifunctional catalysts are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and rotating disk electrode (RDE) techniques. Nanorod, nanodisc and nanoparticle are typical morphologies of LCMO. The electrocatalytic activity of LCMO is significantly improved by the addition of conductive materials such as carbon nanotube. To demonstrate the practical utilization, LCMO in the composition of LaCo0.8Mn0.2O3(LCMO82) is used as air cathode catalysts for rechargeable zinc-air batteries. The battery prototype can sustain 470 h or 40 discharge-charge cycles equivalent.

Selective Fragmentation of Biorefinery Corncob Lignin into p-Hydroxycinnamic Esters with a Supported ZnMoO4 Catalyst.

PubMed

Wang, Shuizhong; Gao, Wa; Li, Helong; Xiao, Ling-Ping; Sun, Run-Cang; Song, Guoyong

2018-04-16

Lignin is the largest renewable resource of bio-aromatics, and catalytic fragmentation of lignin into phenolic monomers is increasingly recognized as an important starting point for lignin valorization. Herein, we reported zinc molybdate (ZnMoO4) supported on MCM-41 can catalyze fragmentation of biorefinery technical lignin, enzymatic mild acidolysis lignin and native lignin derived from corncob, to give lignin oily products containing 15 to 37.8 wt% phenolic monomers, in which the high selectivities towards methyl coumarate 1 and methyl ferulate 2 were obtained (up to 78%). The effects of some key parameters such as the influences of solvent, reaction temperature, time, H2 pressure and catalyst dosage were examined in view of activity and selectivity. The loss of zinc atom in catalyst is appointed as a primary cause of deactivation, and catalytic activity and selectivity can be well-preserved for at least six times by thermal calcination. The high selectivity to compounds 1 and 2 make them easily separated and purified from lignin oily product, thus providing sustainable monomers for preparation of functional polyetheresters and polyesters. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The origin of chromitic chondrules and the volatility of Cr under a range of nebular conditions

NASA Technical Reports Server (NTRS)

Krot, Alexander; Ivanova, Marina A.; Wasson, John T.

1993-01-01

We characterize ten chromatic chondrules, two spinelian chondrules andd one spinel-bearing chondrule and summarize data for 120 chromitic inclusions discovered in an extensive survey of ordinary chondrites. Compositional and petrographic evidence suggests that chromitic chondrules and inclusions are closely related. The Cr/(Cr + Al) ratios in the spinal of these objects range from 0.5 to 0.9 and bulk Al2O3 contents are uniformly high (greater than 10 wt%, except for one with 8 wt%). No other elements having comparable solar abundances are so stongly enriched, and alkali feldspar and merrillite are more common than in normal chondrules. The Cr/Mg ratios in chromitic chondrules are 180-750 times the ratios in the bulk chondrite. With the possible exception of magnetic clumping of chromite in the presolar cloud, mechanical processes cannot account for this enrichment. Examination of nebular equilibrium processes shows that 50%-condensation temperatures of Cr at pH2/pH2O of 1500 are several tens of degrees below those of Mg as Mg2SiO4; the condensation of Cr is primarily as MgCr2O4 dissolved in MgAl2O4 at nebular pressures of 10(exp -4) atm or below. At pH2 = 10(exp -3) atm condesation as Cr in Fe-Ni is favored. Making the nebula much more oxidizing reduces the difference in condensation temperatures but Mg remains more refractory. We conclude that nebular equilibrium processes are not responsible for the enhanced Cr/Mg ratios. We propose that both Cr and Al became enriched in residues formed by incomplete evaporation of presolar lumps. We suggest that spinals remained as solid phases when the bulk of the silicates were incorporated into the evaporating melt; vaporization of Al and Cr were inhibited by the slow kinetics of diffusion. Subsequent melting and crystallization of these residues fractionated Cr from Al. The resulting materials constituted major components in the precursors of chromitic chondrules. Our model implies that chromitic chondrules and inclusions preserve the Cr isotopic record of presolar sources.

Polyethylene glycol assisted growth of Sn-doped ZnO nanorod arrays prepared via sol-gel immersion method

NASA Astrophysics Data System (ADS)

Ismail, A. S.; Mamat, M. H.; Malek, M. F.; Saidi, S. A.; Yusoff, M. M.; Mohamed, R.; Sin, N. D. Md; Suriani, A. B.; Rusop, M.

2018-05-01

Tin-doped zinc oxide (SZO) nanorod films at different concentrations of polyethylene glycol (PEG) were successfully deposited on zinc oxide (ZnO) seeded layer catalyst using sol-gel immersion method. The morphology of the samples were characterized using field emission scanning electron microscopy (FESEM), optical properties using UV-Vis spectrophotometer and electrical properties using I-V measurement system. The current-voltage (I-V) characteristics displayed that 5 wt % sample produced the highest conductivity.

A novel rechargeable zinc-air battery with molten salt electrolyte

NASA Astrophysics Data System (ADS)

Liu, Shuzhi; Han, Wei; Cui, Baochen; Liu, Xianjun; Zhao, Fulin; Stuart, Jessica; Licht, Stuart

2017-02-01

Zinc-air batteries have been proposed for EV applications and large-scale electricity storage such as wind and solar power. Although zinc-air batteries are very promising, there are numerous technological barriers to overcome. We demonstrate for the first time, a new rechargeable zinc-air battery that utilizes a molten Li0.87Na0.63K0.50CO3 eutectic electrolyte with added NaOH. Cyclic voltammetry reveals that a reversible deposition/dissolution of zinc occurs in the molten Li0.87Na0.63K0.50CO3 eutectic. At 550 °C, this zinc-air battery performs with a coulombic efficiency of 96.9% over 110 cycles, having an average charging potential of ∼1.43 V and discharge potential of ∼1.04 V. The zinc-air battery uses cost effective steel and nickel electrodes without the need for any precious metal catalysts. Moreover, the molten salt electrolyte offers advantages over aqueous electrolytes, avoiding the common aqueous alkaline electrolyte issues of hydrogen evolution, Zn dendrite formation, "drying out", and carbonate precipitation.

An Exercise in X-Ray Diffraction Using the Polymorphic Transition of Nickel Chromite.

ERIC Educational Resources Information Center

Chipman, David W.

1980-01-01

Describes a laboratory experiment appropriate for a course in either x-ray crystallography or mineralogy. The experiment permits the direct observation of a polymorphic transition in nickel chromite without the use of a special heating stage or heating camera. (Author/GS)

Chromite symplectites in Mg-suite troctolite 76535 as evidence for infiltration metasomatism of a lunar layered intrusion

NASA Astrophysics Data System (ADS)

Elardo, Stephen M.; McCubbin, Francis M.; Shearer, Charles K.

2012-06-01

Despite the very low chromium concentrations in its cumulus olivine (˜140 ppm), lunar troctolite 76535 contains large amounts of Cr sporadically, but highly concentrated, in symplectite assemblages consisting of Mg-Al-chromite and two pyroxenes. Previously proposed symplectite formation mechanisms include crystallization of trapped interstitial melt, diffusion of Cr from cumulus olivine, and/or remobilization of cumulus chromite grains. These mechanisms would imply that the highly Cr-depleted nature of Mg-suite parental magmas and their source materials inferred from cumulus olivine may be illusory. We have conducted a detailed petrologic and textural study of symplectites, as well as chromite veins, intercumulus assemblages, olivine-hosted melt inclusions and clinopyroxene-troilite veins in 76535 with the goals of constraining the origin of the symplectites, and the degree of Cr-depletion in Mg-suite magmas relative to other lunar basalts. Orthopyroxene and clinopyroxene in melt inclusions are depleted in Cr relative to their symplectite counterparts, averaging 900 and 1200 ppm vs. 7400 and 8100 ppm Cr2O3, respectively. Olivine in contact with symplectite assemblages may exhibit a diffusion profile of Cr going into olivine, whereas olivine boundaries away from symplectites show no diffusion profile. There is also a distinct lack of primary chromite as inclusions in cumulus phases and melt inclusions. Multiple textural observations, melt inclusion chemistry, and modeling of chromite-olivine equilibrium rule out previously proposed symplectite formation mechanisms, and strongly suggest that chromite was not a primary crystallization product of the 76535 parental magma. Accordingly, the post-cumulus addition of Cr and Fe is required to produce the symplectites. After considering multiple models, the addition of Cr and Fe to 76535 via infiltration metasomatism by an exogenous chromite-saturated melt is the model most consistent with multiple textural and geochemical observations. Failure of models that call upon Cr diffusion out of olivine grains imply that the observed Cr-depleted nature of olivine observed in many Mg-suite lithologies is a primary feature of the Cr-depleted nature of the Mg-suite parental magmas and their source materials. This substantial depletion of Cr in the magma relative to mare basalt magmas still requires a satisfactory explanation in order to be consistent with Mg-suite petrogenetic models and currently accepted bulk-Moon compositions. Additionally, if the intimate interaction of migrating melts with early lunar crustal lithologies was a widespread phenomenon after LMO solidification, it provides another mechanism by which to reset or delay closure of radiogenic isotopic systems and explain the Mg-suite-ferroan anorthosite age overlap.

Paragenesis of multiple platinum-group mineral populations in Shetland ophiolite chromitite: 3D X-ray tomography and in situ Os isotopes

NASA Astrophysics Data System (ADS)

Prichard, H. M.; Barnes, Stephen J.; Dale, C. W.; Godel, B.; Fisher, P. C.; Nowell, G. M.

2017-11-01

Chromitite from the Harold's Grave locality in the mantle section of the Shetland ophiolite complex is extremely enriched in Ru, Os and Ir, at μg/g concentrations. High-resolution X-ray computed tomography on micro-cores from these chromitites was used to determine the location, size, distribution and morphology of the platinum-group minerals (PGM). There are five generations of PGM in these chromitites. Small (average 5 μm in equivalent sphere diameter, ESD) euhedral laurites, often with Os-Ir alloys, are totally enclosed in the chromite and are likely to have formed first by direct crystallisation from the magma as the chromite crystallised. Also within the chromitite there are clusters of larger (50 μm ESD) aligned elongate crystals of Pt-, Rh-, Ir-, Os- and Ru-bearing PGM that have different orientations in different chromite crystals. These may have formed either by exsolution, or by preferential nucleation of PGMs in boundary layers around particular growing chromite grains. Thirdly there is a generation of large (100 μm ESD) composite Os-Ir-Ru-rich PGM that are all interstitial to the chromite grains and sometimes form in clusters. It is proposed that Os, Ir and Ru in this generation were concentrated in base metal sulfide droplets that were then re-dissolved into a later sulfide-undersaturated magma, leaving PGM interstitial to the chromite grains. Fourthly there is a group of almost spherical large (80 μm ESD) laurites, hosting minor Os-Ir-Ru-rich PGM that form on the edge or enclosed in chromite grains occurring in a sheet crosscutting a chromitite layer. These may be hosted in an annealed late syn- or post magmatic fracture. Finally a few of the PGM have been deformed in localised shear zones through the chromitites. The vast majority of the PGM - including small PGM enclosed within chromite, larger interstitial PGM and elongate aligned PGM - have Os isotope compositions that give Re-depletion model ages approximately equal to the age of the ophiolite at ∼492 Ma. A number of other PGM - not confined to a single textural group - fall to more or less radiogenic values, with four PGM giving anomalously unradiogenic Os corresponding to an older age of ∼1050 Ma. The 187Os/188Os isotopic ratios for PGM from Cliff and Quoys, from the same ophiolite section, are somewhat more radiogenic than those at Harold's Grave. This may be due to a distinct mantle source history or possibly the assimilation of radiogenic crustal Os.

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

Boppana, Venkata Bharat Ram; Hould, Nathan D.; Lobo, Raul F., E-mail: lobo@udel.ed

We report the first instance of a hydrothermal synthesis of zinc germanate (Zn{sub 2}GeO{sub 4}) nano-materials having a variety of morphologies and photochemical properties in surfactant, template and catalyst-free conditions. A systematic variation of synthesis conditions and detailed characterization using X-ray diffraction, ultraviolet-visible diffuse reflectance spectroscopy, Raman spectroscopy, electron microscopy, X-ray photoelectron spectroscopy and small angle X-ray scattering led to a better understanding of the growth of these particles from solution. At 140 {sup o}C, the zinc germanate particle morphology changes with pH from flower-shaped at pH 6.0, to poly-disperse nano-rods at pH 10 when the Zn to Ge ratiomore » in the synthesis solution is 2. When the Zn to Ge ratio is reduced to 1.25, mono-disperse nano-rods could be prepared at pH 7.5. Nanorod formation is also independent of the addition of cetyltrimethylammonium bromide (CTAB), in contrast to previous reports. Photocatalytic tests show that Zn{sub 2}GeO{sub 4} nano-rods (by weight) and flower shaped (by surface area) are the most active for methylene blue dye degradation among the synthesized zinc germanate materials. -- Graphical abstract: Zinc germanate materials were synthesized possessing unique morphologies dependent on the hydrothermal synthesis conditions in the absence of surfactant, catalyst or template. These novel materials are characterized and evaluated for their photocatalytic activities. Display Omitted highlights: > Zinc germanate synthesized hydrothermally (surfactant free) with unique morphologies. > Flower-shaped, nano-rods, globular particles obtained dependent on synthesis pH. > At 140 {sup o}C, they possess the rhombohedral crystal irrespective of synthesis conditions. > They are photocatalytically active for the degradation of methylene blue. > Potential applications could be photocatalytic water splitting and CO{sub 2} reduction.« less

Self-assembly formation of Bi-functional Co3O4/MnO2-CNTs hybrid catalysts for achieving both high energy/power density and cyclic ability of rechargeable zinc-air battery

PubMed Central

Xu, Nengneng; Liu, Yuyu; Zhang, Xia; Li, Xuemei; Li, Aijun; Qiao, Jinli; Zhang, Jiujun

2016-01-01

α-MnO2 nanotubes-supported Co3O4 (Co3O4/MnO2) and its carbon nanotubes (CNTs)-hybrids (Co3O4/MnO2-CNTs) have been successfully developed through a facile two-pot precipitation reaction and hydrothermal process, which exhibit the superior bi-functional catalytic activity for both ORR and OER. The high performance is believed to be induced by the hybrid effect among MnO2 nanotubes, hollow Co3O4 and CNTs, which can produce a synergetic enhancement. When integrated into the practical primary and electrochemically rechargeable Zn-air batteries, such a hybrid catalyst can give a discharge peak power density as high as 450 mW cm−2. At 1.0 V of cell voltage, a current density of 324 mA cm−2 is achieved. This performance is superior to all reported non-precious metal catalysts in literature for zinc-air batteries and significantly outperforms the state-of-the-art platinum-based catalyst. Particularly, the rechargeable Zn-air battery can be fabricated into all-solid-state one through a simple solid-state approach, which exhibits an excellent peak power density of 62 mW cm−2, and the charge and discharge potentials remain virtually unchanged during the overall cycles, which is comparable to the one with liquid electrolyte. PMID:27646032

Self-assembly formation of Bi-functional Co3O4/MnO2-CNTs hybrid catalysts for achieving both high energy/power density and cyclic ability of rechargeable zinc-air battery.

PubMed

Xu, Nengneng; Liu, Yuyu; Zhang, Xia; Li, Xuemei; Li, Aijun; Qiao, Jinli; Zhang, Jiujun

2016-09-20

α-MnO2 nanotubes-supported Co3O4 (Co3O4/MnO2) and its carbon nanotubes (CNTs)-hybrids (Co3O4/MnO2-CNTs) have been successfully developed through a facile two-pot precipitation reaction and hydrothermal process, which exhibit the superior bi-functional catalytic activity for both ORR and OER. The high performance is believed to be induced by the hybrid effect among MnO2 nanotubes, hollow Co3O4 and CNTs, which can produce a synergetic enhancement. When integrated into the practical primary and electrochemically rechargeable Zn-air batteries, such a hybrid catalyst can give a discharge peak power density as high as 450 mW cm(-2). At 1.0 V of cell voltage, a current density of 324 mA cm(-2) is achieved. This performance is superior to all reported non-precious metal catalysts in literature for zinc-air batteries and significantly outperforms the state-of-the-art platinum-based catalyst. Particularly, the rechargeable Zn-air battery can be fabricated into all-solid-state one through a simple solid-state approach, which exhibits an excellent peak power density of 62 mW cm(-2), and the charge and discharge potentials remain virtually unchanged during the overall cycles, which is comparable to the one with liquid electrolyte.

Melt/mantle interaction and melt evolution in the Sartohay high-Al chromite deposits of the Dalabute ophiolite (NW China)

NASA Astrophysics Data System (ADS)

Zhou, M.-F.; Robinson, P. T.; Malpas, J.; Aitchison, J.; Sun, M.; Bai, W.-J.; Hu, X.-F.; Yang, J.-S.

2001-06-01

The Sartohay block of the Dalabute ophiolite consists chiefly of mantle harzburgite and lherzolite with minor dunite. These rocks host voluminous chromite deposits with lenticular or vein-like shapes. The podiform chromitites are associated with, and cross-cut by, numerous troctolite dykes. Chromite in the chromitites has Al 2O 3 (23-31 wt%), TiO 2 (0.29-0.44 wt%), and Cr 2O 3 contents (<45 wt%) with Cr#s [100Cr/(Cr+Al)] (<60), typical of high-Al chromite deposits. The host peridotites in Sartohay have been texturally and geochemically modified by magmas from which the high-Al chromitites and mafic dykes formed. Dunites commonly envelop the podiform chromite bodies and show transitional contacts with the peridotites. Some of the peridotites and chromitites contain plagioclase that crystallized from impregnated melts. The dunite locally grades into troctolite with increasing plagioclase contents. As a result of melt impregnation, peridotites and dunites show variable Ca and Al contents and LREE enrichment. The parental magma of the chromitites was likely tholeiitic in composition, derived from partial melting of the asthenospheric mantle in a rising diapir. The interaction between this magma and pre-existing lithospheric mantle, composed of depleted lherzolite, would have formed a more silicic, tholeiitic magma from which high-Al chromitites crystallized. During this interaction, harzburgite and dunite were depleted in modal pyroxene and enriched in some incompatible elements (such as Al, Ca and LREE) due to melt impregnation.

Process for the synthesis of aliphatic alcohol-containing mixtures

DOEpatents

Greene, Marvin I.; Gelbein, Abraham P.

1984-01-01

A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200.degree. to 450.degree. C. and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

Process for the synthesis of aliphatic alcohol-containing mixtures

DOEpatents

Greene, M.I.; Gelbein, A.P.

1984-10-16

A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200 to 450 C and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

Geology and economic potential for chromite in the Zhob Valley ultramafic rock complex, Hindubagh, Quetta division, West Pakistan

USGS Publications Warehouse

Rossman, D.L.; Ahmad, Zaki; Rahman, Hamidur

1971-01-01

The ultramafic rocks making up the Zhob Valley igneous complex have yielded small amounts of metallurgical-grade chromite since the early part of the century. From 1968-1970 a cooperative study undertaken by the Geological Survey of Pakistan and the U. S. Geological Survey, under the auspices of the Government of Pakistan and the Agency for International Development, evaluated the chromite potential of the Zhob Valley area and provided data for effective exploration. The Jung Tor Ghar ultramafic rock mass, covering an area of about 45 square miles, is a thrust-fault block completely surrounded and underlain (?) by sedimentary rocks as young as Late Cretaceous in age. The igneous rocks were thrust from the northwest along an east-trending, north-dipping fault in Late Cretaceous or Paleocene time and were peneplaned, dissected, and deeply laterized by mid-Eocene time. The ultramafic rocks consist of interlayered harzburgite and dunite and a cross-cutting dunite here called transgressive dunite. Layered structure passes without discernible deviation from the interlayered harzburgite-dunite through the transgressive dunite. The lowest rocks in the mass, composed mainly of transgressive dunite, grade upward into the interlayered rock about 3,000 feet above the fault block base. The upper transgressive dunites tend to form interconnecting linear networks and probably a few pipe-like structures. The transgressive dunite is thought to have formed by action of water derived from the underlying sedimentary rocks; the water heated by the hot ultramafic rock (at the time of emplacement) altered the pyroxene to olivine and talc, and, with lowering temperature, to serpentine. Other interpretations are possible. Virtually all the chromite in the Jung Tor Ghar lies in or immediately above the masses of transgressive dunite. This fact provides a key to chromite exploration: The most favorable zone for prospecting lies in the vicinity of the upper contacts of the transgressive dunite masses where they. are flatly dipping; if the transgressive dunite masses are steeply dipping or pipe-like, the chromite tends to be more centrally located. The Jung Tor Ghar is believed to contain enough unmined chromite at practical minable depths to equal or exceed that mined to date but the individual deposits are likely to be small.

The amyloid architecture provides a scaffold for enzyme-like catalysts.

PubMed

Al-Garawi, Z S; McIntosh, B A; Neill-Hall, D; Hatimy, A A; Sweet, S M; Bagley, M C; Serpell, L C

2017-08-03

Natural biological enzymes possess catalytic sites that are generally surrounded by a large three-dimensional scaffold. However, the proportion of the protein molecule that participates in the catalytic reaction is relatively small. The generation of artificial or miniature enzymes has long been a focus of research because enzyme mimetics can be produced with high activity at low cost. These enzymes aim to mimic the active sites without the additional architecture contributed by the protein chain. Previous work has shown that amyloidogenic peptides are able to self-assemble to create an active site that is capable of binding zinc and catalysing an esterase reaction. Here, we describe the structural characterisation of a set of designed peptides that form an amyloid-like architecture and reveal that their capability to mimic carbonic anhydrase and serve as enzyme-like catalysts is related to their ability to self-assemble. These amyloid fibril structures can bind the metal ion Zn 2+ via a three-dimensional arrangement of His residues created by the amyloid architecture. Our results suggest that the catalytic efficiency of amyloid-like assembly is not only zinc-dependent but also depends on an active centre created by the peptides which is, in turn, dependent on the ordered architecture. These fibrils have good esterase activity, and they may serve as good models for the evolution of modern-day enzymes. Furthermore, they may be useful in designing self-assembling fibrils for applications as metal ion catalysts. This study also demonstrates that the ligands surrounding the catalytic site affect the affinity of the zinc-binding site to bind the substrate contributing to the enzymatic activity of the assembled peptides.

Comment on "Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts".

PubMed

Nakamura, Junji; Fujitani, Tadahiro; Kuld, Sebastian; Helveg, Stig; Chorkendorff, Ib; Sehested, Jens

2017-09-01

Kattel et al (Reports, 24 March 2017, p. 1296) report that a zinc on copper (Zn/Cu) surface undergoes oxidation to zinc oxide/copper (ZnO/Cu) during carbon dioxide (CO 2 ) hydrogenation to methanol and conclude that the Cu-ZnO interface is the active site for methanol synthesis. Similar experiments conducted two decades ago by Fujitani and Nakamura et al demonstrated that Zn is attached to formate rather than being fully oxidized. Copyright © 2017, American Association for the Advancement of Science.

Effect of Growth Parameters on SnO2 Nanowires Growth by Electron Beam Evaporation Method

NASA Astrophysics Data System (ADS)

Rakesh Kumar, R.; Manjula, Y.; Narasimha Rao, K.

2018-02-01

Tin oxide (SnO2) nanowires were synthesized via catalyst assisted VLS growth mechanism by the electron beam evaporation method at a growth temperature of 450 °C. The effects of growth parameters such as evaporation rate of Tin, catalyst film thickness, and different types of substrates on the growth of SnO2 nanowires were studied. Nanowires (NWs) growth was completely seized at higher tin evaporation rates due to the inability of the catalyst particle to initiate the NWs growth. Nanowires diameters were able to tune with catalyst film thickness. Nanowires growth was completely absent at higher catalyst film thickness due to agglomeration of the catalyst film. Optimum growth parameters for SnO2 NWs were presented. Nanocomposites such as Zinc oxide - SnO2, Graphene oxide sheets- SnO2 and Graphene nanosheets-SnO2 were able to synthesize at a lower substrate temperature of 450 °C. These nanocompsoites will be useful in enhancing the capacity of Li-ion batteries, the gas sensing response and also useful in increasing the photo catalytic activity.

SEM, optical, and Moessbauer studies of submicrometer chromite in Allende

NASA Technical Reports Server (NTRS)

Housley, R. M.

1982-01-01

New scanning electron and optical microscope results are presented showing that sub-micrometer chromite is abundant along healed cracks and grain boundaries in Allende chondrule olivine. Some wider healed cracks also contain pentlandite and euhedral Ni3Fe grains. Also reported are Moessbauer measurements on Allende HF-HCl residues confirming a high Fe(+++)/Fe(++) ratio.

TREATMENT OF HEXAVALENT CHROMIUM IN CHROMITE ORE PROCESSING SOLID WASTE USING A MIXED REDUCTANT SOLUTION OF FERROUS SULFATE AND SODIUM DITHIONITE

EPA Science Inventory

We developed a method for disseminating ferrous iron in the subsurface to enhance chemical reduction of hexavalent chromium (Cr(VI)) in a chromite ore processing solid waste derived from the production of ferrochrome alloy. The method utilizes ferrous sulfate (FeSO4) in combinati...

Novel hybrid materials based on the vanadium oxide nanobelts

NASA Astrophysics Data System (ADS)

Zabrodina, G. S.; Makarov, S. G.; Kremlev, K. V.; Yunin, P. A.; Gusev, S. A.; Kaverin, B. S.; Kaverina, L. B.; Ketkov, S. Yu.

2016-04-01

Novel hybrid materials based on zinc phthalocyanine and nanostructured vanadium oxides have attracted extensive attention for the development of academic research and innovative industrial applications such as flexible electronics, optical sensors and heterogeneous catalysts. Vanadium oxides nanobelts were synthesized via a hydrothermal treatment V2O5·nH2O gel with surfactants (TBAB, CTAB) used as structure-directing agents, where CTAB - cetyltrimethylammonium bromide, TBAB - tetrabutylammonium bromide. Hybrid materials were prepared decoration of (CTA)0.33V2O5 flexible nanobelts with cationic zinc phthalocyanine by the ion-exchange route. Investigations of the thermal stability, morphologies and structures of the (CTA)0.33V2O5, (TBA)0.16V2O5 nanobelts and zinc phthalocyanine exchange product were carried out. The hybrid materials based on the nanostructured vanadium oxide and zinc phthalocyanine were tested as photocatalysts for oxidation of citronellol and 2-mercaptoethanol by dioxygen.

Evidence for photosensitised hydrogen production from water in the absence of precious metals, redox-mediators and co-catalysts.

PubMed

Salzl, S; Ertl, M; Knör, G

2017-03-22

The water-soluble zinc porphyrin complex Zn(TPPS) 4- with TPPS = tetrakis-(4-sulfonatophenyl)porphyrin surprisingly was found to produce significant amounts of hydrogen from aqueous sulfite or amine solutions under visible-light exposure without requiring any other components such as electron relays or additional proton reduction catalysts. Although the production rates and total amounts of chemically stored fuel obtained under these conditions are still much too low to be relevant for practical applications, the background of this unprecedented observation was further studied in its own right. Since the central metal zinc is unlikely to be involved in proton-coupled electron transfer steps upon long-wavelength irradiation and the process does not seem to be much affected by variations of the electron donor added, the mechanism of photocatalytic H 2 release is suggested to involve previously neglected redox features of the in situ generated hydroporphyrin ligand system in aqueous solution.

Highly Efficient Selective Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol over Gold Supported on Zinc Oxide Materials

DOE PAGES

Chen, Hangning; Cullen, David A.; Larese, J. Z.

2015-11-30

We used Au/ZnO catalysts for liquid-phase selective hydrogenation of cinnamaldehyde to cinnamyl alcohol and compared with Au/Fe 2O 3 catalysts. To investigate the influence of the support on the hydrogenation activity and selectivity, three different Au/ZnO catalysts were synthesized, including Au/rod-tetrapod ZnO, Au/porous ZnO, and Au/ZnO-CP prepared using a coprecipitation method. Moreover, the influence of calcination temperature was also systematically investigated in this study. The characterization of Au/ZnO catalysts was performed using ICP, N 2 adsorption/desorption isotherms, X-ray diffraction, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy. Among all the supported Au catalysts prepared in this study, Au/ZnO-CP exhibits bothmore » the highest hydrogenation activity and selectivity. Using a 1.5% Au/ZnO-CP catalyst, 100% selectivity could be achieved with 94.9% conversion. Finally, we find that the Au particle (size and shape), the ZnO support (size and surface texture) and the interaction between Au and ZnO are three important parameters for achieving a highly efficient Au/ZnO catalyst.« less

Biodiesel production from waste cooking oil using copper doped zinc oxide nanocomposite as heterogeneous catalyst.

PubMed

Gurunathan, Baskar; Ravi, Aiswarya

2015-01-01

A novel CZO nanocomposite was synthesized and used as heterogeneous catalyst for transesterification of waste cooking oil into biodiesel using methanol as acyl acceptor. The synthesized CZO nanocomposite was characterized in FESEM with an average size of 80 nm as nanorods. The XRD patterns indicated the substitution of ZnO in the hexagonal lattice of Cu nanoparticles. The 12% (w/w) nanocatalyst concentration, 1:8 (v:v) O:M ratio, 55 °C temperature and 50 min of reaction time were found as optimum for maximum biodiesel yield of 97.71% (w/w). Hence, the use of CZO nanocomposite can be used as heterogeneous catalyst for biodiesel production from waste cooking oil. Copyright © 2015 Elsevier Ltd. All rights reserved.

Degradation of 4-Chlorophenol Under Sunlight Using ZnO Nanoparticles as Catalysts

NASA Astrophysics Data System (ADS)

Rajar, Kausar; Sirajuddin; Balouch, Aamna; Bhanger, M. I.; Sherazi, Tufail H.; Kumar, Raj

2018-03-01

Herein we demonstrate a simplistic microwave assisted chemical precipitation approach regarding the synthesis of zinc oxide nanoparticles. As-prepared ZnO nanoparticles (NPs) were characterized by UV-visible spectroscopy, Fourier transform infra-red spectroscopy, atomic force microscopy and x-ray diffractometry and scrutinized as photo-catalysts for degradation of 4-chlorophenol (4-CP) under sunlight. The study substantiated that 98.5% of 4-CP was degraded within 20 min in the absence of initiator like H2O2 which reflects an outstanding prospective use for ZnO NPs as photo-catalysts. The nanocatalysts were recycled four times and still showed catalytic efficiency up to 95.5% for degradation of 4-CP in the specified 20 min.

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths.

PubMed

Soloviev, Sergiy O; Kapran, Andriy Y; Kurylets, Yaroslava P

2015-02-01

Binary oxide systems (CuCr2O4, CuCo2O4), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al2O3), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O2, NOx, H2O, CO2) and O3 as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO2. Oxidants used can be arranged with reference to decreasing their activity in a following series: O3≫NO2>H2O>NO>O2>CO2. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O3 occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the "cold start" problem. Copyright © 2014. Published by Elsevier B.V.

Time-Resolved and Operando XAS Studies on Heterogeneous Catalysts - From the Gas Phase Towards Reactions in Supercritical Fluids

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

Grunwaldt, Jan-Dierk; Baiker, Alfons

2007-02-02

x-ray absorption spectroscopy is a well-suited technique to uncover the structure of heterogeneous catalysts under reaction conditions. Different aspects of in situ cell design suitable for dynamic and catalytic studies are discussed. In addition, criteria are presented that allow estimating the influence external and internal mass transfer. Starting with studies on gas-solid reactions, including structure-activity relationships, this concept is extended to liquid-solid reactions, reactions at high pressure and in supercritical fluids. The following examples are discussed in more detail: partial oxidation of methane over Pt-Rh/Al2O3, reduction of a Cu/ZnO catalyst, alcohol oxidation over Bi-promoted Pd/Al2O3 in liquid phase and overmore » Pd/Al2O3 in supercritical CO2, and batch reactions (e.g. CO2-fixation over zinc-based catalysts)« less

Response to Comment on "Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts".

PubMed

Kattel, Shyam; Ramírez, Pedro J; Chen, Jingguang G; Rodriguez, José A; Liu, Ping

2017-09-01

In their Comment on the our recent Report, Nakamura et al argue that our x-ray photoelectron spectroscopy (XPS) analysis was affected by the presence of formate species on the catalyst surface. This argument is not valid because the reactant gases were evacuated at temperatures from 525 to 575 kelvin, conditions under which formate is not stable on the catalyst surface. An analysis of the XPS results obtained after exposing zinc oxide/copper (111) [ZnO/Cu(111)] surfaces to hydrogen (H 2 ) and mixtures of carbon dioxide (CO 2 )/H 2 show an absence of carbon (C) 1s signal, no asymmetries in the oxygen (O) 1s peak, and a Zn:O intensity close to 1:1. Thus, the most active phase of these catalysts contained a ZnO-Cu interface. Copyright © 2017, American Association for the Advancement of Science.

Petrology and geochemistry of meta-ultramafic rocks in the Paleozoic Granjeno Schist, northeastern Mexico: Remnants of Pangaea ocean floor

NASA Astrophysics Data System (ADS)

Torres-Sánchez, Sonia Alejandra; Augustsson, Carita; Jenchen, Uwe; Rafael Barboza-Gudiño, J.; Alemán Gallardo, Eduardo; Ramírez Fernández, Juan Alonso; Torres-Sánchez, Darío; Abratis, Michael

2017-08-01

The Granjeno Schist is a meta-volcanosedimentary upper Paleozoic complex in northeastern Mexico. We suggest different tectonic settings for metamorphism of its serpentinite and talc-bearing rocks based on petrographic and geochemical compositions. According to the REE ratios (LaN/YbN = 0.51 -20.0 and LaN/SmN = 0.72-9.1) and the enrichment in the highly incompatible elements Cs (0.1 ppm), U (2.8 ppm), and Zr (60 ppm) as well as depletion in Ba (1 - 15 ppm), Sr (1 -184 ppm), Pb (0.1 -14 ppm), and Ce (0.1 -1.9 ppm) the rocks have mid-ocean ridge and subduction zones characteristics. The serpentinite contains Al-chromite, ferrian chromite and magnetite. The Al-chromite is characterized by Cr# of 0.48 to 0.55 suggesting a MORB origin, and Cr# of 0.93 to 1.00 for the ferrian chromite indicates a prograde metamorphism. We propose at least two serpentinization stages of lithospheric mantle for the ultramafic rock of the Granjeno Schist, (1) a first in an ocean-floor environment at sub-greenschist to greenschist facies conditions and (2) later a serpentinization phase related to the progressive replacement of spinel by ferrian chromite and magnetite at greenschist to low amphibolite facies conditions during regional metamorphism. The second serpentinization phase took place in an active continental margin during the Pennsylvanian. We propose that the origin of the ultramafic rocks is related to an obduction and accretional event at the western margin of Pangea.

Mineral resource assessment of the Dillon 1 degree x 2 degrees Quadrangle, Idaho and Montana

USGS Publications Warehouse

Pearson, Robert Carl; Trautwein, C.M.; Ruppel, E.T.; Hanna, W.F.; Rowan, L.C.; Loen, J.S.; Berger, B.R.

1992-01-01

The Dillon 1°x2° quadrangle in southwestern Montana and east-central Idaho was investigated as part of the U.S. Geological Survey's Conterminous United States Mineral Assessment Program (CUSMAP) to determine its mineral resource potential. An interdisciplinary study was made of geology, geochemistry, geophysics (gravity and aeromagnetics), remote sensing, and mineral deposits. The results of those studies, as well as mineral resource assessment of numerous mineraldeposit types, are published separately as a folio of maps. This report summarizes the studies, provides background information on them, and presents a selected bibliography relevant to the geology and mineral resources of the quadrangle. The quadrangle contains large resources of gold and substantial resources of talc and chlorite, all of which were being mined in the 1980's and early 1990's. Submarginal resources of molybdenum, copper, tungsten, and iron range from moderately large to large. Other commodities that may be present in significant amounts are chromite, lead, zinc, silver, barite, zeolite minerals, and various nonmetallic metamorphic minerals.

A MIXED CHEMICAL REDUCTANT FOR TREATING HEXAVALENT CHROMIUM IN A CHROMITE ORE PROCESSING SOLID WASTE

EPA Science Inventory

We evaluated a method for delivering ferrous iron into the subsurface to enhance chemical reduction of Cr(VI) in a chromite ore processing solid waste (COPSW). The COPSW is characterized by high pH (8.5 -11.5), high Cr(VI) concentrations in the solid phase (up to 550 mg kg-1) and...

Raman spectroscopic features of Al- Fe3+- poor magnesiochromite and Fe2+- Fe3+- rich ferrian chromite solid solutions

NASA Astrophysics Data System (ADS)

Kharbish, Sherif

2018-04-01

Naturally occurring Al- Fe3 +- poor magnesiochromite and Fe2+- Fe3 +- rich ferrian chromite solid solutions have been analyzed by micro-Raman spectroscopy. The results reflect a strong positive correlation between the Fe3 + # [Fe3+/(Fe3 ++Cr + Al)] and the positions of all Raman bands. A positive correlation of the Raman band positions with Mg# [Mg/(Mg + Fe2 +)] is less stringent. Raman spectra of magnesiochromite and ferrian chromite show seven and six bands, respectively, in the spectral region of 800 - 100 cm- 1. The most intense band in both minerals is identified as symmetric stretching vibrational mode, ν 1( A 1 g ). In the intermediate Raman-shift region (400-600 cm- 1), the significant bands are attributed to the ν 3( F 2 g ) > ν 4( F 2 g ) > ν 2( E g ) modes. The bands with the lowest Raman shifts (< 200 cm- 1) are assigned to F 2 g ( trans) translatory lattice modes. Extra bands in magnesiochromite (two bands) and in ferrian chromite (one weak band) are attributed to lowering in local symmetry and order/disorder effects.

Photocatalysis as an Effective Advanced Oxidation Process

EPA Science Inventory

Photocatalysis is generally referred to as the acceleration of a photoreaction by the presence of a semiconductor catalyst such as titanium dioxide (TiO2) or zinc oxide (ZnO). Photocatalytic materials can be prepared by using various methods such as a sol-gel process, solution pr...

Comparative Planetary Mineralogy: Co, Ni Systematics in Chromite from Planetary Basalts

NASA Technical Reports Server (NTRS)

Karner, J. M.; Shearer, C. K.; Papike, J. J.; Righter,K.

2005-01-01

Spinel is a minor but important phase in planetary basalts because its variable composition often reflects basalt petrogenesis. For example, complicated zoning trends in spinel can give clues to melt evolution [1], and V concentrations in chromite lend insight into magma oxygen fugacity (fO2) conditions [2]. Nickel and Co are two elements that are commonly used as a measure of melt fractionation, and their partitioning between olivine and melt is fairly well understood. Less clear is their partitioning into spinel, although [3] has explored Ni and Co systematics in experimental charges. This study documents Ni and Co behavior in early crystallizing spinel (chromite) from several planetary basalts in an attempt to compare our results with [3], and also gain insight into basalt evolution on the three planets.

40 CFR 57.302 - Performance level of interim constant controls.

Code of Federal Regulations, 2011 CFR

2011-07-01

... exceed the following: (i) For sulfuric acid plants on copper smelters, 12-hour running average; (ii) For sulfuric acid plants on lead smelters, 6-hour running average; (iii) For sulfuric acid plants on zinc... limitation shall take into account unavoidable catalyst deterioration in sulfuric acid plants, but may...

Space thermal control development

NASA Technical Reports Server (NTRS)

Hoover, M. J.; Grodzka, P. G.; Oneill, M. J.

1971-01-01

The results of experimental investigations on a number of various phase change materials (PCMs) and PCMs in combination with metals and other materials are reported. The evaluations include the following PCM system performance characteristics: PCM and PCM/filler thermal diffusivities, the effects of long-term thermal cycling, PCM-container compatibility, and catalyst effectiveness and stability. Three PCMs demonstrated performance acceptable enough to be considered for use in prototype aluminum thermal control devices. These three PCMs are lithium nitrate trihydrate with zinc hydroxy nitrate catalyst, acetamide, and myristic acid. Of the fillers tested, aluminum honeycomb filler was found to offer the most increase in system thermal diffusivity.

Mineralogical and geochemical features of the alteration processes of magmatic ores in the Beni Bousera ultramafic massif (north Morocco)

NASA Astrophysics Data System (ADS)

Hajjar, Zaineb; Gervilla, Fernando; Essaifi, Abderrahim; Wafik, Amina

2017-08-01

The Beni Bousera ultramafic massif (Internal Rif, Morocco) is characterized by the presence of two types of small-scale magmatic mineralizations (i) a mineralization consisting mainly of chromite and Ni arsenides associated to orthopyroxene and cordierite (Cr-Ni ores), and (ii) a mineralization mainly composed of magmatic Fe-Ni-Cu sulfides containing variable amounts of graphite and chromite associated to phlogopite, clinopyroxène and plagioclase (S-G ores). Theses ores underwent High-T (450-550 °C) and Low-T (150-300 °C) alteration processes. The High-T alteration processes are tentatively related to intrusion of leucogranite dykes. They are preserved in the Galaros Cr-Ni ore deposit where nickeline is partly dissolved and transformed to maucherite, and orthopyroxene alters to phlogopite. Ni and Co were mobilized to the fluid phase, rising up their availability and promoting their diffusion into chromite and phlogopite, which have significantly higher contents in Ni and Co in phlogopite-rich ores than in orthopyroxene- and nickeline-rich ones. The Low-T alteration processes are related to serpentinization/weathering spatially associated with a regional shear zone. They affected both the Cr-Ni and S-G ores. In the Cr-Ni ores, Ni-arsenides were completely leached out while chromite is fractured within a matrix of chlorite, vermiculite and Ni-rich serpentine. In S-G ores, the silicates were altered into amphibole, Fe-rich chlorite and pectolite in clinopyroxene- and plagioclase-bearing ores while sulfides were completely leached out in phlogopite-bearing ores where iron oxides and hydroxides, and Fe-rich vermiculite were deposited. Chromite composition is not affected by the Low-T alteration processes.

The reduction mechanism of a natural chromite at 1416 °C

NASA Astrophysics Data System (ADS)

Soykan, O.; Eric, R. H.; King, R. P.

1991-02-01

The behavior of a natural chromite from the Bushveld Complex, Transvaal, South Africa, during reduction at 1416 °C by graphite was studied by means of thermogravimetric analysis, X-ray diffraction (XRD) analysis, energy-dispersive X-ray analysis (EDAX), and metallographic analysis. Experimental runs were allowed to proceed up to 120 minutes, resulting in 99 pct reduction. The specific objective of this study was to delineate the reduction mechanism of chromite by graphite. Zoning was observed in partially reduced chromites with degrees of reduction of up to about 70 pct. The inner cores were rich in iron, while the outer cores were depleted of iron. Energy-dispersive X-ray analysis revealed that Fe2+ and Cr3+ ions had diffused outward, whereas Cr2+, Al3+, and Mg2+ ions had diffused inward. The following mechanism of reduction, which is based on the assumption that the composition of the spinel phase remains stoichiometric with increasing degree of reduction, is proposed, (a) Initially, Fe3+ and Fe2+ ions at the surface of the chromite particle are reduced to the metallic state. This is followed immediately by the reduction of Cr3+ ions to the divalent state, (b) Cr2+ ions diffusing toward the center of the particle reduce the Fe3+ ions in the spinel under the surface of the particle to Fe2+ at the interface between the inner and outer cores. Fe2+ ions diffuse toward the surface, where they are reduced to metallic iron, (c) After the iron has been completely reduced, Cr3+ and any Cr2+ that is present are reduced to the metallic state, leaving an iron- and chromium-free spinel, MgAl2O4.

Volatile products from the interaction of KCl(g) with Cr2O3 and LaCrO3 in oxidizing environments

NASA Technical Reports Server (NTRS)

Kohl, F. J.; Miller, R. A.; Stearns, C. A.; Fryburg, G. C.; Dillard, J. G.

1977-01-01

Cooled target collection techniques and high pressure mass spectrometric sampling were used to measure the relative rates of oxidative vaporization and to identify the volatile products emanating from samples of chromia and Mg-doped lanthanum chromite. The materials were exposed to partial pressures of KCl with and without H2O in one atmosphere of slowly flowing oxygen at elevated temperatures. Chromia and fresh samples of lanthanum chromite exhibited enhanced rates of oxidative vaporization upon exposure to these reactants. Mass spectrometric identification showed that the enhancements resulted from the heterogeneous formation of complex molecules of the type KCl sub 1,2,3 CrO3 and KOH sub l,2 CrO3. Lanthanum chromite that had undergone prolonged oxidative vaporization exhibited no enhanced oxidation upon exposure to the reactants.

Stainless steel wire mesh-supported ZnO for the catalytic photodegradation of methylene blue under ultraviolet irradiation.

PubMed

Vu, Tan T; del Río, Laura; Valdés-Solís, Teresa; Marbán, Gregorio

2013-02-15

The aim of this study was to assess the activity of catalysts formed by nanostructured zinc oxide supported on stainless steel wire mesh for the photocatalytic degradation of methylene blue under UV irradiation. Catalysts prepared by means of different low temperature synthesis methods, as described in a previous work (Vu et al., Mater. Res. Bull. 47 (2012) 1577-1586) were tested. A new activity parameter was introduced in order to compare the catalytic activity of the different catalysts. The best catalyst showed a catalytic activity higher than that of the reference material TiO(2) P25 (Degussa-Evonik). This high activity is attributed to a higher quantum yield derived from the small particle length of the ZnO deposited on the wire mesh. The photocatalytic degradation kinetics of methylene blue fitted a potential model with n orders ranging from 0.5 to 6.9. Reaction orders over 1 were attributed to catalyst deactivation during the reaction resulting from the photocorrosion of ZnO. Copyright © 2012 Elsevier B.V. All rights reserved.

Laboratory Validation and Demonstrations of Non-Hexavalent Chromium Conversion Coatings for Steel Substrates (Briefing Charts)

DTIC Science & Technology

2011-02-01

UNCLASSIFIED: Approved for public release; distribution unlimited. Laboratory Validation and Demonstrations of Non-Hexavalent Chromium Conversion...00-00-2011 4. TITLE AND SUBTITLE Laboratory Validation and Demonstrations of Non-Hexavalent Chromium Conversion Coatings for Steel Substrates 5a...Coatings for HHA • SurTec 650 - ChromitAL TCP - Trivalent Chrome Pretreatment Developed by NAVAIR for Aluminum. • Chemetall Oxsilan 9810/2 - Non-chrome

The Effect of Carbonaceous Reductant Selection on Chromite Pre-reduction

NASA Astrophysics Data System (ADS)

Kleynhans, E. L. J.; Beukes, J. P.; Van Zyl, P. G.; Bunt, J. R.; Nkosi, N. S. B.; Venter, M.

2017-04-01

Ferrochrome (FeCr) production is an energy-intensive process. Currently, the pelletized chromite pre-reduction process, also referred to as solid-state reduction of chromite, is most likely the FeCr production process with the lowest specific electricity consumption, i.e., MWh/t FeCr produced. In this study, the effects of carbonaceous reductant selection on chromite pre-reduction and cured pellet strength were investigated. Multiple linear regression analysis was employed to evaluate the effect of reductant characteristics on the aforementioned two parameters. This yielded mathematical solutions that can be used by FeCr producers to select reductants more optimally in future. Additionally, the results indicated that hydrogen (H)- (24 pct) and volatile content (45.8 pct) were the most significant contributors for predicting variance in pre-reduction and compressive strength, respectively. The role of H within this context is postulated to be linked to the ability of a reductant to release H that can induce reduction. Therefore, contrary to the current operational selection criteria, the authors believe that thermally untreated reductants ( e.g., anthracite, as opposed to coke or char), with volatile contents close to the currently applied specification (to ensure pellet strength), would be optimal, since it would maximize H content that would enhance pre-reduction.

The reduction mechanism of chromite in the presence of a silica flux

NASA Astrophysics Data System (ADS)

Weber, P.; Eric, R. H.

1993-12-01

The reduction behavior of a natural chromite from the Bushveld Complex of South Africa was studied at 1300 °C to 1500 °C. Reduction was by graphite in the presence of silica. Thermo-gravimetric analysis, X-ray diffraction (XRD) analysis, energy-dispersive X-ray analysis (EDAX), and metallographic analysis were the experimental techniques used. Silica affected the reduction at and above 1400 °C. A two-stage reduction mechanism was established. The first stage, up to a reduction level of about 40 pct, is primarily confined to iron metallization, and zoning is observed in partially reduced chromites. In this stage, silica does not interfere with the reduction, which proceeds by an outward diffusion of Fe2+ ions and an inward diffusion of Mg2+ and Cr2+ ions. The second stage is primarily confined to chromium metallization, and formation of a silicate slag alters the reduction mechanism. The slag phase agglomerates and even embeds partially reduced chromite particles. An ion-exchange reaction between the re-ducible cations (Cr3+ and Fe2+) in the spinel and the dissolved cations (Al3+ and Mg2+) in the slag allows further reduction. Once the reducible cations are dissolved in the slag phase, they are reduced to the metallic state at sites where there is contact with the reductant.

Kinetics of the reduction of bushveld complex chromite ore at 1416 °C

NASA Astrophysics Data System (ADS)

Soykan, O.; Eric, R. H.; King, R. P.

1991-12-01

The kinetics of the reduction of chromite ore from the LG-6 layer of the Bushveld Complex of the Transvaal in South Africa were studied at 1416 °C by the thermogravimetric analysis (TGA) technique. Spectroscopic graphite powder was employed as the reductant. The aim of this article is to present a kinetic model that satisfactorily describes the solid-state carbothermic reduction of chromite. A generalized rate model based on an ionic diffusion mechanism was developed. The model included the contribution of the interfacial area between partially reduced and unreduced zones in chromite particles and diffusion. The kinetic model described the process for degrees of reduction from 10 to 75 pet satisfactorily. It was observed that at a given particle size, the rate of reduction was controlled mainly by interfacial area up to about 40 pet reduction, after which the rate was dominated by diffusion. On the other hand, for a given degree of reduction, the contribution of the interfacial area to the rate increased, while that of diffusion decreased, with a decrease in the particle size. The value of the diffusion coefficient for the Fe2+ species at 1416 °C was calculated to be 2.63 x 10-2 cm2/s.

Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst

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

Wang, Aiguo; Austin, Danielle; Karmakar, Abhoy

The technical feasibility of coaromatization of acetic acid derived from biomass and methane was investigated under mild reaction conditions (400 °C and 30 bar) over silver-, zinc-, and/or gallium-modified zeolite catalysts. On the basis of GC-MS, Micro-GC, and TGA analysis, more light aromatic hydrocarbons, less phenol formation, lower coke production, and higher methane conversion are observed over 5%Zn-1%Ga/ZSM-5 catalyst in comparison with catalytic performance over the other catalysts. Direct evidence of methane incorporation into aromatics over 5%Zn-1%Ga/ZSM-5 catalyst is witnessed in 1H, 2H, and 13C NMR spectra, revealing that the carbon from methane prefers to occupy the phenyl carbon sitesmore » and the benzylic carbon sites, and the hydrogen of methane favors the aromatic and benzylic substitutions of product molecules. In combination with the 13C NMR results for isotopically labeled acetic acid ( 13CH 3COOH and CH 3 13COOH), it can be seen that the methyl and carbonyl carbons of acetic acid are equally involved in the formation of ortho, meta and para carbons of the aromatics, whereas the phenyl carbons directly bonded with alkyl substituent groups and benzylic carbons are derived mainly from the carboxyl carbon of acetic acid. After various catalyst characterizations by using TEM, XRD, DRIFT, NH 3-TPD, and XPS, the excellent catalytic performance might be closely related to the highly dispersed zinc and gallium species on the zeolite support, moderate surface acidity, and an appropriate ratio of weak acidic sites to strong acidic sites as well as the fairly stable oxidation state during acetic acid conversion under a methane environment. Two mechanisms of the coaromatization of acetic acid and methane have also been proposed after consulting all the collected data in this study. In conclusion, the results reported in this paper could potentially lead to more cost-effective utilization of abundant natural gas and biomass.« less

Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst

DOE PAGES

Wang, Aiguo; Austin, Danielle; Karmakar, Abhoy; ...

2017-04-19

The technical feasibility of coaromatization of acetic acid derived from biomass and methane was investigated under mild reaction conditions (400 °C and 30 bar) over silver-, zinc-, and/or gallium-modified zeolite catalysts. On the basis of GC-MS, Micro-GC, and TGA analysis, more light aromatic hydrocarbons, less phenol formation, lower coke production, and higher methane conversion are observed over 5%Zn-1%Ga/ZSM-5 catalyst in comparison with catalytic performance over the other catalysts. Direct evidence of methane incorporation into aromatics over 5%Zn-1%Ga/ZSM-5 catalyst is witnessed in 1H, 2H, and 13C NMR spectra, revealing that the carbon from methane prefers to occupy the phenyl carbon sitesmore » and the benzylic carbon sites, and the hydrogen of methane favors the aromatic and benzylic substitutions of product molecules. In combination with the 13C NMR results for isotopically labeled acetic acid ( 13CH 3COOH and CH 3 13COOH), it can be seen that the methyl and carbonyl carbons of acetic acid are equally involved in the formation of ortho, meta and para carbons of the aromatics, whereas the phenyl carbons directly bonded with alkyl substituent groups and benzylic carbons are derived mainly from the carboxyl carbon of acetic acid. After various catalyst characterizations by using TEM, XRD, DRIFT, NH 3-TPD, and XPS, the excellent catalytic performance might be closely related to the highly dispersed zinc and gallium species on the zeolite support, moderate surface acidity, and an appropriate ratio of weak acidic sites to strong acidic sites as well as the fairly stable oxidation state during acetic acid conversion under a methane environment. Two mechanisms of the coaromatization of acetic acid and methane have also been proposed after consulting all the collected data in this study. In conclusion, the results reported in this paper could potentially lead to more cost-effective utilization of abundant natural gas and biomass.« less

Preorganized bis-zinc phosphodiester cleavage catalysts possessing natural ligands: a lesson pertinent to bimetallic artificial enzymes.

PubMed

Worm, Karen; Chu, Feiya; Matsumoto, Kazunari; Best, Michael D; Lynch, Vincent; Anslyn, Eric V

2003-02-03

Two preorganized bis-zinc receptors (2 and 3) were synthesized wherein the metals were ligated with ligands present in natural phosphodiesterases: imidazoles and carboxylates. The intrametallic distance is near 4.5 A, that found in natural nucleases and other successful artificial nucleases. With only two imidazoles (2), the zinc binding affinities were not high enough to achieve cooperativity. Yet, with a third ligand, a carboxylate (3), cooperativity was found in the cleavage of HPNPP. The preorganization of 3 was achieved using a "steric gearing" strategy. The enhancement was 80-fold for cooperation between the two metals relative to a mono-metallic analogue (5). However, there was no observable enhancement in the hydrolysis of RNA using 3 relative to 5. Therefore, we conclude that placing two zinc atoms that are ligated with natural ligands at the appropriate distance for catalysis is not sufficient to enhance the cleavage of RNA, but is successful for activated RNA substrate mimics.

Intensified synthesis of medium chain triglycerides using ultrasonic reactors at a capacity of 4L.

PubMed

Mohod, Ashish V; Gogate, Parag R

2018-04-01

Lipids are considered as one of the most crucial nutrients for humans and among the various classes, medium chain triglycerides (MCTs) are considered as the most important functional foods and nutraceuticals. The present work deals with the intensification of synthesis of MCTs at a large capacity of 4L based on the use of ultrasonic bath and ultrasonic longitudinal horn. The effect of operating parameters like molar ratio of the reactants, type of catalyst and catalyst loading as well as the temperature on the extent of conversion has been investigated. The effect of molar ratio of lauric acid and glycerol was investigated over the range of 1:2 to 1:8 whereas the effect of loading of sulfuric acid was studied over the range of 4 ml/L-10 ml/L and zinc chloride loading over the range of 1 g/L-4 g/L. The effect of temperature was also studied using the conventional approach where it has been observed that 90 °C is an optimum temperature giving the extent of conversion as 72%. Also, the use of homogeneous catalyst as sulphuric acid was found to be more effective as compared to the solid catalyst as zinc chloride. It was observed that the maximum extent of conversion as 77.5% was obtained at 8 ml/L of sulfuric acid and molar ratio of 1:6 using ultrasonic longitudinal horn with US bath giving lower conversion as compared to US longitudinal horn but higher than the conventional approach under same operating conditions. The present work clearly established the intensification benefits in terms of reduction in time and higher conversion using cavitational reactors. Copyright © 2017 Elsevier B.V. All rights reserved.

Structural, optical and photocatalytic properties of visible light driven zinc oxide hybridized two-dimensional π-conjugated polymeric g-C3N4 composite

NASA Astrophysics Data System (ADS)

Murugesan, Pramila; Girichandran, Nandalal; Narayanan, Sheeba; Manickam, Matheswaran

2018-01-01

Zinc oxide (ZnO) hybridized with graphitic carbon nitride (g-C3N4) composite was prepared via one step calcination method and well characterized using various physiochemical techniques. The prepared composite exhibits excellent photocatalytic activity and stability for decolorization of methylene blue (MB) dye solution under visible light irradiation. Effect of various rate determining parameters such as catalyst loading, initial dye concentration and pH on the decolorization of MB has been analyzed. The optimum conditions for efficient color removal were found to be 7, 10 ppm and 2 g/L for pH, dye concentration and catalyst dosage respectively. The intermediate compounds formed during the decolorization process were evaluated by GCMS spectra. It was inferred that the ZnO/g-C3N4 (98.83%) composite exhibits highest decolorization efficiency as compare with pure g-C3N4 (35.21%). Such enhancement of photocataytic activity is mainly attributed to the efficient separation of photo induced electron hole pairs via Z-scheme model composed of ZnO and g-C3N4.

Catalytic pyrolysis of Alcea pallida stems in a fixed-bed reactor for production of liquid bio-fuels.

PubMed

Aysu, Tevfik

2015-09-01

Pyrolysis of Alcea pallida stems was performed in a fixed-bed tubular reactor with and without catalyst at three different temperatures. The effects of pyrolysis parameters including temperature and catalyst on the product yields were investigated. It was found that higher temperature resulted in lower liquid (bio-oil) and solid (bio-char) yields and higher gas yields. Catalysts had different effects on product yields and composition of bio-oils. Liquid yields were increased in the presence of zinc chloride and alumina but decreased with calcium hydroxide, tincal and ulexite. The highest bio-oil yield (39.35%) by weight including aqueous phase was produced with alumina catalyst at 500 °C. The yields of bio-char, bio-oil and gas produced, as well as the compositions of the resulting bio-oils were determined by elemental analysis, TGA, FT-IR and GC-MS. 160 different compounds were identified by GC-MS in the bio-oils obtained at 500 °C. Copyright © 2015 Elsevier Ltd. All rights reserved.

Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction

NASA Astrophysics Data System (ADS)

Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian; Feng, Xinliang; Müllen, Klaus

2014-09-01

Development of efficient, low-cost and stable electrocatalysts as the alternative to platinum for the oxygen reduction reaction is of significance for many important electrochemical devices, such as fuel cells, metal-air batteries and chlor-alkali electrolysers. Here we report a highly active nitrogen-doped, carbon-based, metal-free oxygen reduction reaction electrocatalyst, prepared by a hard-templating synthesis, for which nitrogen-enriched aromatic polymers and colloidal silica are used as precursor and template, respectively, followed by ammonia activation. Our protocol allows for the simultaneous optimization of both porous structures and surface functionalities of nitrogen-doped carbons. Accordingly, the prepared catalysts show the highest oxygen reduction reaction activity (half-wave potential of 0.85 V versus reversible hydrogen electrode with a low loading of 0.1 mg cm-2) in alkaline media among all reported metal-free catalysts. Significantly, when used for constructing the air electrode of zinc-air battery, our metal-free catalyst outperforms the state-of the-art platinum-based catalyst.

Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts

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

Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G.

The active sites over commercial copper/zinc oxide/aluminum oxide (Cu/ZnO/Al 2O 3) catalysts for carbon dioxide (CO 2) hydrogenation to methanol, the Zn-Cu bimetallic sites or ZnO-Cu interfacial sites, have recently been the subject of intense debate. Here, we report a direct comparison between the activity of ZnCu and ZnO/Cu model catalysts for methanol synthesis. By combining x-ray photoemission spectroscopy, density functional theory, and kinetic Monte Carlo simulations, we can identify and characterize the reactivity of each catalyst. Both experimental and theoretical results agree that ZnCu undergoes surface oxidation under the reaction conditions so that surface Zn transforms into ZnO andmore » allows ZnCu to reach the activity of ZnO/Cu with the same Zn coverage. These results highlight a synergy of Cu and ZnO at the interface that facilitates methanol synthesis via formate intermediates.« less

Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts

DOE PAGES

Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G.; ...

2017-03-23

The active sites over commercial copper/zinc oxide/aluminum oxide (Cu/ZnO/Al 2O 3) catalysts for carbon dioxide (CO 2) hydrogenation to methanol, the Zn-Cu bimetallic sites or ZnO-Cu interfacial sites, have recently been the subject of intense debate. Here, we report a direct comparison between the activity of ZnCu and ZnO/Cu model catalysts for methanol synthesis. By combining x-ray photoemission spectroscopy, density functional theory, and kinetic Monte Carlo simulations, we can identify and characterize the reactivity of each catalyst. Both experimental and theoretical results agree that ZnCu undergoes surface oxidation under the reaction conditions so that surface Zn transforms into ZnO andmore » allows ZnCu to reach the activity of ZnO/Cu with the same Zn coverage. These results highlight a synergy of Cu and ZnO at the interface that facilitates methanol synthesis via formate intermediates.« less

Comparative Planetary Mineralogy: V/(Cr+Al) Systematics in Chromites as an Indicator of Relative Oxygen Fugacity

NASA Technical Reports Server (NTRS)

Papike, J. J.; Kamer, J. M.; Shearer, C. K.

2004-01-01

As our contribution to the new "Oxygen in the Solar System" initiative of the Lunar and Planetary Institute and the NASA Cosmochemistry Program, we have been developing oxygen barometers based largely on behavior of V which can occur in four valence states V2+, V3+, V4+, and V5+, and record at least 8 orders of magnitude of fO2. Our first efforts in measuring these valence proportions were by XANES techniques in basaltic glasses from Earth, Moon, and Mars. We now address the behavior of V valence states in chromite in basalts from Earth, Moon, and Mars. We have been looking for a "V in chromite oxybarometer" that works with data collected by the electron microprobe and thus is readily accessible to a large segment of the planetary materials community. This paper describes very early results that will be refined over the next two years.

Co-settling of Chromite and Sulfide Melt Droplets and Trace Element Partitioning between Sulfide and Silicate Melts

NASA Astrophysics Data System (ADS)

Manoochehri, S.; Schmidt, M. W.; Guenther, D.

2013-12-01

Gravitational settling of immiscible, dense sulfide melt droplets together with other cumulate phases such as chromite, combined with downward percolation of these droplets through a cumulate pile, is thought to be one of the possible processes leading to the formation of PGE rich sulfide deposits in layered mafic intrusions. Furthermore some chromitite seams in the Merensky Reef (Bushveld Complex) are considered to be acting as a filter or barrier for further downward percolation of sulfide melts into footwall layers. To investigate the feasibility of such mechanical processes and to study the partitioning behavior of 50 elements including transition metals and REEs (but not PGEs) between a silicate and a sulfide melt, two separate series of high temperature (1250-1380 °C) centrifuge-assisted experiments at 1000 g, 0.4-0.6 GPa were conducted. A synthetic silicate glass with a composition representative of the parental magma of the Bushveld Complex (~ 55 wt% SiO2) was mixed with pure FeS powder. For the first series of experiments, 15 or 25 wt% natural chromite with average grain sizes of ~ 5 or 31 μm were added to a mixture of silicate glass and FeS (10 wt%) adding 1 wt% water. For the second series, a mixture of the same glass and FeS was doped with 50 trace elements. These mixtures were first statically equilibrated and then centrifuged. In the first experimental series, sulfide melt droplets settled together with, but did not segregate from chromite grains even after centrifugation at 1000 g for 12 hours. A change in initial chromite grain size and proportions didn't have any effect on segregation. Without chromite, the starting mixture resulted in the formation of large sulfide melt pools together with finer droplets still disseminated through the silicate glass and both at the bottom of the capsule. The incomplete segregation of sulfide melt is interpreted as being due to high interfacial energies between sulfide and silicate melts/crystals which hinder both, the nucleation of newly formed sulfide droplets and the interconnectivity of separate droplets. The interfacial energies between sulfide melt and silicate or oxide crystals is even higher than for silicate melt, consequently in experiments with chromite, sulfide segregation is even more hindered. Partition coefficients of 50 elements between a sulfide and a silicate melt are determined as a function of differing temperature between 1250 - 1380 °C. As a proxy to investigate the bond strength of network modifier cations, the relation between the partition coefficients and ionic potentials of different groups of elements has been determined.

Catalyst for cracking kerosene

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

Hsie, C. H.

1985-06-04

A catalyst capable of cracking kerosene under lower pressure and temperature comprising kerosene; metal powder mixture of chromium powder, copper powder, lead powder, zinc powder, nickel powder, manganese powder in an amount of 12 to 13 parts by weight per 100 parts by weight of said kerosene; sulfuric acid in an amount of 15 to 30 parts by weight per 100 parts by weight of said kerosene; inorganic powder mixture of aluminum oxide powder, serpentine powder, alum powder, magnesium oxide powder, limestone powder, slake lime powder, silica powder, and granite powder in an amount of 150 to 170 parts bymore » weight per 100 parts by weight of said kerosene.« less

Effective treatment of alkaline Cr(VI) contaminated leachate using a novel Pd-bionanocatalyst: Impact of electron donor and aqueous geochemistry

PubMed Central

Watts, Mathew P.; Coker, Victoria S.; Parry, Stephen A.; Thomas, Russell A.P.; Kalin, Robert; Lloyd, Jonathan R.

2015-01-01

Palladium catalysts offer the potential for the effective treatment of a variety of priority reducible pollutants in natural waters. In this study, microbially synthesized magnetite nanoparticles were functionalized with Pd(0), creating a highly reactive, magnetically recoverable, nano-scale catalyst (Pd-BnM). This was then investigated for the treatment of model Cr(VI) contaminated solutions at a range of pH values, and also alkaline Cr(VI) contaminated leachates from chromite ore processing residue (COPR); a contaminant issue of global concern. The sample of COPR used in this study was obtained from a site in Glasgow, UK, where extensive Cr(VI) contamination has been reported. In initial experiments Pd-BnM was supplied with H2 gas or formate as electron donors, and Cr(VI) removal from model synthetic solutions was quantified at various pH values (2–12). Effective removal was noted at neutral to environmentally relevant alkaline (pH 12) pH values, while the use of formate as an electron donor resulted in loss of performance under acidic conditions (pH 2). Reaction kinetics were then assessed with increasing Pd-BnM loading in both model pH 12 Cr(VI) solutions and the COPR leachate. When formate was used as the electron donor for Pd-BnM, to treat COPR leachate, there was significant inhibition of Cr(VI) removal. In contrast, a promotion of reaction rate, was observed when H2 was employed. Upon sustained reaction with model Cr(VI) solutions, in the presence of excess electron donor (formate or H2), appreciable quantities of Cr(VI) were removed before eventual inactivation of the catalyst. Faster onset of inactivation was reported in the COPR leachates, removing 4% and 64% of Cr(VI) observed from model Cr(VI) solutions, when formate and H2 were used as electron donors, respectively. XAS, TEM-EDX and XPS analysis of the catalysts that had been inactivated in the model solution, showed that the surface had an extensive covering of reduced Cr(III), most likely as a CrOOH phase. COPR reacted catalysts recorded a lower abundance of Cr(III) alongside a high abundance of the leachate components Ca and Si, implicating these elements in the faster onset of inactivation. PMID:26146457

Conditional estimates of the number of podiform chromite deposits

USGS Publications Warehouse

Singer, D.A.

1994-01-01

A desirable guide for estimating the number of undiscovered mineral deposits is the number of known deposits per unit area from another well-explored permissive terrain. An analysis of the distribution of 805 podiform chromite deposits among ultramafic rocks in 12 subareas of Oregon and 27 counties of California is used to examine and extend this guide. The average number of deposits in this sample of 39 areas is 0.225 deposits per km2 of ultramafic rock; the frequency distribution is significantly skewed to the right. Probabilistic estimates can be made by using the observation that the lognormal distribution fits the distribution of deposits per unit area. A further improvement in the estimates is available by using the relationship between the area of ultramafic rock and the number of deposits. The number (N) of exposed podiform chromite deposits can be estimated by the following relationship: log10(N)=-0.194+0.577 log10(area of ultramafic rock). The slope is significantly different from both 0.0 and 1.0. Because the slope is less than 1.0, the ratio of deposits to area of permissive rock is a biased estimator when the area of ultramafic rock is different from the median 93 km2. Unbiased estimates of the number of podiform chromite deposits can be made with the regression equation and 80 percent confidence limits presented herein. ?? 1994 Oxford University Press.

Properties of Amorphous Carbon Microspheres Synthesised by Palm Oil-CVD Method

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

Zobir, S. A. M.; Nano-SciTech Centre,; Zainal, Z.

2011-03-30

Amorphous carbon microspheres were synthesized using a dual-furnace chemical vapour deposition method at 800-1000 deg. C. Palm oil-based cooking oil (PO) and zinc nitrate solution was used as a carbon source and catalyst precursor, respectively with PO to zinc nitrate ratio of 30:20 (v/v) and a silicon wafer as the sample target. Regular microsphere shape of the amorphous carbons was obtained and a uniform microsphere structure improved as the carbonization temperature increased from 800 to 1000 deg. C. At 800 deg. C, no regular microspheres were formed but more uniform structure is observed at 900 deg. C. Generally the microspheresmore » size is uniform when the heating temperature was increased to 1000 deg. C, but the presence of mixed sizes can still be observed. X-ray diffraction patterns show the presence of oxide of carbon, ZnO phase together with Zn oxalate phase. Raman spectra show two broad peaks characteristic to amorphous carbon at 1344 and 1582 cm{sup -1} for the D and G bands, respectively. These bands become more prominent as the preparation temperature increased from 800 to 1000 deg. C. This is in agreement with the formation of amorphous carbon microspheres as shown by the FESEM study and other Zn-based phases as a result of the oxidation process of the palm oil as the carbon source and the zinc nitrate as the catalyst precursor, respectively.« less

Photoinduced Biohydrogen Production from Biomass

PubMed Central

Amao, Yutaka

2008-01-01

Photoinduced biohydrogen production systems, coupling saccharaides biomass such as sucrose, maltose, cellobiose, cellulose, or saccharides mixture hydrolysis by enzymes and glucose dehydrogenase (GDH), and hydrogen production with platinum colloid as a catalyst using the visible light-induced photosensitization of Mg chlorophyll-a (Mg Chl-a) from higher green plant or artificial chlorophyll analog, zinc porphyrin, are introduced. PMID:19325796

Structural and surface properties of CuO-ZnO-Cr{sub 2}O{sub 3} catalysts and their relationship with selectivity to higher alcohol synthesis

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

Campos-Martin, J.M.; Fierro, J.L.G.; Guerrero-Ruiz, A.

1995-10-01

A series of copper-zinc-chromium catalysts of different compositions and calcination temperatures has been prepared, characterized by several techniques (BET specific surface area, XRD, gravimetric TPR, TPD-CO, and XPS), and tested under high alcohol synthesis (HAS) conditions. CO hydrogenation was carried out at reaction temperatures of 523-598 K and 50 bar total pressure. The influence of catalyst composition, calcination temperature, and surface characteristics on the HAS selectivity was studied. The optimum HAS yields were found in the low Cr content region, but chromium was needed. Although chromium oxide does not seem to be involved in the catalytic site, its presence inmore » the catalyst composition is essential, owing to the larger specific surfaces and catalyst stability obtained at the highest reaction temperatures. For low Cr content composition, the temperature-programmed reduction (TPR) profiles were shifted to higher temperatures and simultaneously larger CO{sub 2} amounts were found in the temperature-programmed desorption profiles of adsorbed CO (TPD-CO). Photoelectron spectra (XPS) revealed that the oxidation state of copper is Cu{sup 2+} in the calcined catalysts and Cu{sup O} in the reduced ones; Cu{sup +} was only stabilized in a CuCr{sub 2}O{sub 4} spinel in the Cr-rich catalysts. These features derived from catalyst characterization are discussed in the framework of the catalytic behaviour for HAS synthesis. 53 refs., 7 figs., 4 tabs.« less

Typology of mafic-ultramafic complexes in Hoggar, Algeria: Implications for PGE, chromite and base-metal sulphide mineralisation

NASA Astrophysics Data System (ADS)

Augé, Thierry; Joubert, Marc; Bailly, Laurent

2012-02-01

With the aims to bring new information about the typology and mineral potential of mafic-ultramafic complexes of the Hoggar, detailed petrological and chemical characterisation were performed on serpentinite bands and layered intrusions. The serpentinite bands locally contain pods, layers and disseminations of chromite showing all the characteristics (mode of occurrence, composition, nature and composition of silicate inclusions, etc.) of an "ophiolite" chromite. Some chromite concentrations in the serpentinite bands also contain inclusions of platinum-group minerals (described for the first time in the Hoggar) such as ruarsite (RuAsS), an Os, Ru, Ir alloy, and complex Os, Ir, Ru sulfarsenides and arsenides. The serpentinite probably corresponds to remnants of oceanic lithosphere—more specifically from the upper part of the mantle sequence, generally where chromitite pods are most abundant, and the basal part of the cumulate series with stratiform chromite concentrations—and marks suture zones; the rest of the oceanic crust has not been preserved. Considering the typology of the serpentinites bands, their potential for precious- and base-metals is suspected to be low. Of the two layered mafic-ultramafic intrusions that were studied, the In Tedeini intrusion has a wehrlite core intruded by olivine gabbronorite and surrounded by an olivine gabbro aureole; three orthocumulate units, containing disseminated magmatic base-metal sulphides and with a plagioclase composition varying around An 58.1 and An 63.3, that could have been derived from a single magma. The East Laouni intrusion has a basal unit of olivine gabbronorite with specific silicate oxide intergrowths, and an upper unit of more differentiated gabbro, both units containing disseminated magmatic Ni-Cu sulphides indicative of early sulphide immiscibility; the mineral composition of these two cumulate units indicates that they also could have been derived from a single magmatic episode. The characteristic of the two intrusions appears very favourable for the presence of a significant Ni-Cu-(PGE) sulphide mineralisation.

Stages in molecular beam epitaxy growth of GaAs nanowires studied by x-ray diffraction.

PubMed

Mariager, Simon O; Lauridsen, Søren L; Sørensen, Claus B; Dohn, Asmus; Willmott, Phillip R; Nygård, Jesper; Feidenhans'l, Robert

2010-03-19

GaAs nanowires were grown by molecular beam epitaxy and studied by glancing-angle x-ray diffraction during five different stages of the growth process. An entire forest of randomly positioned epitaxial nanowires was sampled simultaneously and a large variation in the Au-Ga catalyst was found. Au, AuGa, AuGa(2) and the hexagonal beta phase were all identified in several orientations and in similar amounts. The nanowires are shown to consist of regular zinc blende crystal, its twin and the hexagonal wurtzite. The evolution of the various Au-Ga catalysts and the development in the twin to the wurtzite abundance ratio indicate that the Au catalyst is saturated upon initiation of growth leading to an increased amount of wurtzite structure in the wires. A specular x-ray scan identifies the various Au-Ga alloys, three Au lattice constants and a rough interface between nanowires and catalyst. Reciprocal space maps were obtained around Au Bragg points and show the development of the Au catalyst from a distribution largely oriented with respect to the lattice to a non-uniform distribution with several well-defined lattice constants.

Ag-Cu nanoalloyed film as a high-performance cathode electrocatalytic material for zinc-air battery

NASA Astrophysics Data System (ADS)

Lei, Yimin; Chen, Fuyi; Jin, Yachao; Liu, Zongwen

2015-04-01

A novel Ag50Cu50 film electrocatalyst for oxygen reduction reaction (ORR) was prepared by pulsed laser deposition (PLD) method. The electrocatalyst actually is Ag-Cu alloyed nanoparticles embedded in amorphous Cu film, based on transmission electron microscopy (TEM) characterization. The rotating disk electrode (RDE) measurements provide evidence that the ORR proceed via a four-electron pathway on the electrocatalysts in alkaline solution. And it is much more efficient than pure Ag catalyst. The catalytic layer has maximum power density of 67 mW cm-2 and an acceptable cell voltage at 0.863 V when current densities increased up to 100 mA cm-2 in the Ag50Cu50-based primary zinc-air battery. The resulting rechargeable zinc-air battery exhibits low charge-discharge voltage polarization of 1.1 V at 20 mAcm-2 and high durability over 100 cycles in natural air.

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

Rabo, J.A.

Of the twelve catalysts tested in this quarter, none showed any significant effectiveness. The principal value of the quarter's work has been in whatever guidance may be derived from the negative findings, especially what they may tell us about the design parameters of a good catalyst. The most effective catalyst developed to date, Catalyst 6 (Run 11677-11) of the Third Annual Report, was composed of Co/Th/X/sub 4//UCC-103+UCC-101. This quarter's findings suggest three specifics of that catalyst which should prove useful in shaping further work. First, that the X/sub 4/ component is probably a key contributor to stability. Second, that themore » source of the X/sub 4/ is important; the X/sub 4/ must be free of known catalyst poisons, or have those poisons completely removed without impairing the cobalt Fischer-Tropsch activity. And third, that extra, physically mixed UCC-101 apparently contributes little if anything to stability. Eight of the twelve runs were devoted to tests of water gas shift catalysts in different formulations and methods of preparation, and under different operating conditions. Many attempts have been made to develop a copper-zinc water gas shift catalyst which will function effectively in combination with a Fischer-Tropsch catalyst and at the Fischer-Tropsch operating temperatures. The failure of these trials to date suggests that the water gas shift components may be deactivated by intermediates or products of Fischer-Tropsch synthesis. Yet attempts to isolate the water gas shift component from the Fischer-Tropsch products have been equally fruitless. 177 figs., 30 tabs.« less

Ilmenite exsolution schemes in Apollo-17 high-Ti basalts

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

Vaniman, D.; Heiken, G.; Muhich, T.

1990-01-01

Combined electron microprobe and scanning electron microscope (SEM) x-ray image analyses are used to obtain semiquantitative data on the relations between ilmenite grains and their exsolved chromite and rutile. Comparisons of these data for ilmenites in four Apollo-17 high-Ti basalts with a database of electron microprobe analyses from the literature indicates that Cr expulsion from ilmenite can be as important as Fe{sup 2+} reduction in causing subsolidus exsolution of chromite and rutile from ilmenite. 12 refs., 4 figs., 5 tabs.

Structure and function of real catalysts

NASA Astrophysics Data System (ADS)

Klier, K.

1984-11-01

This paper addresses issues such as the relation between the physical and chemical nature of active centers, activation of reactant molecules, mechanisms of catalytic reactions and distribution of promoters in real catalysts which are invariably multicomponent multiphase systems. Interactions among the catalyst components and phases often result in the formation of compounds and defects that do not exist in the separate components. Although such interactions give rise to a great variety of morphologic, chemical, and electronic properties of the real catalysts, they can be controlled, mostly by careful preparation and doping procedures, to the degree that the catalyst displays reproducible activity and selectivity. Most of the examples given in this paper are based on the results from the author's laboratory concerning the activity and selectivity of copper-based catalysts for the hydrogenation of carbon monoxide and carbon dioxide, the water gas shift reaction, and some reactions of amines. Evidence is presented for the interactions between the copper and zinc oxide then analyzed in terms of defect equilibria using models and constants partially known from the literature and adapted for the present system. It is shown on the basis of boundary layer theory for small particles that charge transfer between copper metal particles, also present in the system, and the zinc oxide phase is insignificant. On the other hand, electron equilibria between the solute copper species and the zinc oxide matrix are dictated primarily by intrinsic ionization Cu 0 → Cu + + e - and oxygen vacancy formation. Optical absorption spectroscopy strongly corroborates the theoretical contention that a significant portion of the copper is in electron deficient state, and there is some evidence based on Auger spectroscopy for the presence of Cu + species on the catalyst surface. It is reiterated, as has been proposed before in our earlier work, that these copper species activate substrates such as carbon monoxide or unsaturated hydrocarbons through back-bonding of the copper d-orbitals into the π ∗ orbitals of the substrates. In a paper by D.L. Roberts and G.L. Griffin at this Symposium, additional evidence is presented that the same finely dispersed Cu species are the chemisorption and activation sites for hydrogen. Some significant mechanistic features of carbon monoxide hydrogenation are demonstrated by the enhancement of methanol synthesis rates and carbon-carbon bond formation in the presence of alkali promoters. The nature and concentration of the alkali ions on the catalyst surface determine the outcome of the carbon monoxide hydrogenations in the following way: (i) of all the alkali and alkaline earth promoters, cesium displays the most pronounced effects; (ii) at high temperatures and low hydrogen-to-carbon monoxide ratios, maximum amount of n-propanol and 2-methyl-propanol is observed in the product over the Cs/Cu/ZnO catalysts, consistent with the function of the alkali as base catalysts in aldol condensation of aldehydic or enolic surface intermediates; (iii) at low temperatures and high hydrogen-to-carbon monoxide ratios, cesium enhances methanol synthesis as well as water gas shift rates in water- and CO 2-free synthesis gas, retards the methanol synthesis rate in synthesis gas containing intermediate amounts of water, primarily due to loss of surface area upon cesium doping, and again accelerates the synthesis in water-rich synthesis gas. These latter effects point to a mechanism in which the rate of formation of surface formate is enhanced by cesium in water-free synthesis gas and a rapid removal of surface hydroxyls free sites that activate hydrogen in water-rich synthesis gas. The role of Group VIII metals as promoters of the Cu/ZnO catalysts for low alcohol and hydrocarbon synthesis is represented by the effects of small additions of iron. Product composition is intermediate between that in methanol and Fischer-Tropsch syntheses, with significant amount of low alcohols formed. Characterization of the 1%Fe/Cu/ZnO catalyst by analytical electron microscopy reveals two forms of iron, a fine dispersion in the Cu/ZnO catalyst and metallic particles, suggesting that the alcohol and hydrocarbon products are formed over two different parts of the catalyst. In the concluding remarks it is contended that in many systems the catalytic activity and selectivity is primarily controlled by chemical entities, defects with respect to the pure components, that are induced and stabilized by solid state reactions involving a significant part of the bulk of the catalyst particles. As the various spectroscopic techniques as well as the tools of high resolution and analytical electron microscopy are used in an increasingly refined way for the analysis of real catalysts, it seems inevitable that the traditional art of catalyst preparation will take advantage of the new understanding of catalyst structure and will become a branch of materials science firmly footed in solid state chemistry and physics.

Response to Comment on “Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts”

DOE PAGES

Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G.; ...

2017-09-01

In their Comment on our recent paper, Nakamura et al. argue that our x-ray photoelectron spectroscopy (XPS) analysis was affected by the presence of formate species on the catalyst surface. This argument is not valid because the reactant gases were evacuated at temperatures from 525 to 575 kelvin, conditions under which formate is not stable on the catalyst surface. An analysis of the XPS results obtained after exposing zinc oxide/copper (111) [ZnO/Cu(111)] surfaces to hydrogen (H 2) and mixtures of carbon dioxide (CO 2)/H 2 show an absence of carbon (C) 1s signal, no asymmetries in the oxygen (O) 1smore » peak, and a Zn:O intensity close to 1:1. Thus and finally, the most active phase of these catalysts contained a ZnO-Cu interface.« less

Diatom frustules decorated with zinc oxide nanoparticles for enhanced optical properties

NASA Astrophysics Data System (ADS)

Lamastra, F. R.; Grilli, M. L.; Leahu, G.; Belardini, A.; Li Voti, R.; Sibilia, C.; Salvatori, D.; Cacciotti, I.; Nanni, F.

2017-09-01

Zinc oxide (ZnO) nanoparticles were synthesized on diatomite (DE) surface by a low temperature sol gel technique, starting from zinc acetate dihydrate (Zn(CH3COO)2 · 2H2O) solution in water/ethyl alcohol, in presence of triethanolamine (TEA) with functions of Zn2+ chelating agent, catalyst and mediator of nanoparticle growth on DE surface. Microstructural features were investigated by field emission scanning electron microscopy and x-ray diffraction. ZnO crystalline nanoparticles, well distributed both on the surface and into the porous architecture of diatomite, were obtained just after the synthesis carried out at 80 °C without the need of calcination treatments. The optical properties of ZnO/DE hybrid powders were measured for the first time by means of photoacoustic spectroscopy (PAS). A new method to retrieve both the optical absorption and scattering coefficients from PAS is here discussed for powder aggregates. The fingerprint of the zinc oxide nanoparticles has been highlighted in the Mie scattering resonance in the UV-Vis range, and in the enhancement of the optical absorption with respect to diatomite.

Problems of Determining the Content of Cr(VI) in Raw Materials and Materials Containing Chromite Ore.

PubMed

Stec, Katarzyna

2017-11-02

Materials made with chromite ore are widely applied in the industry metallurgy as well as in the foundry industry. The oxidation number of chromium in these materials is both (III) and (VI). Currently there are no procedures allowing proper determination of chrome in chromite ores and ore-containing materials. The analytical methods applied, which are dedicated to a very narrow range of materials, e.g., cement, and cannot be applied in the case of materials which, apart from trace amounts of Cr(VI), contain mainly compounds of Cr(III), Fe(III) as well as trace compounds of Cu(II), Ni(II) and V(V). In the work particular attention has been paid to the preparation of test samples and creating measurement conditions in which interferences from Cr(III) and Fe(III) spectral lines could be minimized. Two separate instrumental measurement techniques have been applied: Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP AES) and the spectrophotometric method using diphenylcarbazide.

Optimization of Lactide synthesis from Lactic Acid in biorefinery of palm oil waste using Response Surface Methodology

NASA Astrophysics Data System (ADS)

Gozan, M.; Kamilah, F.; Whulanza, Y.; Rahmayetty

2018-03-01

Ring open polymerization is one of the production polylactic acid by formation of monomer before. Lactic acid is converted into lactide in two stages, polycondensation and depolymerization. Yield lactide will determine the molecular weight which produced. This study is to optimize the lactide production from lactic acid 90% by the variations of temperature (190-220°C), vacuum pressure (5-15 cmHg), and zinc acetate catalyst (0,3-0,6% w/w). As the temperature, vacuum pressure, and catalyst is increased, lactide that is produced also increases. Optimum condition of lactide production is obtained by Response surface methodology at the temperature 220°C, catalyst 0,45%w/w, and 10 cmHg in vacuum pressure. Equation or model from this study by using RSM is yield lactide = -258,75 + 7,79A + 2,90B + 3,51C + 0,48AB - 0,06AC – 3,97x10-3BC – 105,42A2 – 7,17B2– 0,10C2(A:catalyst; B:temperature; C:pressure).

Functionalization of multi-walled carbon nanotubes with iron phthalocyanine via a liquid chemical reaction for oxygen reduction in alkaline media

NASA Astrophysics Data System (ADS)

Yan, Xiaomei; Xu, Xiao; Liu, Qin; Guo, Jia; Kang, Longtian; Yao, Jiannian

2018-06-01

Iron single-atom catalyst in form of iron-nitrogen-carbon structure possesses the excellent catalytic activity in various chemical reactions. However, exploring a sustainable and stable single-atom metal catalyst still faces a great challenge due to low yield and complicated synthesis. Here, we report a functional multi-wall carbon nanotubes modified with iron phthalocyanine molecules via a liquid chemical reaction and realize the performance of similar single-atom catalysis for oxygen reduction reaction. A serial of characterizations strongly imply the structure change of iron phthalocyanine molecule and its close recombination with multi-wall carbon nanotubes, which are in favor of ORR catalysis. Compared to commercial platinum-carbon catalyst, composites exhibit superior activity for oxygen reduction reaction with higher half-wave potential (0.86 V), lower Tafel slope (38 mV dec-1), higher limiting current density and excellent electrochemical stability. The corresponding Zinc-air battery also presents higher maximum power density and discharge stability. Therefore, these findings provide a facile route to synthesize a highly efficient non-precious metal carbon-based catalyst.

The leguminous species Anthyllis vulneraria as a Zn-hyperaccumulator and eco-Zn catalyst resources.

PubMed

Grison, Claire M; Mazel, Marine; Sellini, Amandine; Escande, Vincent; Biton, Jacques; Grison, Claude

2015-04-01

Anthyllis vulneraria was highlighted here as a Zn-hyperaccumulator for the development of a pilot phytoextraction process in the mine site of Les Avinières in the district of Saint-Laurent-Le-Minier. A. vulneraria appeared to hyperaccumulate the highest concentration of Zn in shoots with a better metal selectivity relative to Cd and Pb than the reference Zn-hyperaccumulator Noccea caerulescens. A bigger biomass production associated to a higher Zn concentration conducted A. vulneraria to the highest total zinc gain per hectare per year. As a legume, A. vulneraria was infected by rhizobia symbionts. Inoculation of A. vulneraria seeds showed a positive impact on Zn hyperaccumulation. A large-scale culture process of symbiotic rhizobia of A. vulneraria was investigated and optimized to allow large-scale inoculation process. Contaminated shoots of A. vulneraria were not considered as wastes and were recovered as Eco-Zn catalyst in particular, examples of organic synthesis, electrophilic aromatic substitution. Eco-Zn catalyst was much more efficient than conventional catalysts and allowed greener chemical processes.

Zinc-oxide-silica-silver nanocomposite: Unique one-pot synthesis and enhanced catalytic and anti-bacterial performance.

PubMed

Kokate, Mangesh; Garadkar, Kalyanrao; Gole, Anand

2016-12-01

We describe herein a unique approach to synthesize zinc oxide-silica-silver (ZnO-SiO2-Ag) nanocomposite, in a simple, one-pot process. The typical process for ZnO synthesis by alkaline precipitation of zinc salts has been tweaked to replace alkali by alkaline sodium silicate. The free acid from zinc salts helps in the synthesis of silica nanoparticles, whereas the alkalinity of sodium silicate precipitates the zinc salts. Addition of silver ions into the reaction pot prior to addition of sodium silicate, and subsequent reduction by borohydride, gives additional functionality of metallic centres for catalytic applications. The synthesis strategy is based on our recent work typically involving acid-base type of cross-reactions and demonstrates a novel strategy to synthesize nanocomposites in a one-pot approach. Each component in the composite offers a unique feature. ZnO besides displaying mild catalytic and anti-bacterial behaviour is an excellent and a cheap 3-D support for heterogeneous catalysis. Silver nanoparticles enhance the catalytic & anti-bacterial properties of ZnO. Silica is an important part of the composite; which not only "glues" the two nanoparticles thereby stabilizing the nanocomposite, but also significantly enhances the surface area of the composite; which is an attractive feature of any catalyst composite. The nanocomposite is found to show excellent catalytic performance with very high turnover frequencies (TOFs) when studied for catalytic reduction of Rhodamine B (RhB) and 4-Nitrophenol (4-NP). Additionally, the composite has been tested for its anti-bacterial properties on three different bacterial strains i.e. E. coli, B. Cereus and Bacillus firmus. The mechanism for enhancement of catalytic performance has been probed by understanding the role of silica in offering accessibility to the catalyst via its porous high surface area network. The nanocomposite has been characterized by a host of different analytical techniques. The uniqueness of our product and process stems from the novel synthesis strategy, the choice and combination of the three moieties, increased surface area offered by silica, and cost effectiveness, thereby making our product and process commercially viable and sustainable for industrial applications. Copyright © 2016 Elsevier Inc. All rights reserved.

The effects of starting materials in the synthesis of (Ga(1-x)Znx)(N(1-x)O(x)) solid solution on its photocatalytic activity for overall water splitting under visible light.

PubMed

Hisatomi, Takashi; Maeda, Kazuhiko; Lu, Daling; Domen, Kazunari

2009-01-01

The influence of starting materials on the physicochemical and photocatalytic properties of (Ga(1-x)Zn(x))(N(1-x)O(x)) were investigated in an attempt to optimize the preparation conditions. The catalyst was successfully prepared by nitriding a starting mixture of ZnO and Ga2O3. A mixture of metallic zinc and GaN, however, did not afford the desired compound. The crystallinity, surface area, composition, and absorption characteristics of the resultant (Ga(1-x)Zn(x))(N(1-x)O(x)) solid solution are found to be dependent on the morphology of ZnO but largely insensitive to the choice of Ga2O3 polymorph. The use of coarser-grained ZnO results in a coarser-grained catalyst with elevated zinc and oxygen content and reduced uniformity in composition and crystallinity. The results demonstrate the importance of selecting appropriate ZnO and Ga2O3 starting materials for maximizing the photocatalytic activity of (Ga(1-x)Zn(x))(N(1-x)O(x)) for overall water splitting under visible light.

Synthesis and structures of bis-ligated zinc complexes supported by tridentate ketoimines that initiate L-lactide polymerization.

PubMed

Gerling, Kimberly A; Rezayee, Nomaan M; Rheingold, Arnold L; Green, David B; Fritsch, Joseph M

2014-11-21

Eight bis-ligated, homoleptic, zinc complexes were synthesized through the reaction of NNO Schiff base ketoimines bearing varying substituents with diethyl zinc in an inert atmosphere glovebox at room temperature and isolated in 62-95% yield. The complexes were characterized with (1)H, (13)C, and (19)F nuclear magnetic resonance spectroscopy, absorbance spectroscopy, high resolution mass spectrometry, elemental analysis, and single crystal X-ray crystallography. The complexes were shown to adopt distorted octahedral coordination geometry around zinc. The (1)H and (19)F NMR spectra of complexes 1-7 showed stable zinc coordination at 300 K while the effect of steric encumbrance and two trifluoromethyl groups in complex 8 was investigated with variable temperature NMR. The bis-ligated zinc complexes were effective initiators for the ring opening polymerization of L-lactide into poly-L-lactic acid (PLLA). With [L-lac]/[Zn complex] = 50, the bis-ligated zinc complexes yielded percentage conversion of 14-98% with polymerization times varying from 15-1440 min, where the longest reaction times were required when two trifluoromethyl groups were present. The addition of 4-fluorophenol co-catalyst resulted in up to a 5-fold increase in the percentage conversion in toluene solution and up to a 14-fold increase in bulk melt polymerization with reductions in the poly-dispersity index values for the isolated PLLA. Addition of 4-fluorophenol to complex 1 was studied with (1)H and (19)F NMR and appeared to yield an in situ generated zinc alkoxide complex.

Elucidation of structural, vibrational and dielectric properties of transition metal (Co2+) doped spinel Mg-Zn chromites

NASA Astrophysics Data System (ADS)

Choudhary, Pankaj; Varshney, Dinesh

2018-05-01

Co2+ doped Mg-Zn spinel chromite compositions Mg0.5Zn0.5-xCoxCr2O4 (0.0 ≤ x ≤ 0.5) have been synthesized by the high-temperature solid state method. Synchrotron and X-ray diffraction (XRD) studies show single-phase crystalline nature. The structural analysis is validated by Rietveld refinement confirms the cubic structure with space group Fd3m. Crystallite size is estimated from Synchrotron XRD which was found to be 30-34 nm. Energy dispersive analysis confirms stoichiometric Mg0.5Zn0.5-xCoxCr2O4 composition. Average crystallite size distribution is estimated from imaging software (Image - J) of SEM is in the range of 100-250 nm. Raman spectroscopy reveals four active phonon modes, and a pronounced red shift is due to enhanced Co2+ concentration. Increased Co2+ concentration in Mg-Zn chromites shows a prominent narrowing of band gap from 3.46 to 2.97 eV. The dielectric response is attributed to the interfacial polarization, and the electrical modulus study supports non-Debye type of dielectric relaxation. Ohmic junctions (minimum potential drop) at electrode interface are active at lower levels of doping (x < 0.2) give rise to a low-frequency semicircle as evidenced from the complex impedance analysis. The low dielectric loss and high ac conductivity of Co2+ doped Mg-Zn spinel chromites are suitable for power transformer applications at high frequencies.

Biodegradation of the metallic carcinogen hexavalent chromium Cr(VI) by an indigenously isolated bacterial strain

PubMed Central

Mishra, Susmita

2010-01-01

Background: Hexavalent chromium [Cr(VI)], a potential mutagen and carcinogen, is regularly introduced into the environment through diverse anthropogenic activities, including electroplating, leather tanning, and pigment manufacturing. Human exposure to this toxic metal ion not only causes potential human health hazards but also affects other life forms. The World Health Organization, the International Agency for Research on Cancer, and the Environmental Protection Agency have determined that Cr(VI) compounds are known human carcinogens. The Sukinda valley in Jajpur District, Orissa, is known for its deposit of chromite ore, producing nearly 98% of the chromite ore in India and one of the prime open cast chromite ore mines in the world (CES, Orissa Newsletter). Materials and Methods: Our investigation involved microbial remediation of Cr(VI) without producing any byproduct. Bacterial cultures tolerating high concentrations of Cr were isolated from the soil sample collected from the chromite-contaminated sites of Sukinda, and their bioaccumulation properties were investigated. Strains capable of growing at 250 mg/L Cr(VI) were considered as Cr resistant. Results: The experimental investigation showed the maximum specific Cr uptake at pH 7 and temperature 30°C. At about 50 mg/L initial Cr(VI) concentrations, uptake of the selected potential strain exceeded 98% within 12 h of incubation. The bacterial isolate was identified by 16S rRNA sequencing as Brevebacterium casei. Conclusion: Results indicated promising approach for microbial remediation of effluents containing elevated levels of Cr(VI). PMID:20976016

Chemical scavenging of post-consumed clothes.

PubMed

Barot, Amit A; Sinha, Vijay Kumar

2015-12-01

Aiming toward the rectification of fiber grade PET waste accumulation as well as recycling and providing a technically viable route leading to preservation of the natural resources and environment, the post consumed polyester clothes were chemically recycled. Post consumed polyester clothes were recycled into bis(2-hydroxyethyl) terephthalate (BHET) monomer in the presence of ethylene glycol as depolymerising agent and zinc acetate as catalyst. Depolymerized product was characterized by chemical as well as analytical techniques. The fiber grade PET was eventually converted into BHET monomer with nearly 90% yield by employing 1% catalyst concentration and at optimum temperature of 180°C without mechanical input of stirring condition. Copyright © 2015 Elsevier Ltd. All rights reserved.

Seed/catalyst-free growth of zinc oxide nanostructures on multilayer graphene by thermal evaporation

PubMed Central

2014-01-01

We report the seed/catalyst-free growth of ZnO on multilayer graphene by thermal evaporation of Zn in the presence of O2 gas. The effects of substrate temperatures were studied. The changes of morphologies were very significant where the grown ZnO structures show three different structures, i.e., nanoclusters, nanorods, and thin films at 600°C, 800°C, and 1,000°C, respectively. High-density vertically aligned ZnO nanorods comparable to other methods were obtained. A growth mechanism was proposed based on the obtained results. The ZnO/graphene hybrid structure provides several potential applications in electronics and optoelectronics. PMID:24533793

Process Developed for Generating Ceramic Interconnects With Low Sintering Temperatures for Solid Oxide Fuel Cells

NASA Technical Reports Server (NTRS)

Zhong, Zhi-Min; Goldsby, Jon C.

2005-01-01

Solid oxide fuel cells (SOFCs) have been considered as premium future power generation devices because they have demonstrated high energy-conversion efficiency, high power density, and extremely low pollution, and have the flexibility of using hydrocarbon fuel. The Solid-State Energy Conversion Alliance (SECA) initiative, supported by the U.S. Department of Energy and private industries, is leading the development and commercialization of SOFCs for low-cost stationary and automotive markets. The targeted power density for the initiative is rather low, so that the SECA SOFC can be operated at a relatively low temperature (approx. 700 C) and inexpensive metallic interconnects can be utilized in the SOFC stack. As only NASA can, the agency is investigating SOFCs for aerospace applications. Considerable high power density is required for the applications. As a result, the NASA SOFC will be operated at a high temperature (approx. 900 C) and ceramic interconnects will be employed. Lanthanum chromite-based materials have emerged as a leading candidate for the ceramic interconnects. The interconnects are expected to co-sinter with zirconia electrolyte to mitigate the interface electric resistance and to simplify the processing procedure. Lanthanum chromites made by the traditional method are sintered at 1500 C or above. They react with zirconia electrolytes (which typically sinter between 1300 and 1400 C) at the sintering temperature of lanthanum chromites. It has been envisioned that lanthanum chromites with lower sintering temperatures can be co-fired with zirconia electrolyte. Nonstoichiometric lanthanum chromites can be sintered at lower temperatures, but they are unstable and react with zirconia electrolyte during co-sintering. NASA Glenn Research Center s Ceramics Branch investigated a glycine nitrate process to generate fine powder of the lanthanum-chromite-based materials. By simultaneously doping calcium on the lanthanum site, and cobalt and aluminum on the chromium site, we could sinter the materials below 1400 C. The doping concentrations were adjusted so that the thermal expansion coefficient matched that of the zirconia electrolyte. Also, the investigation was focused on stoichiometric compositions so that the materials would have better stability. Co-sintering and chemical compatibility with zirconia electrolyte were examined by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy (line scanning and dot map). The results showed that the materials bond well, but do not react, with zirconia electrolyte. The electric conductivity of the materials measured at 900 C in air was about 20 S/cm.

Dielectric properties and activation behavior of gadolinium doped nanocrystalline yttrium chromite

NASA Astrophysics Data System (ADS)

Sinha, R.; Basu, S.; Meikap, A. K.

2018-04-01

Gadolinium doped Yttrium Chromite nanoparticles are synthesized following sol-gel method. The formation of the nanoparticles are confirmed by XRD and TEM measurements. Dielectric permittivity and dielectric loss are estimated within the temperature range 298K to 523K and in the frequency range 20 Hz to 1 MHz. Dielectric permittivity follows the power law ɛ'(f) ∝ Tm. It is observed that the temperature exponent m increases with the decreasing frequency. The temperature variation of resistivity shows that the samples have semiconducting behavior. The activation energy is also measured.

Biofabricated zinc oxide nanoparticles coated with phycomolecules as novel micronutrient catalysts for stimulating plant growth of cotton

NASA Astrophysics Data System (ADS)

Priyanka, N.; Venkatachalam, P.

2016-12-01

This study describes the bioengineering of phycomolecule-coated zinc oxide nanoparticles (ZnO NPs) as a novel type of plant-growth-enhancing micronutrient catalyst aimed at increasing crop productivity. The impact of natural engineered phycomolecule-loaded ZnO NPs on plant growth characteristics and biochemical changes in Gossypium hirsutum L. plants was investigated after 21 days of exposure to a wide range of concentrations (0, 25, 50, 75, 100, and 200 mg l-l). ZnO NP exposure significantly enhanced growth and biomass by 125.4% and 132.8%, respectively, in the treated plants compared to the untreated control. Interestingly, photosynthetic pigments, namely, chlorophyll a (134.7%), chlorophyll b (132.6%), carotenoids (160.1%), and total soluble protein contents (165.4%) increased significantly, but the level of malondialdehyde (MDA) content (73.8%) decreased in the ZnO-NP-exposed plants compared to the control. The results showed that there were significant increases in superoxide dismutase (SOD, 267.8%) and peroxidase (POX, 174.5%) enzyme activity, whereas decreased catalase (CAT, 83.2%) activity was recorded in the NP-treated plants compared to the control. ZnO NP treatment did not show distinct alterations (the presence or absence of DNA) in a random amplified polymorphic DNA (RAPD) banding pattern. These results suggest that bioengineered ZnO NPs coated with natural phycochemicals display different biochemical effects associated with enhanced growth and biomass in G. hirsutum. Our results imply that ZnO NPs have tremendous potential in their use as an effective plant-growth-promoting micronutrient catalyst in agriculture.

Photosensitized H2 Production Using a Zinc Porphyrin-Substituted Protein, Platinum Nanoparticles, and Ascorbate with No Electron Relay: Participation of Good's Buffers.

PubMed

Clark, Emily R; Kurtz, Donald M

2017-04-17

Development of efficient light-driven splitting of water, 2H 2 O → 2H 2 + O 2 , often attempts to optimize photosensitization of the reductive and oxidative half-reactions individually. Numerous homogeneous and heterogeneous systems have been developed for photochemical stimulation of the reductive half reaction, 2H + + 2e - → H 2 . These systems generally consist of various combinations of a H + reduction catalyst, a photosensitizer (PS), and a "sacrificial" electron donor. Zinc(II)-porphyrins (ZnPs) have frequently been used as PSs for H 2 generation, but they are subject to various self-quenching processes in aqueous solutions. Colloidal platinum in nanoparticle form (Pt NP) is a classical H + reduction catalyst using ZnP photosensitizers, but efficient photosensitized H 2 generation requires an electron relay molecule between ZnP and Pt NP. The present report describes an aqueous system for visible (white) light-sensitized generation of H 2 using a protein-embedded Zn(II)-protoporphyrin IX as PS and Pt NP as H + reduction catalyst without an added electron relay. This system operated efficiently in piperazino- and morpholino-alkylsulfonic acid (Good's buffers), which served as sacrificial electron donors. The system also required ascorbate at relatively modest concentrations, which stabilized the Zn(II)-protoporphyrin IX against photodegradation. In the absence of an electron relay molecule, the photosensitized H 2 generation must involve formation of at least a transient complex between a protein-embedded Zn(II)-protoporphyrin IX species and Pt NP.

Mechanistic Studies of Hafnium-Pyridyl Amido-Catalyzed 1-Octene Polymerization and Chain Transfer Using Quench-Labeling Methods.

PubMed

Cueny, Eric S; Johnson, Heather C; Anding, Bernie J; Landis, Clark R

2017-08-30

Chromophore quench-labeling applied to 1-octene polymerization as catalyzed by hafnium-pyridyl amido precursors enables quantification of the amount of active catalyst and observation of the molecular weight distribution (MWD) of Hf-bound polymers via UV-GPC analysis. Comparison of the UV-detected MWD with the MWD of the "bulk" (all polymers, from RI-GPC analysis) provides important mechanistic information. The time evolution of the dual-detection GPC data, concentration of active catalyst, and monomer consumption suggests optimal activation conditions for the Hf pre-catalyst in the presence of the activator [Ph 3 C][B(C 6 F 5 ) 4 ]. The chromophore quench-labeling agents do not react with the chain-transfer agent ZnEt 2 under the reaction conditions. Thus, Hf-bound polymeryls are selectively labeled in the presence of zinc-polymeryls. Quench-labeling studies in the presence of ZnEt 2 reveal that ZnEt 2 does not influence the rate of propagation at the Hf center, and chain transfer of Hf-bound polymers to ZnEt 2 is fast and quasi-irreversible. The quench-label techniques represent a means to study commercial polymerization catalysts that operate with high efficiency at low catalyst concentrations without the need for specialized equipment.

IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer

DOE PAGES

Schumann, Julia; Kröhnert, Jutta; Frei, Elias; ...

2017-08-28

Carbon monoxide was applied as probe molecule to compare the surface of a ZnO-containing (Cu/ZnO:Al) and a ZnO-free (Cu/MgO) methanol synthesis catalyst (copper content 70 atomic %) after reduction in hydrogen at 523 K by DRIFT spectroscopy. Nano-structured, mainly metallic copper was detected on the surface of the Cu/MgO catalyst. In contrast, the high energy of the main peak in the spectrum of CO adsorbed on reduced Cu/ZnO:Al (2125 cm -1) proves that metallic copper is largely absent on the surface of this catalyst. The band is assigned to Zn δ+–CO. The presence of not completely reduced Cu δ+–CO speciesmore » cannot be excluded. The results are interpreted in terms of a partial coverage of the copper nano-particles in the Cu/ZnO:Al catalyst by a thin layer of metastable, defective zinc oxide. Minor contributions in the spectrum at 2090 and 2112 cm -1 due to nano-structured Cu 0–CO and CO adsorbed on highly defective Cu 0, respectively, indicate that the coverage of metallic copper is not complete.« less

IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer

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

Schumann, Julia; Kröhnert, Jutta; Frei, Elias

Carbon monoxide was applied as probe molecule to compare the surface of a ZnO-containing (Cu/ZnO:Al) and a ZnO-free (Cu/MgO) methanol synthesis catalyst (copper content 70 atomic %) after reduction in hydrogen at 523 K by DRIFT spectroscopy. Nano-structured, mainly metallic copper was detected on the surface of the Cu/MgO catalyst. In contrast, the high energy of the main peak in the spectrum of CO adsorbed on reduced Cu/ZnO:Al (2125 cm -1) proves that metallic copper is largely absent on the surface of this catalyst. The band is assigned to Zn δ+–CO. The presence of not completely reduced Cu δ+–CO speciesmore » cannot be excluded. The results are interpreted in terms of a partial coverage of the copper nano-particles in the Cu/ZnO:Al catalyst by a thin layer of metastable, defective zinc oxide. Minor contributions in the spectrum at 2090 and 2112 cm -1 due to nano-structured Cu 0–CO and CO adsorbed on highly defective Cu 0, respectively, indicate that the coverage of metallic copper is not complete.« less

Zn-BTC MOFs with active metal sites synthesized via a structure-directing approach for highly efficient carbon conversion.

PubMed

Huang, Xianqiang; Chen, Yifa; Lin, Zhengguo; Ren, Xiaoqian; Song, Yuna; Xu, Zhenzhu; Dong, Xinmei; Li, Xingguo; Hu, Changwen; Wang, Bo

2014-03-11

Three zinc-trimesic acid (Zn-BTC) MOFs, BIT-101, BIT-102 and BIT-103, have been synthesized via a structure-directing strategy. Interestingly, BIT-102 and -103 exhibit extraordinary catalytic performance (up to Conv. 100% and Sele. 95.2%) in the cycloaddition of CO2 under solvent- and halogen-free conditions without any additives or co-catalysts.

Formation and modification of chromitites in the mantle

NASA Astrophysics Data System (ADS)

Arai, Shoji; Miura, Makoto

2016-11-01

Podiform chromitites have long supplied us with unrivaled information on various mantle processes, including the peridotite-magma reaction, deep-seated magmatic evolution, and mantle dynamics. The recent discovery of ultrahigh-pressure (UHP) chromitites not only sheds light on a different aspect of podiform chromitites, but also changes our understanding of the whole picture of podiform chromitite genesis. In addition, new evidence was recently presented for hydrothermal modification/formation chromite/chromitite in the mantle, which is a classical but innovative issue. In this context, we present here an urgently needed comprehensive review of podiform chromitites in the upper mantle. Wall-rock control on podiform chromitite genesis demonstrates that the peridotite-magma reaction at the upper mantle condition is an indispensable process. We may need a large system in the mantle, far larger than the size of outcrops or mining areas, to fulfill the Cr budget requirement for podiform chromitite genesis. The peridotite-magma reaction over a large area may form a melt enriched with Na and other incompatible elements, which mixes with a less evolved magma supplied from the depth to create chromite-oversaturated magma. The incompatible-element-rich magma trapped by the chromite mainly precipitates pargasite and aspidolite (Na analogue of phlogopite), which are stable under upper mantle conditions. Moderately depleted harzburgites, which contain chromite with a moderate Cr# (0.4-0.6) and a small amount of clinopyroxene, are the best reactants for the chromitite-forming reaction, and are the best hosts for podiform chromitites. Arc-type chromitites are dominant in ophiolites, but some are of the mid-ocean ridge type; chromitites may be common beneath the ocean floor, although it has not yet been explored for chromitite. The low-pressure (upper mantle) igneous chromitites were conveyed through mantle convection or subduction down to the mantle transition zone to form ultrahigh-pressure chromitites. Some of these reappear at the shallower mantle, and can coexist with newly formed low-pressure igneous chromitites. High-temperature hydrothermal fluids can dissolve and precipitate chromite, and hydrothermal chromitites (chromitites precipitated from aqueous fluids) are possibly formed within the mantle where the circulation of hydrous fluid is available, e.g., at the mantle wedge.

Respiratory health of workers exposed to low levels of chromium in stainless steel production.

PubMed Central

Huvinen, M; Uitti, J; Zitting, A; Roto, P; Virkola, K; Kuikka, P; Laippala, P; Aitio, A

1996-01-01

OBJECTIVES: To determine whether occupational exposure to chromite, trivalent chromium, or hexavalent chromium causes respiratory diseases, an excess of respiratory symptoms, a decrease in pulmonary function, or signs of pneumoconiosis among workers in an integrated chain of stainless steel production. METHODS: This cross sectional study was carried out in 1993 and the inclusion criterion was a minimum of eight years of employment in the same production department. A self administered questionnaire was collected, and spirometry, measurement of diffusing capacity, chest radiography, and laboratory tests were carried out by a mobile research unit. RESULTS: There were 221 workers in the exposure groups and 95 in the control group. The average duration of employment was 18 years. No significant differences in the odds ratios (ORs) of the symptoms were found between the exposure and the control groups. In a logistic regression analysis age and smoking significantly explained the occurrence of most of the respiratory symptoms. The smokers in the chromite group had significantly lower forced vital capacity (FVC), forced expiratory volume in one second (FEV1), and diffusing capacity than the corresponding values of the control group. The analysis of variance between study groups, smoking, and exposure time, without modelling for interactions, showed that the chromite group had lower values for FVC, FEV1, and diffusing capacity than the other groups. The occurrence of small opacities was more frequent on the chest radiographs of the workers in the chromite group. CONCLUSIONS: An average exposure time of 18 years in ferrochromium and stainless steel production and exposure to dusts containing low concentrations of hexavalent or trivalent chromium do not lead to any respiratory changes detectable by lung function tests or radiography nor to any increase in symptoms of respiratory diseases. The lung function values were lower and the occurrence of radiological findings was more frequent among the workers from the chromite mine than among the controls. The difference was partly caused by differences in age and smoking habits, but evidently also partly by higher exposures more than two decades ago or by the fibrous components of the dust. PMID:9038797

Mineral resource potential map of the Mount Eddy and Castle Crags Roadless Areas, Shasta, Siskiyou, and Trinity counties, California

USGS Publications Warehouse

Peterson, Jocelyn A.; Caress, Mary E.; Denton, David K.; Spear, James M.

1983-01-01

Although ultramafic terranes such as that underlying the Mount Eddy and Castle Crags Roadless Areas may contain chromite, nickel, platinum-group metals, cobalt, and asbestos, there are no significant identified concentrations of these resources within the roadless areas. Platinum-group metals were sought but not detected in stream-sediment concentrates, although this does not rule out their possible occurrence. Nickel and cobalt did not occur in anomalous amounts although slightly higher nickel values in the northern part of the Mount Eddy Roadless Area may indicate low-grade mineralization within small dunite bodies, if the nickel occurs in sulfide phases rather than in olivine. The region has been examined on the surface for chromite and asbestos. Although both minerals are ubiquitous there is probably only a low potential for asbestos on the basis of the small size of veins at the surface. Only a few small areas of chromite were noted in the Mount Eddy Roadless Area; without subsurface data, however, any dunite body must be considered to have potential for chromite. The geochemical data for boron, barium, and mercury plus abundant quartz veining in gabbro and hornblende diorite suggest pervasive hydrothermal alteration, which could have formed mercury or vein gold deposits. Sand and gravel deposits occur in the Castle Crags Roadless Area but they cannot compete with superior deposits closer to markets. At a borrow pit northwest of the Mount Eddy Roadless Area, sheared serpentinite is quarried for road metal; similar rock occurs in the roadless area; however, better material is more readily available elsewhere.

Sorption of noble gases by solids, with reference to meteorites. II - Chromite and carbon. III - Sulfides, spinels, and other substances; on the origin of planetary gases

NASA Technical Reports Server (NTRS)

Yang, J.; Anders, E.

1982-01-01

The trapping of noble gases by chromite and carbon, two putative carriers of primordial noble gases in meteorites, was studied by synthesizing 19 samples in a Ne-Ar-Kr-Xe atmosphere at 440-720 K. Noble gas contents are found to approximately obey Henry's Law, but only slight correlations are found with composition, surface area, or adsorption temperature. Geometric mean distribution coefficients for bulk samples and HCl residues in 10 cu cm STP/g atm are: Xe 100, Kr 15, Ar 3.5, and Ne 0.62. Elemental fractionation data support the suggestion of Lewis et al. (1977) that chromite and carbon in C2 and C3 chondrites were formed by the reaction: Fe, Cr + 4CO yields (Fe, Cr)3O4 + 4C + carbides. In contrast to meteoritic minerals, the synthetic specimens show no isotopic fractionation of noble gases. In a subsequent study, attention is given to the cases of sulfides and spinels, on the way to consideration of the origin of planetary gases. Sulfides showed three distinctive trends relative to chromite or magnetite. The elemental fractionation pattern of Ar, Kr and Xe in meteorites, terrestrial rocks and planets resembles the adsorption patterns on the carbons, spinels, sulfides, and other solids studied. The high release temperature of meteoritic noble gases may be explained by transformation of the physisorbed or chemisorbed gas. The ready loss of meteoritic heavy gases on surficial oxidation is consistent with adsorption, as is the high abundance.

Effect of basicity on beneficiated chromite sand smelting process using submerged arc furnace

NASA Astrophysics Data System (ADS)

Nurjaman, F.; Subandrio, S.; Ferdian, D.; Suharno, Bambang

2018-05-01

Ferrochrome is an important alloy in stainless steel making due to its contribution to high strength and corrosion resistance. In this present study, ferrochrome was derived from Indonesian chromite sand with low-grade Cr/Fe ratio. In order to improve the ratio, beneficiation process such as pre-magnetic separation and reduction process at 1000°C for 60 minutes was required. The process followed by another magnetic separation, thus the Cr/Fe ratio was increased from 0.9 to 1.6. The reduction process used coconut shell charcoal as reductant and limestone as an additive. The beneficiated sand chromite was briquette using bentonite as a binder in 2 wt.% before it was smelted in a submerged electric arc furnace to produce ferrochrome. Basicity was controlled by the addition of limestone and it was varied from 0.4-1.6. Furthermore, the composition of ferrochrome was analyzed by using X-Ray Fluorescence. From this experiment, the result showed that chromium recovery and specific energy was decreased with the increasing of slag basicity.

Environmental status of groundwater affected by chromite ore processing residue (COPR) dumpsites during pre-monsoon and monsoon seasons.

PubMed

Matern, Katrin; Weigand, Harald; Singh, Abhas; Mansfeldt, Tim

2017-02-01

Chromite ore processing residue (COPR) is generated by the roasting of chromite ores for the extraction of chromium. Leaching of carcinogenic hexavalent chromium (Cr(VI)) from COPR dumpsites and contamination of groundwater is a key environmental risk. The objective of the study was to evaluate Cr(VI) contamination in groundwater in the vicinity of three COPR disposal sites in Uttar Pradesh, India, in the pre-monsoon and monsoon seasons. Groundwater samples (n = 57 pre-monsoon, n = 70 monsoon) were taken in 2014 and analyzed for Cr(VI) and relevant hydrochemical parameters. The site-specific ranges of Cr(VI) concentrations in groundwater were <0.005 to 34.8 mg L -1 (Rania), <0.005 to 115 mg L -1 (Chhiwali), and <0.005 to 2.0 mg L -1 (Godhrauli). Maximum levels of Cr(VI) were found close to the COPR dumpsites and significantly exceeded safe drinking water limits (0.05 mg L -1 ). No significant dependence of Cr(VI) concentration on monsoons was observed.

Microbial leaching of chromite overburden from Sukinda mines, Orissa, India using Aspergillus niger

NASA Astrophysics Data System (ADS)

Biswas, Supratim; Samanta, Saikat; Dey, Rajib; Mukherjee, Siddhartha; Banerjee, Pataki C.

2013-08-01

Leaching of nickel and cobalt from two physical grades (S1, 125-190 μm, coarser and S3, 53-75 μm, finer) of chromite overburden was achieved by treating the overburden (2% pulp density) with 21-d culture filtrate of an Aspergillus niger strain grown in sucrose medium. Metal dissolution increases with ore roasting at 600°C and decreasing particle size due to the alteration of microstructural properties involving the conversion of goethite to hematite and the increase in surface area and porosity as evident from X-ray diffraction (XRD), thermogravimetry-differential thermal analysis (DT-TGA), and field emission scanning electron microscopy (FESEM). About 65% Ni and 59% Co were recovered from the roasted S3 ore employing bioleaching against 26.87% Ni and 31.3% Co using an equivalent amount of synthetic oxalic acid under identical conditions. The results suggest that other fungal metabolites in the culture filtrate played a positive role in the bioleaching process, making it an efficient green approach in Ni and Co recovery from lateritic chromite overburden.

Durable rechargeable zinc-air batteries with neutral electrolyte and manganese oxide catalyst

NASA Astrophysics Data System (ADS)

Sumboja, Afriyanti; Ge, Xiaoming; Zheng, Guangyuan; Goh, F. W. Thomas; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

2016-11-01

Neutral chloride-based electrolyte and directly grown manganese oxide on carbon paper are used as the electrolyte and air cathode respectively for rechargeable Zn-air batteries. Oxygen reduction and oxygen evolution reactions on manganese oxide show dependence of activities on the pH of the electrolyte. Zn-air batteries with chloride-based electrolyte and manganese oxide catalyst exhibit satisfactory voltage profile (discharge and charge voltage of 1 and 2 V at 1 mA cm-2) and excellent cycling stability (≈90 days of continuous cycle test), which is attributed to the reduced carbon corrosion on the air cathode and decreased carbonation in neutral electrolyte. This work describes a robust electrolyte system that improves the cycle life of rechargeable Zn-air batteries.

Geology of the Zambales ophiolite, Luzon, Philippines

USGS Publications Warehouse

Rossman, D.L.; Castanada, G.C.; Bacuta, G.C.

1989-01-01

The Zambales ophiolite of western Luzon, Philippines, exposes a typical succession of basalt flows, diabasic dikes, gabbro and tectonized harzburgite. The age established by limiting strata is late Eocene. Lack of evidence of thrust faulting and the general domal disposition of the lithologie units indicate that the ophiolitic rocks are exposed by uplift. Highly complex internal layered structures within the complex are related to processes developed during formation of the ophiolite and the Zambales ophiolite may be one of the least disturbed (by emplacement) ophiolitic masses known. The exposed mass trends north and the upper surface plunges at low angles (a few degrees) to the north and south. The chemistry and composition of the rocks in the northwest part of the Zambales area (Acoje block) is distinct from that in the southeastern segment (Coto block). The Acoje block, according to Evans (1983) and Hawkins and Evans (1983), resembles (on a chemical basis) arc-tholeiite series rocks from intra-island arcs and the rocks in the Coto block are typical back-arc basin rock series. The present writer believes that the ophiolite composes a single genetic unit and that the changes in composition are the result of changes that took place during the initial formation. The gabbro probably formed below a spreading center in an elongate, in cross section, V-shaped, magma chamber. The gabbro is estimated by the writer to be less than 2 km thick and may be less than 1 km in places. Numerous erosional windows through the gabbro in the northern and eastern side of the Zambales area show that the gabbro remaining in those areas is likely to be only a few hundred meters thick. Harzburgite is exposed to a depth of about 800 m in the Bagsit River area and this may be the deepest part of the ophiolite accessible for study on which there is any control on depth. A transitional zone, about 200 m thick lying between the gabbro and harzburgite, is composed of serpentinized dunite. Commonly the dunite contains disseminated sulfide minerals and at the Acoje Mines, platinum-group elements. A compositional layering within the gabbro is in places cumulate in the lower part of the unit but may have formed by nucleation higher up on the relatively steep sides of the magma chamber. A widespread gneissic banding in the gabbro forms large mappable structures which are many times more complex than is the disposition of the major rock units. These structures are believed to be the result of extensive slumping in the magma chamber. The structure produced by the cumulate layering merges with the gneissic banding, commonly without discernible change in attitude. This tectonic layered structure crosses the gabbro-peridotite boundary at any angle without seeming to disturb the original rock distribution. At greater depths below the boundary (ca. 800 m), the harzburgite contains low dipping banding, which probably reflects the result of differential movement within the mantle. Chromite occurs almost exclusively in a zone that generally lies no more than 200-300 m below the gabbro-peridotite boundary. Refractory-grade chromite is found in this zone below the olivine gabbro in the Goto block and as low-grade metallurgical grade chromite below norite in the Acoje block. At Acoje Mines the chromite is present in layers in dunite, which the writer interprets as being distributed in a zone along the gently dipping (ca. 25??) gabbro-peridotite boundary. The steeply dipping (ca. 60-80 ?? ) individual layers lie en echelon along the boundary at an angle (ca. 50 ?? ) to the contact. At Coto the chromite forms large discontinuous masses in the lowest dunite and in the uppermost harzburgite. Except for the chromite present as layers at Acoje, the regional tectonic layering crosses the chromite deposits without structural deviation. The chromite deposits and associated peridotite may be cumulate in origin, but have been modified to such an extent that cumulate textures are gener

Low Stress Mechanical Properties of Plasma-Treated Cotton Fabric Subjected to Zinc Oxide-Anti-Microbial Treatment.

PubMed

Kan, Chi-Wai; Lam, Yin-Ling

2013-01-22

Cotton fabrics are highly popular because of their excellent properties such as regeneration, bio-degradation, softness, affinity to skin and hygroscopic properties. When in contact with the human body, cotton fabrics offer an ideal environment for microbial growth due to their ability to retain oxygen, moisture and warmth, as well as nutrients from spillages and body sweat. Therefore, an anti-microbial coating formulation (Microfresh and Microban together with zinc oxide as catalyst) was developed for cotton fabrics to improve treatment effectiveness. In addition, plasma technology was employed in the study which roughened the surface of the materials, improving the loading of zinc oxides on the surface. In this study, the low stress mechanical properties of plasma pre-treated and/or anti-microbial-treated cotton fabric were studied. The overall results show that the specimens had improved bending properties when zinc oxides were added in the anti-microbial coating recipe. Also, without plasma pre-treatment, anti-microbial-treatment of cotton fabric had a positive effect only on tensile resilience, shear stress at 0.5° and compressional energy, while plasma-treated specimens had better overall tensile properties even after anti-microbial treatment.

Low Stress Mechanical Properties of Plasma-Treated Cotton Fabric Subjected to Zinc Oxide-Anti-Microbial Treatment

PubMed Central

Kan, Chi-Wai; Lam, Yin-Ling

2013-01-01

Cotton fabrics are highly popular because of their excellent properties such as regeneration, bio-degradation, softness, affinity to skin and hygroscopic properties. When in contact with the human body, cotton fabrics offer an ideal environment for microbial growth due to their ability to retain oxygen, moisture and warmth, as well as nutrients from spillages and body sweat. Therefore, an anti-microbial coating formulation (Microfresh and Microban together with zinc oxide as catalyst) was developed for cotton fabrics to improve treatment effectiveness. In addition, plasma technology was employed in the study which roughened the surface of the materials, improving the loading of zinc oxides on the surface. In this study, the low stress mechanical properties of plasma pre-treated and/or anti-microbial-treated cotton fabric were studied. The overall results show that the specimens had improved bending properties when zinc oxides were added in the anti-microbial coating recipe. Also, without plasma pre-treatment, anti-microbial-treatment of cotton fabric had a positive effect only on tensile resilience, shear stress at 0.5° and compressional energy, while plasma-treated specimens had better overall tensile properties even after anti-microbial treatment. PMID:28809311

Structurally ordered Pt–Zn/C series nanoparticles as efficient anode catalysts for formic acid electrooxidation

DOE PAGES

Zhu, Jing; Zheng, Xin; Wang, Jie; ...

2015-09-15

Controlling the size, composition, and structure of bimetallic nanoparticles is of particular interest in the field of electrocatalysts for fuel cells. In the present work, structurally ordered nanoparticles with intermetallic phases of Pt 3Zn and PtZn have been successfully synthesized via an impregnation reduction method, followed by post heat-treatment. The Pt 3Zn and PtZn ordered intermetallic nanoparticles are well dispersed on a carbon support with ultrasmall mean particle sizes of ~5 nm and ~3 nm in diameter, respectively, which are credited to the evaporation of the zinc element at high temperature. These catalysts are less susceptible to CO poisoning relativemore » to Pt/C and exhibited enhanced catalytic activity and stability toward formic acid electrooxidation. The mass activities of the as-prepared catalysts were approximately 2 to 3 times that of commercial Pt at 0.5 V (vs. RHE). As a result, this facile synthetic strategy is scalable for mass production of catalytic materials.« less

Biosourced polymetallic catalysis: A surprising and efficient means to promote the Knoevenagel condensation

NASA Astrophysics Data System (ADS)

Deyris, Pierre-Alexandre; Bert, Valérie; Diliberto, Sébastien; Boulanger, Clotilde; Petit, Eddy; Legrand, Yves-Marie; Grison, Claude

2018-03-01

Zn hyperaccumulator (Arabidobsis halleri) and Zn accumulator Salix ‘Tordis’ (Salix schwerinii x S. viminalis) have shown their interest in the phytoextraction of polluted brownfields. Herein, we explore an innovative methodology based on the chemical valorization of Zn-rich biomass produced by these metallophyte plants. The approach is based on the direct use of polymetallic salts derived from plants as “Lewis acid” catalysts in organic chemistry. The formed ecocatalysts were characterized via ICP-MS, XRD, FT-IR in order to elucidate the chemical composition, structure and behavior of the formed materials. The Doebner-Knoevenagel reaction was chosen as model reaction to study their synthetic potential. Significant differences to conventional catalysts such as zinc (II) chloride are observed. They can principally be related to a mixture of unusual mineral species. DFT calculations were carried out on these salts in the context of the Gutmann theory. They allow the rationalization of experimental results. Finally, these new bio-based polymetallic catalysts illustrated the interest of this concept for green and sustainable catalysis.

Achieving Simultaneous CO2 and H2 S Conversion via a Coupled Solar-Driven Electrochemical Approach on Non-Precious-Metal Catalysts.

PubMed

Ma, Weiguang; Wang, Hong; Yu, Wei; Wang, Xiaomei; Xu, Zhiqiang; Zong, Xu; Li, Can

2018-03-19

Carbon dioxide (CO 2 ) and hydrogen sulfide (H 2 S) are generally concomitant with methane (CH 4 ) in natural gas and traditionally deemed useless or even harmful. Developing strategies that can simultaneously convert both CO 2 and H 2 S into value-added products is attractive; however it has not received enough attention. A solar-driven electrochemical process is demonstrated using graphene-encapsulated zinc oxide catalyst for CO 2 reduction and graphene catalyst for H 2 S oxidation mediated by EDTA-Fe 2+ /EDTA-Fe 3+ redox couples. The as-prepared solar-driven electrochemical system can realize the simultaneous conversion of CO 2 and H 2 S into carbon monoxide and elemental sulfur at near neutral conditions with high stability and selectivity. This conceptually provides an alternative avenue for the purification of natural gas with added economic and environmental benefits. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

BBD Optimization of K-ZnO Catalyst Modification Process for Heterogeneous Transesterification of Rice Bran Oil to Biodiesel

NASA Astrophysics Data System (ADS)

Kabo, K. S.; Yacob, A. R.; Bakar, W. A. W. A.; Buang, N. A.; Bello, A. M.; Ruskam, A.

2016-07-01

Environmentally benign zinc oxide (ZnO) was modified with 0-15% (wt.) potassium through wet impregnation and used in transesterification of rice bran oil (RBO) to form biodiesel. The catalyst was characterized by X-Ray powder Diffraction (XRD), its basic sites determined by back titration and Response Surface Methodology (RSM) Box-Behnken Design (BBD) was used to optimize the modification process variables on the basic sites of the catalyst. The transesterification product, biodiesel was analyzed by Nuclear Magnetic Resonance (NMR) spectroscopy. The result reveals K-modified ZnO with highly increased basic sites. Quadratic model with high regression R2 = 0.9995 was obtained from the ANOVA of modification process, optimization at maximum basic sites criterion gave optimum modification conditions of K-loading = 8.5% (wt.), calcination temperature = 480 oC and time = 4 hours with response and basic sites = 8.14 mmol/g which is in close agreement with the experimental value of 7.64 mmol/g. The catalyst was used and a value of 95.53% biodiesel conversion was obtained and effect of potassium leaching was not significant in the process

Synthesis, characterization and application of two-dimensional layered metal hydroxides for environmental remediation purposes

NASA Astrophysics Data System (ADS)

Machingauta, Cleopas

Two-dimensional layered nano composites, which include layered double hydroxides (LDHs), hydroxy double salts (HDSs) and layered hydroxide salts (LHSs) are able to intercalate different molecular species within their gallery space. These materials have a tunable structural composition which has made them applicable as fire retardants, adsorbents, catalysts, catalyst support materials, and ion exchangers. Thermal treatment of these materials results in destruction of the layers and formation of mixed metal oxides (MMOs) and spinels. MMOs have the ability to adsorb anions from solution and may also regenerate layered structures through a phenomenon known as memory effect. Zinc-nickel hydroxy nitrate was used for the uptake of a series of halogenated acetates (HAs). HAs are pollutants introduced into water systems as by-products of water chlorination and pesticide degradation; their sequestration from water is thus crucial. Optimization of layered materials for controlled uptake requires an understanding of their ion-exchange kinetics and thermodynamics. Exchange kinetics of these anions was monitored using ex-situ PXRD, UV-vis, HPLC and FTIR. It was revealed that exchange rates and uptake efficiencies are related to electronic spatial extents and the charge on carboxyl-oxygen atoms. In addition, acetate and nitrate-based HDSs were used to explore how altering the hydroxide layer affects uptake of acetate/nitrate ions. Changing the metal identities affects the interaction of the anions with the layers. From FTIR, we observed that nitrates coordinate in a D3h and Cs/C 2v symmetry; the nitrates in D3h symmetry were easily exchangeable. Interlayer hydrogen bonding was also revealed to be dependent on metal identity. Substituting divalent cations with trivalent cations produces materials with a higher charge density than HDSs and LHSs. A comparison of the uptake efficiency of zinc-aluminum, zinc-gallium and zinc-nickel hydroxy nitrates was performed using trichloroacetic acid as target anion. Uptake efficiency was better for LDHs than HDS, and between the LDHs, zinc-aluminum hydroxy nitrate was the best material for the uptake of tClAc. Calcined LDHs were applied for the uptake of methyl-orange, model azo-dye. The ability to regenerate the layered structures was helpful for improving adsorption efficiency. It has been reveal that calcined LDHs are also better adsorbents than calcined HDSs.

Room temperature synthesis and enhanced photocatalytic property of CeO2/ZnO heterostructures

NASA Astrophysics Data System (ADS)

Wang, Chao; Fan, Huiqing; Ren, Xiaohu; Fang, Jiawen

2018-02-01

To achieve better photocatalytic performance, we proposed a facile solid-state reaction method to produce CeO2/ZnO heterostructures. Ceria and zinc oxide were synthesized simultaneously by thoroughly grinding the mixture of zinc acetate dihydrate, cerium nitrate hexahydrate and sodium hydroxide. The morphology of the as-prepared heterostructures varies dramatically as different amount of ceria was introduced in the composition. The photocatalytic performance of CeO2/ZnO heterojunctions was 4.6 times higher than that of pure ZnO. The enhanced photocatalytic activity could be ascribed to that more electrons and holes could transport to the surface of catalysts and react with the pollution due to the extended light-responsive range, accelerated migration, increased specific surface area and suppressed recombination of photogenerated carriers.

Enantioselective ProPhenol-catalyzed addition of 1,3-diynes to aldehydes to generate synthetically versatile building blocks and diyne natural products.

PubMed

Trost, Barry M; Chan, Vincent S; Yamamoto, Daisuke

2010-04-14

A highly enantioselective method for the catalytic addition of terminal 1,3-diynes to aldehydes was developed using our dinuclear zinc ProPhenol (1) system. Furthermore, triphenylphosphine oxide was found to interact synergistically with the catalyst to substantially enhance the chiral recognition. The generality of this catalytic transformation was demonstrated with aryl, alpha,beta-unsaturated and saturated aldehydes, of which the latter were previously limited in alkynyl zinc additions. The chiral diynol products are also versatile building blocks that can be readily elaborated; this was illustrated through highly selective trans-hydrosilylations, which enabled the synthesis of a beta-hydroxyketone and enyne. Additionally, the development of this method allowed for the rapid total syntheses of several biologically important diynol-containing natural products.

Combustion engine system

NASA Technical Reports Server (NTRS)

Houseman, John (Inventor); Voecks, Gerald E. (Inventor)

1986-01-01

A flow through catalytic reactor which selectively catalytically decomposes methanol into a soot free hydrogen rich product gas utilizing engine exhaust at temperatures of 200 to 650 C to provide the heat for vaporizing and decomposing the methanol is described. The reactor is combined with either a spark ignited or compression ignited internal combustion engine or a gas turbine to provide a combustion engine system. The system may be fueled entirely by the hydrogen rich gas produced in the methanol decomposition reactor or the system may be operated on mixed fuels for transient power gain and for cold start of the engine system. The reactor includes a decomposition zone formed by a plurality of elongated cylinders which contain a body of vapor permeable, methanol decomposition catalyst preferably a shift catalyst such as copper-zinc.

Atomic-absorption determination of rhodium in chromite concentrates

USGS Publications Warehouse

Schnepfe, M.M.; Grimaldi, F.S.

1969-01-01

Rhodium is determined in chromite concentrates by atomic absorption after concentration either by co-precipitation with tellurium formed by the reduction of tellurite with tin(II) chloride or by fire assay into a gold bead. Interelement interferences in the atomic-absorption determination are removed by buffering the solutions with lanthanum sulphate (lanthanum concentration 1%). Substantial amounts of Ag, Al, Au, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ho, Hg, K, La, Mg, Mn, Mo, Na, Ni, Pb, Te, Ti, V, Y, Zn and platinum metals can be tolerated. A lower limit of approximately 0.07 ppm Rh can be determined in a 3-g sample. ?? 1969.

Development and understanding of La0.85Sr0.15Cr1-xNixO3-δ anodes for La5.6WO11.4-δ-based Proton Conducting Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Solís, Cecilia; Navarrete, Laura; Balaguer, María; Serra, José M.

2014-07-01

Porous electrodes based on the system La0.85Sr0.15Cr1-xNixO3-δ (x = 0.1 and 0.2) have been investigated as anodes for proton conducting solid oxide fuel cells based on the La5.6WO11.4-δ (LWO) electrolyte material. The microstructure of the anodes was optimized by varying both the starting powder morphology and the final anode sintering temperature. Two different electrode thicknesses were studied, i.e. 15 and 30 μm. The importance of the catalytic role of Ni was also studied by using different concentrations of Ni (10% and 20%) in the chromite and by tuning the Ni particle sizes through the control of the reduction temperature. Additionally, a ceramic-ceramic (cer-cer) composite electrode comprising a physical mixture of the optimized chromite and LWO phase was also considered. Finally, a kinetics study and modeling based on Langmuir-Hinshelwood mechanism was carried out in order to quantitatively describe the rate of dissociative adsorption of H2 on the Ni particles spread on the chromite surface.

Intensive Variables in Primary Kimberlite Magmas (Lac de Gras, N.W.T., Canada) and Application for Diamond Preservation

NASA Astrophysics Data System (ADS)

Fedortchouk, Y.; Canil, D.; Carlson, J. A.

2002-12-01

Crystallization temperatures (T) and oxygen fugacity (fO2) are not well constrained for kimberlites. Knowledge of these intensive variables of kimberlite melt is important for understanding the origin and evolution of kimberlites and prediction of diamond preservation in the magma. Difficulties in interpreting the equilibrium mineral assemblages in kimberlites and the high degree of secondary alteration usually complicate use of mineral geothermometers and oxygen barometers. Some of Lac de Gras (N.W.T., Canada) kimberlites are extremely fresh and provide opportunity to apply mineral thermobarometers. The presence of numerous chromite inclusions in the rims of olivine phenocrysts allows application of the olivine-spinel thermometer and oxygen barometer to constrain T and fO2 of the melt. We performed T and fO2 calculations on samples from three kimberlite pipes - the Leslie, Aaron and Grizzly. The T obtained from olivine - chromite pairs for crystallization of olivine phenocryst rims are 1050° to 1100°C +/- 50°C (calculated at 1 GPa). Few olivine - chromite pairs from Leslie and Grizzly record higher temperatures of 1250° - 1350°C. The cores of olivine phenocrysts usually lack chromite inclusions and their crystallization T and fO2 could not be estimated. The fO2 recorded by coexisting olivine and chromite are +0.3 to 1.0 +/- 0.4 log units more oxidized than the nickel-nickel oxide (NNO) buffer. The established fO2 of kimberlites would require fO2 in their mantle source to be higher than that of cratonic mantle and oceanic lithosphere producing MORB's but comparable to the source of subduction-related magmas. The T and fO2 for the Lac de Gras kimberlites constrain the path of any mantle material entrained in these magmas in fO2-T-P space and provide limits on diamond destructive processes. Diamonds are not stable in kimberlite magma and are oxidized to CO2 or converted into graphite. The former process is more favorable for their preservation. The results of out thermo-barometric calculations show that at any pressure the Lac de Gras kimberlites were above the Graphite (Diamond)-CCO buffer. Diamonds entrained in these kimberlites were moved into stability field of CO2 without graphitization, favoring better preservation of diamonds.

A concise and practical stereoselective synthesis of ipragliflozin L-proline

PubMed Central

Ma, Shuai; Liu, Zhenren; Pan, Jing; Zhang, Shunli

2017-01-01

A concise and practical stereoselective synthesis of ipragliflozin L-proline was presented starting from 2-[(5-iodo-2-fluorophenyl)methyl]-1-benzothiophene and 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide without catalyst via iodine–lithium–zinc exchange. The overall yield was 52% in three steps and the product purity was excellent. Two key diastereomers were prepared with efficient and direct access to the α-C-arylglucoside. PMID:28684985

Late Eocene 3He and Ir anomalies associated with ordinary chondritic spinels

NASA Astrophysics Data System (ADS)

Boschi, Samuele; Schmitz, Birger; Heck, Philipp R.; Cronholm, Anders; Defouilloy, Céline; Kita, Noriko T.; Monechi, Simonetta; Montanari, Alessandro; Rout, Surya S.; Terfelt, Fredrik

2017-05-01

During the late Eocene there was an enigmatic enhancement in the flux of extraterrestrial material to Earth. Evidence comes from sedimentary 3He records indicating an increased flux of interplanetary dust during ca. 2 Myr, as well as two very large impact structures, Popigai (100 km diameter) and Chesapeake Bay (40-85 km), that formed within 10-20 kyr at the peak of the 3He delivery. The Massignano section in Italy has one of the best sedimentary records of these events, including a well-defined 3He record, an Ir-rich ejecta bed related to the Popigai impact event, and two smaller Ir anomalies. Recently we showed that the Popigai ejecta is associated with a significant enrichment of chromite grains (>63 μm) with an H-chondritic elemental composition (17 grains in 100 kg of rock). Most likely these grains are unmelted fragments from the impactor. Slightly higher up (ca. 20 cm) in the section, where a small Ir anomaly possibly related to the Chesapeake Bay impact has been measured, we found a weak enrichment in L-chondritic grains (8 grains in 208 kg of rock). Here we report an extended data set increasing the total amount of sediment dissolved in acid and searched for extraterrestrial chromite grains from 658 to 1168 kg. In altogether 760 kg of background sediment from 17 levels over 14 m of strata outside the interval corresponding to the Popigai and Chesapeake Bay impacts, we only found 2 extraterrestrial chromite grains. Both grains have L-chondritic compositions and were found in a 100 kg sample from the ca. 10.25 m level in the section where the second of the smaller Ir anomalies has been reported. A correlation appears to exist between Ir, 3He and chromite from ordinary chondrites. We also report oxygen three-isotope measurements of the extraterrestrial chromite grains associated with the Popigai ejecta and confirm an H-chondritic composition. The new results strengthen our scenario that the upper Eocene 3He and Ir enrichments originate from the asteroid belt rather than the Oort cloud as originally proposed when the 3He anomaly was discovered. The generally low background concentrations of extraterrestrial chromite through the section speak against any major single asteroid breakup event such as in the mid-Ordovician after the break-up of the L-chondrite parent body. Instead the data reconcile with a small, possibly a factor of 2-3, increase in the flux of extraterrestrial material to Earth, but of both H- and L-chondritic composition. We also report the composition of all the 2310 terrestrial chrome spinel grains recovered, and show that their chemical composition indicates a dominantly regional ophiolitic source. Four anomalous chrome spinel grains with high Ti and V concentrations were found in the Popigai ejecta. These grains originate from Siberian Traps basalts in the Popigai crater at the time of impact.

Biosourced Polymetallic Catalysis: A Surprising and Efficient Means to Promote the Knoevenagel Condensation

PubMed Central

Deyris, Pierre-Alexandre; Bert, Valérie; Diliberto, Sébastien; Boulanger, Clotilde; Petit, Eddy; Legrand, Yves-Marie; Grison, Claude

2018-01-01

Zn hyperaccumulator (Arabidobsis halleri) and Zn accumulator Salix “Tordis” (Salix schwerinii × Salix viminalis) have shown their interest in the phytoextraction of polluted brownfields. Herein, we explore a novel methodology based on the chemical valorization of Zn-rich biomass produced by these metallophyte plants. The approach is based on the use of polymetallic salts derived from plants as bio-based catalysts in organic chemistry. The formed ecocatalysts were characterized via ICP-MS, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) in order to precise the chemical composition, structure, and behavior of the formed materials. The Doebner-Knoevenagel reaction was chosen as model reaction to study their synthetic potential. Significant differences to usual catalysts such as zinc (II) chloride are observed. They can principally be related to a mixture of unusual mineral species. DFT calculations were carried out on these salts in the context of the Gutmann theory. They allow the rationalization of experimental results. Finally, these new bio-based polymetallic catalysts illustrated the interest of this concept for green and sustainable catalysis. PMID:29637065

Biosourced Polymetallic Catalysis: A Surprising and Efficient Means to Promote the Knoevenagel Condensation.

PubMed

Deyris, Pierre-Alexandre; Bert, Valérie; Diliberto, Sébastien; Boulanger, Clotilde; Petit, Eddy; Legrand, Yves-Marie; Grison, Claude

2018-01-01

Zn hyperaccumulator ( Arabidobsis halleri ) and Zn accumulator Salix "Tordis" ( Salix schwerinii × Salix viminalis ) have shown their interest in the phytoextraction of polluted brownfields. Herein, we explore a novel methodology based on the chemical valorization of Zn-rich biomass produced by these metallophyte plants. The approach is based on the use of polymetallic salts derived from plants as bio-based catalysts in organic chemistry. The formed ecocatalysts were characterized via ICP-MS, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) in order to precise the chemical composition, structure, and behavior of the formed materials. The Doebner-Knoevenagel reaction was chosen as model reaction to study their synthetic potential. Significant differences to usual catalysts such as zinc (II) chloride are observed. They can principally be related to a mixture of unusual mineral species. DFT calculations were carried out on these salts in the context of the Gutmann theory. They allow the rationalization of experimental results. Finally, these new bio-based polymetallic catalysts illustrated the interest of this concept for green and sustainable catalysis.

Novel polyoxometalate silica nano-sized spheres: efficient catalysts for olefin oxidation and the deep desulfurization process.

PubMed

Nogueira, Lucie S; Ribeiro, Susana; Granadeiro, Carlos M; Pereira, Eulália; Feio, Gabriel; Cunha-Silva, Luís; Balula, Salete S

2014-07-07

A novel method to prepare silica nano-sized particles incorporating polyoxometalates was developed leading to a new efficient heterogeneous oxidative catalyst. Zinc-substituted polyoxotungstate [PW11Zn(H2O)O39](5-) (PW11Zn) was encapsulated into silica nanoparticles using a cross-linked organic-inorganic core, performed through successive spontaneous reactions in water. The potassium salt of PW11Zn and the composite formed, PW11Zn-APTES@SiO2, were characterized by a myriad of solid-state methods such as FT-IR, FT-Raman, (31)P and (13)C CP/MAS solid-state NMR, elemental analysis and SEM-EDS, confirming the integrity of the PW11Zn structure immobilized in the silica nanoparticles. The new composite has shown to be a versatile catalyst for the oxidation of olefins and also to catalyze the desulfurization of a model oil using H2O2 as the oxidant and acetonitrile as the solvent. The novel composite material was capable of being recycled without significant loss of activity and maintaining its structural stability for consecutive desulfurization and olefin oxidative cycles.

Flower-Like ZnO-Assisted One-Pot Encapsulation of Noble Metal Nanoparticles Supported Catalysts with ZIFs

NASA Astrophysics Data System (ADS)

Lin, Lu; Liu, Haiou; Zhang, Xiongfu

2018-03-01

Rational design of efficient approaches to fabricate MOFs-coated core-shell composites is promising but challenging. We report here the encapsulation of Pd nanoparticles (Pd NPs) supported flower-like ZnO (F-ZnO) microspheres with ZIF-8 shell through a facile strategy, in which the formation and immobilization of Pd NPs on F-ZnO supports and the subsequent growth of ZIF-8 shells over them are effectively integrated into one-pot synthetic route. Importantly, the utilization of ZnO both as support of Pd NPs and Zn2+ source of ZIF-8 is favorable for the implement of one-pot synthesis, due to its functions in anchoring Pd NPs and inducing ZIF-8 formation. Further insights into the morphological influence of zinc oxide particles on the resulting materials indicate that the flower-like microspheres with 2D nanosheets as subunits also benefit the coating of Pd NPs supported cores with ZIF-8, resulting in a well-defined core-shell catalyst. The achieved catalyst deliveries remarkable performance in terms of selectivity, anti-poisoning and recyclability in the liquid hydrogenations of alkenes.

1,6-Conjugate addition of zinc alkyls to para-quinone methides in a continuous-flow microreactor.

PubMed

Jadhav, Abhijeet S; Anand, Ramasamy Vijaya

2016-12-20

An efficient method for the synthesis of alkyl diarylmethanes through the 1,6-conjugate addition of dialkylzinc reagents to para-quinone methides (p-QMs) has been developed under continuous flow conditions using a microreactor. This protocol allows to access unsymmetrical alkyl diarylmethanes in moderate to excellent yields using a wide range of p-QMs and dialkylzinc reagents. Interestingly, this transformation worked well without the requirement of a catalyst.

Genesis of hexavalent chromium from natural sources in soil and groundwater.

PubMed

Oze, Christopher; Bird, Dennis K; Fendorf, Scott

2007-04-17

Naturally occurring Cr(VI) has recently been reported in ground and surface waters. Rock strata rich in Cr(III)-bearing minerals, in particular chromite, are universally found in these areas that occur near convergent plate margins. Here we report experiments demonstrating accelerated dissolution of chromite and subsequent oxidation of Cr(III) to aqueous Cr(VI) in the presence of birnessite, a common manganese mineral, explaining the generation of Cr(VI) by a Cr(III)-bearing mineral considered geochemically inert. Our results demonstrate that Cr(III) within ultramafic- and serpentinite-derived soils/sediments can be oxidized and dissolved through natural processes, leading to hazardous levels of aqueous Cr(VI) in surface and groundwater.

Genesis of hexavalent chromium from natural sources in soil and groundwater

PubMed Central

Oze, Christopher; Bird, Dennis K.; Fendorf, Scott

2007-01-01

Naturally occurring Cr(VI) has recently been reported in ground and surface waters. Rock strata rich in Cr(III)-bearing minerals, in particular chromite, are universally found in these areas that occur near convergent plate margins. Here we report experiments demonstrating accelerated dissolution of chromite and subsequent oxidation of Cr(III) to aqueous Cr(VI) in the presence of birnessite, a common manganese mineral, explaining the generation of Cr(VI) by a Cr(III)-bearing mineral considered geochemically inert. Our results demonstrate that Cr(III) within ultramafic- and serpentinite-derived soils/sediments can be oxidized and dissolved through natural processes, leading to hazardous levels of aqueous Cr(VI) in surface and groundwater. PMID:17420454

Synthesis of renewable bisphenols from creosol.

PubMed

Meylemans, Heather A; Groshens, Thomas J; Harvey, Benjamin G

2012-01-09

A series of renewable bisphenols has been synthesized from creosol (2-methoxy-4-methylphenol) through stoichiometric condensation with short-chain aldehydes. Creosol can be readily produced from lignin, potentially allowing for the large scale synthesis of bisphenol A replacements from abundant waste biomass. The renewable bisphenols were isolated in good yields and purities without resorting to solvent-intense purification methods. Zinc acetate was shown to be a selective catalyst for the ortho-coupling of formaldehyde, but was unreactive when more sterically demanding aldehydes were used. Dilute HCl and HBr solutions were shown to be effective catalysts for the selective coupling of aldehydes in the position meta to the hydroxyl group. The acid solutions could be recycled and reused multiple times without decrease in activity or yield. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the formation of well-aligned ZnO nanowall networks by catalyst-free thermal evaporation method

NASA Astrophysics Data System (ADS)

Yin, Zhigang; Chen, Nuofu; Dai, Ruixuan; Liu, Lei; Zhang, Xingwang; Wang, Xiaohui; Wu, Jinliang; Chai, Chunlin

2007-07-01

Two-dimensional ZnO nanowall networks were grown on ZnO-coated silicon by thermal evaporation at low temperature without catalysts or additives. All of the results from scanning electronic spectroscope, X-ray diffraction and Raman scattering confirmed that the ZnO nanowalls were vertically aligned and c-axis oriented. The room-temperature photoluminescence spectra showed a dominated UV peak at 378 nm, and a much suppressed orange emission centered at ˜590 nm. This demonstrates fairly good crystal quality and optical properties of the product. A possible three-step, zinc vapor-controlled process was proposed to explain the growth of well-aligned ZnO nanowall networks. The pre-coated ZnO template layer plays a key role during the synthesis process, which guides the growth direction of the synthesized products.

Effect of Organic Manures on the Growth of Cymbopogon citratus and Chrysopogon zizanioides for the Phytoremediation of Chromite-Asbestos Mine Waste: A Pot Scale Experiment.

PubMed

Kumar, Adarsh; Maiti, Subodh Kumar

2015-01-01

The abandoned chromite-asbestos mines are located in the Roro hills, West Singhbhum, Jharkhand, India, where mining operation ceased in 1983, and since then these mines are causing environmental pollution. The present study was planned to phytoremediate these metalloid and metal contaminated mine waste by using two aromatic grasses, Cymbopogon citratus and Chrysopogon zizanioides by applying different proportions of amendments (chicken manure, farmyard manure and garden soil). Mine waste has neutral pH, low electrical conductivity and organic carbon with higher concentration of total metals (Cr and Ni) as compared to soil. Application of manures resulted significant improvements of mine waste characteristics and plant growth, reduction in the availability of total extractable toxic metals (Cr, Ni) and increase in Mn, Zn and Cu concentration in the substrate. The maximum growth and biomass production for C. citratus and C. zizanioides were found in T-IV combination comprising of mine waste (90%), chicken manure (2.5%), farmyard manure (2.5%) and garden soil (5%). Addition of T-IV combination also resulted in low Cr and Ni accumulation in roots and reduction in translocation to shoots. Study indicates that C. citratus and C. zizanioides can be used for phytostabilization of abandoned chromite-asbestos mine waste with amendments.

The Popigai impact ejecta layer in the Monte Vaccaro section, Piobbico, Italy

NASA Astrophysics Data System (ADS)

Boschi, S.; Schmitz, B.; Terfelt, F.

2017-12-01

Previously the ejecta from the impact creating the ca. 100 km large Popigai crater in Siberia has been found in Late Eocene sediments in the Massignano section, near Ancona in Italy. Here the ejecta layer is associated with an iridium anomaly, shocked quartz, and abundant clinopyroxene-bearing spherules weathered to so called pancake spherules. Recently we showed that the ejecta is also associated with an enrichment of H-chondritic chromite grains (>63 μm), possibly representing unmelted fragments of the impactor (Boschi et al., 2017). Here we report the first discovery of the Popigai ejecta at another locality in Italy. We found the ejecta in the Monte Vaccaro section, 90 km northwest of Ancona, at the same biostratigraphic level as in the Massignano section. The ejecta layer contains shocked quartz, abundant pancake spherules and an iridium anomaly, just like at Massignano. We measure peak Ir concentrations of 686 ppt, a factor of three higher than the Ir anomaly in the Massignano section. The limestone across the ejecta in the Monte Vaccaro section contains fewer terrestrial spinel grains than at Massignano, making searches for extraterrestrial chromite grains also in size fractions <63 μm feasible. Grains in the size fractions 32-63 μm generally tend to be a factor 10-30 more common than >63 μm grains. The smaller the size fraction of a sedimentary extraterrestrial chromite residue that can be studied, the more statistically robust inferences can be made. The preliminary results for grains in the 32-63 μm fraction from the Monte Vaccaro section indicate a more complex scenario than that based on the >63 μm fraction of chromites recovered from the Massignano section. ReferencesBoschi, S., Schmitz, B., Heck, P.R., Cronholm, A., Defouilloy, C., Kita, N. T.,Monechi, S., Montanari, A., Rout, S. S., Terfelt, F., 2017. Late Eocene 3He and Ir anomalies associated with ordinary chondritic spinels. Geochim. Cosmochim. Acta 204, 205-218.

Mineralogy and origin of stichtite in chromite-bearing serpentinites

NASA Astrophysics Data System (ADS)

Ashwal, Lewis D.; Cairncross, Bruce

Stichtite, a rare (14 known localities worldwide) hydrated carbonate-hydroxide of Mg and Cr with ideal formula Mg6Cr2 (OH)16 CO3 . 4H2O, occurs exclusively in Cr-rich serpentinites of ophiolites or greenstone belts. Physical properties (hardness=1.5-2, specific gravity=2.16-2.2, perfect basal [0001] cleavage, grain size commonly < 100 μm) resemble talc, but the mineral has an attractive purple to lilac color; chemical analyses demonstrate it to be a non-silicate. Stichtite generally occurs as irregular to rounded masses (< 1 cm - 30 cm across) and as veinlets (< 1 mm - > 2 cm wide) within serpentinite. Macroscopic and microscopic textures, such as crosscutting veinlets and stringers, demonstrate that stichtite formation invariably post-dated serpentinization. In some specimens stichtite surrounds relict grains of Cr-rich spinel; in others stichtite has completely replaced euhedral or subhedral chromites. Chemical analyses of stichtites reveal substantial substitution of Al and Fe3+ for Cr in specimens from many localities, reflecting a possible compositional continuum between stichtite and rhombohedral polymorphs hydrotalcite (Mg6Al2 (OH)16 CO3 . 4H2O) and pyroaurite (Mg6Fe2 (OH)16 CO3 . 4H2O). We report the first electron microprobe analyses of stichtites from seven localities, and summarize all available published chemical data. Stichtites very likely inherited part of their trivalent cation chemistry from precursor Cr-rich spinels, but stichtite growth apparently post-dated characteristic ``ferritchromit'' alteration, as demonstrated by the depletion of Al and enrichment in Fe3+ in stichtite relative to primary chromite core compositions. Stichtite appears to form by reaction between serpentine and altered chromite, during addition of substantial fluid, either as separate H2O and CO2 phases, or as a mixed volatile phase. Such reactions must involve removal of substantial SiO2, possibly by transport and remote deposition of silica by throughgoing aqueous and carbonic fluid.

Airborne concentrations of metals and total dust during solid catalyst loading and unloading operations at a petroleum refinery.

PubMed

Lewis, Ryan C; Gaffney, Shannon H; Le, Matthew H; Unice, Ken M; Paustenbach, Dennis J

2012-09-01

Workers handle catalysts extensively at petroleum refineries throughout the world each year; however, little information is available regarding the airborne concentrations and plausible exposures during this type of work. In this paper, we evaluated the airborne concentrations of 15 metals and total dust generated during solid catalyst loading and unloading operations at one of the largest petroleum refineries in the world using historical industrial hygiene samples collected between 1989 and 2006. The total dust and metals, which included aluminum, cadmium, chromium, cobalt, copper, iron, lead, manganese, molybdenum, nickel, platinum, silicon, silver, vanadium, and zinc, were evaluated in relation to the handling of four different types of solid catalysts associated with three major types of catalytic processes. Consideration was given to the known components of the solid catalysts and any metals that were likely deposited onto them during use. A total of 180 analytical results were included in this analysis, representing 13 personal and 54 area samples. Of the long-term personal samples, airborne concentrations of metals ranged from <0.001 to 2.9mg/m(3), and, in all but one case, resulted in concentrations below the current U.S. Occupational Safety and Health Administration's Permissible Exposure Limits and the American Conference of Governmental Industrial Hygienists' Threshold Limit Values. The arithmetic mean total dust concentration resulting from long-term personal samples was 0.31mg/m(3). The data presented here are the most complete set of its kind in the open literature, and are useful for understanding the potential exposures during solid catalyst handling activities at this petroleum refinery and perhaps other modern refineries during the timeframe examined. Copyright © 2011 Elsevier GmbH. All rights reserved.

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

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

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu

To significantly reduce the cost of proton exchange membrane (PEM) fuel cells, current Pt must be replaced by platinum-metal-group (PGM)-free catalysts for the oxygen reduction reaction (ORR) in acid. We report here a new class of high-performance atomic iron dispersed carbon catalysts through controlled chemical doping of iron ions into zinc-zeolitic imidazolate framework (ZIF), a type of metal-organic framework (MOF). The novel synthetic chemistry enables accurate size control of Fe-doped ZIF catalyst particles with a wide range from 20 to 1000 nm without changing chemical properties, which provides a great opportunity to increase the density of active sites that ismore » determined by the particle size. We elucidated the active site formation mechanism by correlating the chemical and structural changes with thermal activation process for the conversion from Fe-N4 complex containing hydrocarbon networks in ZIF to highly active FeNx sites embedded into carbon. A temperature of 800oC was identified as the critical point to start forming pyridinic nitrogen doping at the edge of the graphitized carbon planes. Further increasing heating temperature to 1100oC leads to increase of graphitic nitrogen, generating possible synergistic effect with FeNx sites to promote ORR activity. The best performing catalyst, which has well-defined particle size around 50 nm and abundance of atomic FeNx sites embedded into carbon structures, achieve a new performance milestone for the ORR in acid including a half-wave potential of 0.85 V vs RHE and only 20 mV loss after 10,000 cycles in O2 saturated H2SO4 electrolyte. The new class PGM-free catalyst with approaching activity to Pt holds great promise for future PEM fuel cells.« less

A Descriptive Overview of Japanese Shipbuilding Surface Preparation and Coating Methods

DTIC Science & Technology

1982-09-01

INORGANIC SHOP PRIMER I Materials I Weight BASE PASTE Total Alkyl-silicate Catalyst Alcohol Special organic resin Tinting pigment Anti-sagging agent... Alcohol Zinc powder 32.0 2.0 6.0 0.5 8.0 40.0 100.0 Shop Primer Composition (Courtesy of Chugoku Marine Paints 51 Limited) 4.2.1 Shop Primer...at a pH of 10 is added to minimize the oxydizing reactions which lead to salt formation and adhesion failure. “Galvanite” is the trade name for the

The non-serpentine phases in serpentinites from the Braszowice-Brzeźnica Massif (SW Poland) as traces of magmatic processes within oceanic mantle

NASA Astrophysics Data System (ADS)

Wojtulek, Piotr; Puziewicz, Jacek; Ntaflos, Theodoros

2016-04-01

The Braszowice-Brzeźnica Massif - BBM (SW Poland) is a part of the Variscan Central-Sudetic Ophiolite. It is located at the southern termination of the Niemcza Shear Zone and consists of gabbros and serpentinites. The ultramafic rocks occurring in the BBM are (from E to W) serpentinites with abundant relics of olivine and tremolite, lizardite-chrysotile serpentinites and antigorite serpentinites. Clinopyroxene, olivine and zoned chromite grains were found in the central part of the BBM (Mnich Hill) within antigoritic serpentinites. The non-serpentine phases occur in the following microstructures: (1) olivine-chromite aggregates: olivine (Fo = 90.0-91.0) contains 0.35-0.44 wt.% NiO, elongated or amaeboidal chromite I (Cr# = 0.49-0.50, TiO2 = 0.14-0.15 wt.%) is rimmed by chromite II (Cr# = 0.98, TiO2 = 0.01 wt.%); (2) coarse and dismembered diopside grains (Cpx I, Mg# = 0.91-0.92) containing 0.70-0.80 wt.% TiO2, 3.0-4.0 wt.% Al2O3, 1.0-1.4 Cr2O3 and 0.3-0.5 wt.% Na2O; Cpx I is enriched in REE relative to primitive mantle, the REE pattern reveals HREE enrichment relative to LREE and negative Eu anomaly; (3) olivine-clinopyroxene aggregates: olivine (Fo = 90.4-91.3) contains 0.27-0.35 wt.% NiO, anhedral, often elongated clinopyroxene (Cpx II, Mg# = 0.91-0.92) has <0.1 wt.% TiO2, 3.00-4.00 wt.% Al2O3, 1.00-1.40 Cr2O3 and <0.20 wt.% Na2O, (4) magnetite-bearing olivine grains, locally in aggregates with minute clinopyroxene ones; olivine has variable Fo (86.0-96.0) and NiO concentration (0.02-0.55 wt.%), clinopyroxene (Cpx III, Mg# = 0.93-0.97) contains <0.40 wt.% Al2O3 and <0.20 Cr2O3. Cpx III rims also locally Cpx II. The non-serpentine phases from the BBM massif have various compositions and mode of occurrence, thus they record various crystallization events. Composition of chromite I is similar to primary chromite grains occurring in oceanic peridotites of the Romanche and Kurchatov F.Z. (Dick and Bullen, 1984), thus the olivine-chromite aggregates represent probably primary mantle phases. Cpx I contains similar amount of the Al2O3, Cr2O3 and Na2O to primary diopsides described from the Marie Celeste FZ and Indomed FZ (Johnson et al., 1990). REE pattern of the Cpx I suggests depletion in mobile trace elements due to melt extraction. Cpx II has Al2O3, Cr2O3 and TiO2 contents similar to those of diopside originated from the melt-percolation reactions, olivine coexisting with Cpx II crystallized probably in the same event. The Cpx III has Al, Cr and Na contents typical for secondary, metamorphic clinopyroxene. Magnetite-bearing olivine is similar to olivine crystallized at expense of serpentine+magnetite precursors, thus is has secondary, metamorphic origin. This abstract was prepared as a part of the project of the National Science Centre of Poland ("Evolution of serpentinic members of the Lower Silesia ophiolites", DEC-2012/07/N/ST10/03934). References Dick, H.J.B., Bullen, T., 1984. Chromian spinel as a petrogenetic indicator in abyssal and alpine-type peridotites and spatially associated lavas. Contributions to Mineralogy and Petrology 86, 54-76. Johnson K.T.M., Dick H.J.B., Shimizu N., 1990. Melting in the Oceanic Upper Mantle - an ion microprobe study of Diopsides in Abyssal Peridotites. Journal of Geophysical Research 95, 2661-2678.

Pyrazole bridged dinuclear Cu(II) and Zn(II) complexes as phosphatase models: Synthesis and activity

NASA Astrophysics Data System (ADS)

Naik, Krishna; Nevrekar, Anupama; Kokare, Dhoolesh Gangaram; Kotian, Avinash; Kamat, Vinayak; Revankar, Vidyanand K.

2016-12-01

Present work describes synthesis of dibridged dinuclear [Cu2L2(μ2-NN pyr)(NO3)2(H2O)2] and [Zn2L(μ-OH)(μ-NNpyr)(H2O)2] complexes derived from a pyrazole based ligand bis(2-hydroxy-3-methoxybenzylidene)-1H-pyrazole-3,5-dicarbohydrazide. The ligand shows dimeric chelate behaviour towards copper against monomeric for zinc counterpart. Spectroscopic evidences affirm octahedral environment around the metal ions in solution state and non-electrolytic nature of the complexes. Both the complexes are active catalysts towards phosphomonoester hydrolysis with first order kcat values in the range of 2 × 10-3s-1. Zinc complex exhibited promising catalytic efficiency for the hydrolysis. The dinuclear complexes hydrolyse via Lewis acid activation, whereby the phosphate esters are preferentially bound in a bidentate bridging fashion and subsequent nucleophilic attack to release phosphate group.

ZnO nanodisk based UV detectors with printed electrodes.

PubMed

Alenezi, Mohammad R; Alshammari, Abdullah S; Alzanki, Talal H; Jarowski, Peter; Henley, Simon John; Silva, S Ravi P

2014-04-08

The fabrication of highly functional materials for practical devices requires a deep understanding of the association between morphological and structural properties and applications. A controlled hydrothermal method to produce single crystal ZnO hexagonal nanodisks, nanorings, and nanoroses using a mixed solution of zinc sulfate (ZnSO4) and hexamethylenetetramine (HMTA) without the need of catalysts, substrates, or templates at low temperature (75 °C) is introduced. Metal-semiconductor-metal (MSM) ultraviolet (UV) detectors were fabricated based on individual and multiple single-crystal zinc oxide (ZnO) hexagonal nanodisks. High quality single crystal individual nanodisk devices were fabricated with inkjet-printed silver electrodes. The detectors fabricated show record photoresponsivity (3300 A/W) and external quantum efficiency (1.2 × 10(4)), which we attribute to the absence of grain boundaries in the single crystal ZnO nanodisk and the polarity of its exposed surface.

Heterodinuclear titanium/zinc catalysis: synthesis, characterization and activity for CO2/epoxide copolymerization and cyclic ester polymerization.

PubMed

Garden, Jennifer A; White, Andrew J P; Williams, Charlotte K

2017-02-21

The preparation of heterodinuclear complexes, especially those comprising early-late transition metals coordinated by a simple or symmetrical ancillary ligand, represents a fundamental challenge and an opportunity to prepare catalysts benefitting from synergic properties. Here, two new mixed titanium(iv)-zinc(ii) complexes, [LTi(O i Pr) 2 ZnEt] and [LTi(O i Pr) 2 ZnPh], both coordinated by a diphenolate tetra(amine) macrocyclic ligand (L), are prepared. The synthesis benefits from the discovery that reaction of the ligand with a single equivalent of titanium tetrakis(iso-propoxide) allows the efficient formation of a mono-Ti(iv) complex, [LTi(O i Pr) 2 ]. All new complexes are characterized by a combination of single crystal X-ray diffraction, multinuclear NMR spectroscopy and mass spectrometry techniques. The two heterobimetallic complexes, [LTi(O i Pr) 2 ZnEt] and [LTi(O i Pr) 2 ZnPh], feature trianionic coordination by the macrocyclic ligand and bridging alkoxide groups coordinate to both the different metal centres. The heterodinuclear catalysts are compared to the mono-titanium analogue, [LTi(O i Pr) 2 ], in various polymerization reactions. In the alternating copolymerizations of carbon dioxide and cyclohexene oxide, the mono-titanium complex is totally inactive whilst the heterodinuclear complexes show moderate activity (TOF = 3 h -1 ); it should be noted the activity is measured using just 1 bar pressure of carbon dioxide. In the ring opening polymerization of lactide and ε-caprolactone, the mono-Ti(iv) complex is totally inactive whilst the heterodinuclear complexes show moderate-high activities, qualified by comparison to other known titanium polymerization catalysts (l-lactide, k obs = 11 × 10 -4 s -1 at 70 °C, 1 M in [lactide]) and ε-caprolactone (k obs = 5 × 10 -4 s -1 at 70 °C, 0.9 M in [ε-caprolactone]).

Heavily Graphitic-Nitrogen Self-doped High-porosity Carbon for the Electrocatalysis of Oxygen Reduction Reaction

NASA Astrophysics Data System (ADS)

Feng, Tong; Liao, Wenli; Li, Zhongbin; Sun, Lingtao; Shi, Dongping; Guo, Chaozhong; Huang, Yu; Wang, Yi; Cheng, Jing; Li, Yanrong; Diao, Qizhi

2017-11-01

Large-scale production of active and stable porous carbon catalysts for oxygen reduction reaction (ORR) from protein-rich biomass became a hot topic in fuel cell technology. Here, we report a facile strategy for synthesis of nitrogen-doped porous nanocarbons by means of a simple two-step pyrolysis process combined with the activation of zinc chloride and acid-treatment process, in which kidney bean via low-temperature carbonization was preferentially adopted as the only carbon-nitrogen sources. The results show that this carbon material exhibits excellent ORR electrocatalytic activity, and higher durability and methanol-tolerant property compared to the state-of-the-art Pt/C catalyst for the ORR, which can be mainly attributed to high graphitic-nitrogen content, high specific surface area, and porous characteristics. Our results can encourage the synthesis of high-performance carbon-based ORR electrocatalysts derived from widely-existed natural biomass.

Monomolecular Siloxane Film as a Model of Single Site Catalysts

DOE PAGES

Martynowycz, Michael W.; Hu, Bo; Kuzmenko, Ivan; ...

2016-09-06

Achieving structurally well-defined catalytic species requires a fundamental understanding of surface chemistry. Detailed structural characterization of the catalyst binding sites in situ, such as single site catalysts on silica supports, is technically challenging or even unattainable. Octadecyltrioxysilane (OTOS) monolayers formed from octadecyltrimethoxysilane (OTMS) at the air-liquid interface after hydrolysis and condensation at low pH were chosen as a model system of surface binding sites in silica-supported Zn 2+ catalysts. We characterize the system by grazing incidence X-ray diffraction, X-ray reflectivity (XR), and X-ray fluorescence spectroscopy (XFS). Previous X-ray and infrared surface studies of OTMS/OTOS films at the airliquid interface proposedmore » the formation of polymer OTOS structures. According to our analysis, polymer formation is inconsistent with the X-ray observations and structural properties of siloxanes; it is energetically unfavorable and thus highly unlikely. We suggest an alternative mechanism of hydrolysis/condensation in OTMS leading to the formation of structurally allowed cyclic trimers with the six-membered siloxane rings, which explain well both the X-ray and infrared results. XR and XFS consistently demonstrate that tetrahedral [Zn(NH 3) 4] 2+ ions bind to hydroxyl groups of the film at a stoichiometric ratio of OTOS:Zn ~ 2:1. The high binding affinity of zinc ions to OTOS trimers suggests that the six-membered siloxane rings are binding locations for single site Zn/SiO 2 catalysts. Finally, our results show that OTOS monolayers may serve as a platform for studying silica surface chemistry or hydroxyl-mediated reactions.« less

THE EFFECT OF SULFUR ON METHANE PARTIAL OXIDATION AND REFORMING PROCESSES FOR LEAN NOX TRAP CATALYSIS

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

Parks, II, James E; Ponnusamy, Senthil

2006-01-01

Lean NOx trap catalysis has demonstrated the ability to reduce NOx emissions from lean natural gas reciprocating engines by >90%. The technology operates in a cyclic fashion where NOx is trapped on the catalyst during lean operation and released and reduced to N2 under rich exhaust conditions; the rich cleansing operation of the cycle is referred to as "regeneration" since the catalyst is reactivated for more NOx trapping after NOx purge. Creating the rich exhaust conditions for regeneration can be accomplished by catalytic partial oxidation of methane in the exhaust system. Furthermore, catalytic reforming of partial oxidation exhaust can enablemore » increased quantities of H2 which is an excellent reductant for lean NOx trap regeneration. It is critical to maintain clean and efficient partial oxidation and reforming processes to keep the lean NOx trap functioning properly and to reduce extra fuel consumption from the regeneration process. Although most exhaust constituents do not impede partial oxidation and reforming, some exhaust constituents may negatively affect the catalysts and result in loss of catalytic efficiency. Of particular concern are common catalyst poisons sulfur, zinc, and phosphorous. These poisons form in the exhaust through combustion of fuel and oil, and although they are present at low concentrations, they can accumulate to significant levels over the life of an engine system. In the work presented here, the effects of sulfur on the partial oxidation and reforming catalytic processes were studied to determine any durability limitations on the production of reductants for lean NOx trap catalyst regeneration.« less

Composite tin and zinc oxide nanocrystalline particles for enhanced charge separation in sensitized degradation of dyes.

PubMed

Bandara, J; Tennakone, K; Jayatilaka, P P B

2002-10-01

Composite ZnO/SnO2 catalyst has been studied for the sensitized degradation of dyes e.g. Eosin Y (2', 4', 5', 7'-tetrabromofluorescein disodium salt) in relation to efficient charge separation properties of the catalyst. Improved photocatalytic activity was observed in the case of ZnO/SnO2 composite catalyst compared to the catalytic activity of ZnO, SnO2 or TiO2 powder. The suppression of charge recombination in the composite ZnO/SnO2 catalyst led to higher catalytic activity for the degradation of Eosin Y. Degradation of Eosin follows concomitant formation of CO2 and formation of CO2 followed a pseudo-first-order rate. Photoelectrochemical cells constructed using SnO2, ZnO, ZnO/SnO2 sensitized with Eosin Y showed V(oc) of 175, 306, 512 mV/cm2 and I(sc) of 50, 70, 200 microA/cm2 respectively. A higher irreversible degradation of Eosin Y and higher V(oc) observed on composite ZnO/SnO2 than ZnO and SnO2 separately can be considered as a proof of enhanced charge separation of ZnO/SnO2 catalyst. Eosin Y showed a higher emission decreases on ZnO/SnO2 composite than on individual ZnO, SnO2 or TiO2 indicating dominance of the charge injection process. Photoinjected electrons are tunneled from ZnO to SnO2 particles accumulating injected electrons in the conduction bands allowing wider separation of excited carriers.

Structural and optical characterization of ZnO nanowires grown on alumina by thermal evaporation method.

PubMed

Mute, A; Peres, M; Peiris, T C; Lourenço, A C; Jensen, Lars R; Monteiro, T

2010-04-01

Zinc oxide nanowires have been grown on alumina substrate by thermal evaporation of zinc nanopowder in the presence of oxygen flow. The growth was performed under ambient pressure and without the use of foreign catalyst. Scanning electron microscopy (SEM) observation showed that the as-grown sample consists of bulk ZnO crystal on the substrate surface with nanowires growing from this base. Growth mechanism of the observed morphology is suggested to be governed by the change of zinc vapour supersaturation during the growth process. X-ray diffraction (XRD) measurement was used to identify the crystalline phase of the nanowires. Optical properties of the nanowires were investigated using Raman scattering and photoluminescence (PL). The appearance of dominant, Raman active E2 (high) phonon mode in the Raman spectrum has confirmed the wurtzite hexagonal phase of the nanowires. With above bandgap excitation the low temperature PL recombination is dominated by donor bound exciton luminescence at -3.37 eV with a narrow full width at half maximum. Free exciton emission is also seen at low temperature and can be observed up to room temperature. The optical data indicates that the grown nanowires have high optical quality.

Synthesis, characterization and photocatalytic activity of magnetically separable hexagonal Ni/ZnO nanostructure

NASA Astrophysics Data System (ADS)

Senapati, Samarpita; Srivastava, Suneel K.; Singh, Shiv B.

2012-09-01

The hexagonal zinc oxide coated nickel (Ni/ZnO) nanostructure photocatalyst has successfully been prepared by the reduction of nickel chloride hexahydrate using hydrazine hydrate through the solvothermal process at 140 °C followed by surface modification of the product by the reflux method at 110 °C for 1 h. The X-ray diffraction (XRD) pattern showed that the `as prepared' sample consists of face centered cubic Ni and hexagonal wurtzite ZnO without any traces of impurity. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) images confirmed the formation of nickel nanoparticles under solvothermal conditions. These nickel nanoparticles, when subjected to reflux, formed the hexagonal zinc oxide coated nickel nanostructure. Fourier transform infrared (FTIR) spectra, photoluminescence (PL) and Raman studies also confirmed the presence of zinc oxide in the hybrid nanostructure. The growth mechanism for the development of the hexagonal zinc oxide coated nickel (Ni/ZnO) nanostructure has also been proposed. The appearance of the hysteresis loop, in the as-prepared Ni/ZnO hybrid nanostructure, demonstrated its ferromagnetic character at room temperature. The hexagonal Ni/ZnO nanostructure also acts as an efficient photocatalyst in the degradation of methylene blue under ultraviolet light irradiation. It is observed that the catalytic efficiency of the hybrid nanocatalyst is better compared to pure zinc oxide. Most importantly, the Ni/ZnO catalyst could also be easily separated, simply by applying an external magnetic field, and reused.The hexagonal zinc oxide coated nickel (Ni/ZnO) nanostructure photocatalyst has successfully been prepared by the reduction of nickel chloride hexahydrate using hydrazine hydrate through the solvothermal process at 140 °C followed by surface modification of the product by the reflux method at 110 °C for 1 h. The X-ray diffraction (XRD) pattern showed that the `as prepared' sample consists of face centered cubic Ni and hexagonal wurtzite ZnO without any traces of impurity. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) images confirmed the formation of nickel nanoparticles under solvothermal conditions. These nickel nanoparticles, when subjected to reflux, formed the hexagonal zinc oxide coated nickel nanostructure. Fourier transform infrared (FTIR) spectra, photoluminescence (PL) and Raman studies also confirmed the presence of zinc oxide in the hybrid nanostructure. The growth mechanism for the development of the hexagonal zinc oxide coated nickel (Ni/ZnO) nanostructure has also been proposed. The appearance of the hysteresis loop, in the as-prepared Ni/ZnO hybrid nanostructure, demonstrated its ferromagnetic character at room temperature. The hexagonal Ni/ZnO nanostructure also acts as an efficient photocatalyst in the degradation of methylene blue under ultraviolet light irradiation. It is observed that the catalytic efficiency of the hybrid nanocatalyst is better compared to pure zinc oxide. Most importantly, the Ni/ZnO catalyst could also be easily separated, simply by applying an external magnetic field, and reused. Electronic supplementary information (ESI) available: Fig. S1 Ni/ZnO hybrid nanostructure prepared using (a) 0.195 and (b) 0.25 M [Zn2+] at 90 °C Fig. S2 FTIR spectra of nickel nanoparticles prepared at 140 °C (a), and Ni/ZnO hybrid nanostructure prepared using (b) 0.063, (c) 0.125, (d) 0.195 and (e) 0.25 M [Zn2+]; Fig. S3 Raman spectra of Ni/ZnO nanostructure prepared using (a) 0.063, (b) 0.125, (c) 0.195 and (d) 0.25 M [Zn2+]; Fig. S4 Room temperature PL spectra of (a) ZnO and (b) Ni/ZnO nanostructure prepared using 0.25 M [Zn2+]. See DOI: 10.1039/c2nr31831h

Zinc Tantalum Oxynitride (ZnTaO2N) Photoanode Modified with Cobalt Phosphate Layers for the Photoelectrochemical Oxidation of Alkali Water

PubMed Central

T. Weller, Mark

2018-01-01

Photoanodes fabricated by the electrophoretic deposition of a thermally prepared zinc tantalum oxynitride (ZnTaO2N) catalyst onto indium tin oxide (ITO) substrates show photoactivation for the oxygen evolution reaction (OER) in alkaline solutions. The photoactivity of the OER is further boosted by the photodeposition of cobalt phosphate (CoPi) layers onto the surface of the ZnTaO2N photoanodes. Structural, morphological, and photoelectrochemical (PEC) properties of the modified ZnTaO2N photoanodes are studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet visible (UV−Vis) diffuse reflectance spectroscopy, and electrochemical techniques. The presence of the CoPi layer significantly improved the PEC performance of water oxidation in an alkaline sulphate solution. The photocurrent-voltage behavior of the CoPi-modified ZnTaO2N anodes was improved, with the influence being more prominent at lower oxidation potentials. A stable photocurrent density of about 2.3 mA·cm−2 at 1.23 V vs. RHE was attained upon visible light illumination. Relative to the ZnTaO2N photoanodes, an almost three-fold photocurrent increase was achieved at the CoPi/ZnTaO2N photoelectrode. Perovskite-based oxynitrides are modified using an oxygen-evolution co-catalyst of CoPi, and provide a new dimension for enhancing the photoactivity of oxygen evolution in solar-assisted water-splitting reactions. PMID:29346306

In situ growth of NiFe alloy nanoparticles embedded into N-doped bamboo-like carbon nanotube as a bifunctional electrocatalyst for Zn-air battery.

PubMed

Bin, Duan; Yang, Beibei; Li, Chao; Liu, Yao; Zhang, Xiao; Wang, Yong-Gang; Xia, Yongyao

2018-06-26

Developing low-cost catalysts for electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with superior performance in alkaline solution is of significance for large-scale application in aqueous zinc-air batteries (ZABs). Herein, we describe in situ design of embedded NiFe nanoparticles into the N-doped bamboo-like carbon nanotube (NBCNT) with high catalytic performance and stability. The obtained NiFe@NBCNT hybrid exhibits a high electrochemical activity and stability with an unexpectedly low overpotential of ~195 mV for OER at 10 mA cm-2, and an onset potential at 1.03 V for ORR, superior to the state-of-the-art Pt/C and RuO2 catalysts. Additionally, compared to the mixture Pt/C and RuO2 cathode, the ZAB based on the NiFe@NBCNT cathode displays lower overpotential (0.80 V), higher stable round-trip efficiency (58.3%) and improved power density for 200 cycles at 10 mA cm-2. Apparently, the obtained results indicate that NiFe@NBCNT hybird is proven to be one of the best non-noble metal catalysts for achieving commercial implementation of rechargeable ZABs.

Mare basalt magma source region and mare basalt magma genesis

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

Binder, A.B.

1982-11-15

Given the available data, we find that the wide range of mare basaltic material characteristics can be explained by a model in which: (1) The mare basalt magma source region lies between the crust-mantle boundary and a maximum depth of 200 km and consists of a relatively uniform peridotite containing 73--80% olivine, 11--14% pyroxene, 4--8% plagioclase, 0.2--9% ilmenite and 1--1.5% chromite. (2) The source region consists of two or more density-graded rhythmic bands, whose compositions grade from that of the very low TiO/sub 2/ magma source regions (0.2% ilmenite) to that of the very high TiO/sub 2/ magma source regionsmore » (9% ilmenite). These density-graded bands are proposed to have formed as co-crystallizing olivine, pyroxene, plagioclase, ilmenite, and chromite settled out of a convecting magma (which was also parental to the crust) in which these crystals were suspended. Since the settling rates of the different minerals were governed by Stoke's law, the heavier minerals settled out more rapidly and therefore earlier than the lighter minerals. Thus the crystal assemblages deposited nearest the descending side of each convection cell were enriched in heavy ilmenite and chromite with respect to lighter olivine and pyroxene and very much lighter plagioclase. The reverse being the case for those units deposited near the ascending sides of the convection cells.« less

Application of Sequential Extractions and X-ray Absorption Spectroscopy to Determine the Speciation of Chromium in Northern New Jersey Marsh Soils Developed in Chromite ore Processing Residue (COPR)

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

Elzinga, E.; Cirmo, A

2010-01-01

The Cr speciation in marsh soils developed in weathering chromite ore processing residue (COPR) was characterized using sequential extractions and synchrotron microbeam and bulk X-ray absorption spectroscopic (XAS) analyses. The sequential extractions suggested substantial Cr associated with reducible and oxidizable soil components, and significant non-extractable residual Cr. Notable differences in Cr speciation estimates from three extraction schemes underscore the operationally defined nature of Cr speciation provided by these methods. Micro X-ray fluorescence maps and {mu}-XAS data indicated the presence of {micro}m-sized chromite particles scattered throughout the weathered COPR matrix. These particles derive from the original COPR material, and have relativelymore » high resistance towards weathering, and therefore persist even after prolonged leaching. Bulk XAS data further indicated Cr(III) incorporated in Fe(OH){sub 3}, and Cr(III) associated with organic matter. The low Cr contents of the weathered material (200-850 ppm) compared to unweathered COPR (20,000-60,000 ppm) point to substantial Cr leaching during COPR weathering, with partial repartitioning of released Cr into secondary Fe(OH){sub 3} phases and organics. The effects of anoxia on Cr speciation, and the potential of active COPR weathering releasing Cr(VI) deeper in the profile require further study.« less

Cobalt doped lanthanum chromite material suitable for high temperature use

DOEpatents

Ruka, Roswell J.

1986-01-01

A high temperature, solid electrolyte electrochemical cell, subject to thermal cycling temperatures of between about 25.degree. C. and about 1200.degree. C., capable of electronic interconnection to at least one other electrochemical cell and capable of operating in an environment containing oxygen and a fuel, is made; where the cell has a first and second electrode with solid electrolyte between them, where an improved interconnect material is applied along a portion of a supporting electrode; where the interconnect is made of a chemically modified lanthanum chromite, containing cobalt as the important additive, which interconnect allows for adjustment of the thermal expansion of the interconnect material to more nearly match that of other cell components, such as zirconia electrolyte, and is stable in oxygen containing atmospheres such as air and in fuel environments.

Origins of chromite and magnetite in sedimentary rocks deposited in a shallow water environment in the 3.2 Ga Moodies Group, South Africa

NASA Astrophysics Data System (ADS)

Otake, T.; Sakamoto, Y.; Itoh, S.; Yurimoto, H.; Kakegawa, T.

2012-12-01

*Otake, T. totake@eng.hokudai.ac.jp Div. of Sustainable Resources Engineering, Hokkaido Univ., Sapporo, Japan Sakamoto, Y. yu.sakamoto12@gmail.com Dep. of Earth Science, Tohoku Univ., Sendai, Japan Itoh, S. sitoh@ep.sci.hokudai.ac.jp Dep. of Natural History Sciences, Hokkaido Univ., Sapporo, Japan Yurimoto. H. yuri@ep.sci.hokudai.ac.jp Dep. of Natural History Sciences, Hokkaido Univ., Sapporo, Japan Kakegawa, T. kakegawa@m.tohoku.ac.jp Dep. of Earth Science, Tohoku Univ., Sendai, Japan Geochemical data from ferruginous chemical sedimentary rocks (e.g., Banded Iron Formation: BIF) have been used to reconstruct the surface environments of early Earth. However, only a few studies have investigated the geochemical characteristics of BIFs deposited in a shallow water environment during the Archean, which may have differed from those deposited in a deep water environment. Therefore, we investigated geological, petrographic and geochemical characteristics of ferruginous rocks deposited in a shallow water environment in the Moodies group, in the Barberton Greenstone Belt, South Africa. We obtained ferruginous rock samples in the Moodies group from both an outcrop and underground gold mine, and compared the characteristics of these samples. The 70 sedimentary rock samples were divided into groups based on the dominant Fe minerals they contain: Hematite-rich jaspilite (HM group), Magnetite-rich iron formation/shale/sandstone (MT group), and Siderite-rich sandstone (SD group). Samples in the HM group are predominantly composed of fine-grained quartz (< 20 μm) and hematite (< 5 μm), which are interpreted to be chemical precipitates. Samples in the MT group contain quartz, magnetite, siderite, ankerite, chlorite, biotite and chromite. The grain size of magnetite is much larger (20-150 μm) than that of hematite in the HM group. The magnetite is interpreted as a secondary mineral transformed from hematite during early diagenesis. Results of in situ oxygen isotope analysis by SIMS showed that magnetite in the Moodies group has similar δ18O values to those in the least metamorphosed BIFs. All chromite observed in the MT group is overgrown by magnetite. Samples in the SD group contain quartz, siderite, chlorite, biotite, and chromite; the chromite is included in Mg-rich siderite or silicate minerals (e.g., chlorite and biotite). Oxygen isotope compositions indicate that chromite in both the MT and SD groups, was hydrothermally altered. Results of geochemical analyses of the bulk outcrop samples showed that FeTotal/Ti and Cr/Ti ratios of outcrop samples increase concordantly in the ferruginous zone, particularly in the MT group. The Cr/Ti ratios of the underground samples also increase with increasing the Fetotal/Ti ratios. On the other hand, Th/U ratios of both the outcrop and underground samples decrease with increasing FeTotal/Ti ratios. The correlations of Fetotal/Ti ratios with U/Th and Cr/Ti ratios indicate that dissolved Cr and U species in the ocean were coprecipitated with ferric (hydr)oxides during the formation of ferruginous rocks of the Moodies Group. These results suggest that Cr and U were chemically mobile, possibly as oxidized species, in the Earth's surface environment at ~3.2 Ga.

Development of zinc oxide nanoparticle by sonochemical method and study of their physical and optical properties

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

Khan, Samreen Heena, E-mail: samreen.heena.khan@gmail.com; Suriyaprabha, R.; Pathak, Bhawana, E-mail: bhawana.pathak@cug.ac.in

With the miniaturization of crystal size, the fraction of under-coordinated surface atoms becomes dominant, and hence, materials in the nano-regime behave very differently from the similar material in a bulk. Zinc oxide (ZnO), particularly, exhibits extraordinary properties such as a wide direct band gap (3.37 eV), large excitation binding energy (60 meV), low refractive index (1.9), stability to intense ultraviolet (UV) illumination, resistance to high-energy irradiation, and lower toxicity as compared to other semiconductors. This very property makes Zinc Oxide a potential candidate in many application fields, particularly as a prominent semiconductor. Zinc Oxide plays a significant role in manymore » technological advances with its application in semiconductor mediated photocatalytic processes and sensor, solar cells and others. In present study, Zinc Oxide (ZnO) has been synthesized using three different precursors by sonochemical method. Zinc Acetate Dihydrate, Zinc Nitrate Hexahydrate and Zinc Sulphate Heptahydrate used as a precursor for the synthesis process. The synthesized ZnO nanoparticle has been found under the range of ∼50 nm. Zinc oxide nanoparticles were characterized using different characterizing tools. The as-synthesized ZnO was characterized by Fourier Transform-Infrared Spectroscopy (FT-IR) for the determination of functional group; Scanning Electron Microscopy equipped with Energy Dispersive Spectroscopy (SEM-EDS) for Morphology and elemental detection respectively, Transmission Electron Microscopy for Particle size distribution and morphology and X-Ray Diffraction (XRD) for the confirmation of crystal structure of the nanomaterial. The optical properties of the ZnO were examined by UV-VIS spectroscopy equipped with Diffuse Reflectance spectroscopy (DRS) confirmed the optical band gap of ZnO-3 around 3.23 eV resembles with the band gap of bulk ZnO (3.37eV). The TEM micrograph of the as-synthesized material showed perfectly spherical shaped nanoparticle under the size range of 50nm. The XRD data showed that the ZnO-3 which was synthesized using Zinc Nitrate Hexahydrate as precursor showed the hexagonal wurtzite crystal structure. The XRD data obtained were compared with the JCPDS standard data. The precursor Zinc Nitrate Hexahydrate (ZnO-3) showed the good yield, monodispersity and size of nanoparticle under the range of 50 nm. The ZnO nanoparticles synthesize using different precursor was found effective in order of ZnO-3, followed by ZnO-1 & ZnO-2. The Synthesized ZnO has wider application in environmental remediation and clean-up as a potential nano-catalyst.« less

Heterobimetallic Metal–Organic Framework as a Precursor to Prepare a Nickel/Nanoporous Carbon Composite Catalyst for 4-Nitrophenol Reduction

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

Yang, Ying; Zhang, Ying; Sun, Cheng Jun

2014-11-01

Nickel/nanoporous carbon (Ni/NPC) composites are facilely prepared by direct pyrolysis of nonporous heterobimetallic zinc-nickel-terephthalate frameworks (Zn1-xNixMOF, x approximate to 0-1, MOF= metal-organic framework) at 1223 K in situ. Tailoring the Ni/Zn ratio creates densely populated and small Ni nanocrystals (Ni NCs) while maintaining sufficient porosity and surface area in the final product, which exhibits the largest activity factor (9.2 s(-1)g(-1)) and excellent stability toward 4-nitrophenol reduction.

Respiratory health effects of long-term exposure to different chromium species in stainless steel production.

PubMed

Huvinen, M; Uitti, J; Oksa, P; Palmroos, P; Laippala, P

2002-06-01

The aim of this study was to determine whether occupational exposure to chromite, trivalent chromium (Cr(3+)) or hexavalent chromium (Cr(6+)) causes respiratory diseases, an excess of respiratory symptoms, a decrease in pulmonary function or signs of pneumoconiosis among workers in stainless steel production. Altogether, 203 exposed workers and 81 referents with an average employment of 23 years were investigated for indicators of respiratory health on two occasions, in 1993 and in 1998. Data collection with a self-administered questionnaire, flow volume spirometry, measurement of diffusing capacity, chest radiography and laboratory tests were carried out by a mobile research unit. Exposure to different chromium species and other metals was monitored regularly and studied separately. No adverse respiratory health effects were observed in the group exposed to Cr(6+), either in comparison with the control group in the first cross-sectional study or during the additional 5 year follow-up. Among the Cr (3+) exposed people, the production of phlegm, shortness of breath and breathlessness on exertion were significantly more frequent than in the control group, but the frequency of the symptoms did not increase during the follow-up; no differences were observed in the lung function tests and the radiographic findings did not progress. In the chromite group, the prevalence of breathlessness on exertion was higher than in the control group. However, in the follow-up, the occurrence of symptoms did not differ from 1993 to 1998. In the first study, most parameters of lung function were lower among the smokers in the chromite group than among the smoking controls, but in 1998 the difference was less marked. An average exposure time of 23 years in modern ferrochromium and stainless steel production and low exposure to dusts and fumes containing Cr(6+), Cr(3+), nickel and molybdenum do not lead to respiratory changes detectable by lung function tests or radiography. The workers exposed to Cr(3+) had more respiratory symptoms than those in the control group. The workers in the chromite mine had lower lung function test results than the control group due to earlier exposure to higher dust concentrations.

Linking precious metal enrichment and halogen cycling in mafic magmatic systems: insights from the Rum layered intrusion, NW Scotland

NASA Astrophysics Data System (ADS)

Kelly, A. P.; O'Driscoll, B.; Clay, P. L.; Burgess, R.

2017-12-01

Layered intrusions host the world's largest known concentrations of the platinum-group elements (PGE). Emphasis has been attached to the role of halogen-bearing fluids in concentrating the precious metals, but whether this occurs at the magmatic stage, or via subsequent metasomatism, is actively debated. One obstacle to progress has been the analytical difficulty of measuring low abundances of the halogens in the cumulate products of layered intrusions. To elucidate the importance of the halogens in facilitating PGE-mineralisation, as well as fingerprint halogen provenance and assess the importance of halogen cycling in mafic magma systems more generally, a suite of samples encompassing different stages of activity of the Palaeogene Rum layered intrusion was investigated. Halogen abundances were measured by neutron irradiation noble gas mass spectrometric analysis, permitting the detection of relatively low (ppm-ppb) abundances of Cl, Br and I in mg-sized samples. The samples include PGE-enriched chromite seams, various cumulates (e.g., peridotites), picrites (approximating the Rum parental magma), and pegmatites representing volatile-rich melts that circulated the intrusion at a late-stage in its solidification history. The new data reveal that PGE-bearing chromite seams contain relatively low Cl concentrations (2-3 ppm), with high molar ratios of Br/Cl and I/Cl (0.005 and 0.009, respectively). The picrites and cumulates have Br/Cl and I/Cl ratios close to sub-continental lithospheric mantle values of approximately 0.0013 and 0.00002, respectively, and thus likely reflect the Rum magma source region. A positive correlation between Cl and Br signifies comparable partitioning behaviour in all samples. However, I is more variable, displaying a positive correlation with Cl for more primitive samples (e.g. picrite and peridotite), and seemingly decoupling from Br and Cl in chromite seams and pegmatites. The relative enrichment of I over Cl in the chromite seams points to the local involvement of an organic-rich sedimentary assimilant and potentially represents an important trigger for PGE-mineralisation. Similarly high I/Cl signatures in some of the late-stage pegmatites suggest that fluids with this distinctive composition circulated the cooling Rum intrusion for a protracted period of time.

Trace metals in the brain: allosteric modulators of ligand-gated receptor channels, the case of ATP-gated P2X receptors.

PubMed

Huidobro-Toro, J Pablo; Lorca, Ramón A; Coddou, Claudio

2008-03-01

Zinc and copper are indispensable trace metals for life with a recognized role as catalysts in enzyme actions. We now review evidence supporting the role of trace metals as novel allosteric modulators of ionotropic receptors: a new and fundamental physiological role for zinc and copper in neuronal and brain excitability. The review is focussed on ionotropic receptor channels including nucleotide receptors, in particular the P2X receptor family. Since zinc and copper are stored within synaptic vesicles in selected brain regions, and released to the synaptic cleft upon electrical nerve ending depolarization, it is plausible that zinc and copper reach concentrations in the synapse that profoundly affect ligand-gated ionic channels, including the ATP-gated currents of P2X receptors. The identification of key P2X receptor amino acids that act as ligands for trace metal coordination, carves the structural determinants underlying the allosteric nature of the trace metal modulation. The recognition that the identified key residues such as histidines, aspartic and glutamic acids or cysteines in the extracellular domain are different for each P2X receptor subtype and may be different for each metal, highlights the notion that each P2X receptor subtype evolved independent strategies for metal coordination, which form upon the proper three-dimensional folding of the receptor channels. The understanding of the molecular mechanism of allosteric modulation of ligand-operated ionic channels by trace metals is a new contribution to metallo-neurobiology.

One-Pot Catalytic Enantio- and Diastereoselective Syntheses of anti-, syn-cis-Disubstituted, and syn-Vinyl Cyclopropyl Alcohols

PubMed Central

Kim, Hun Young; Salvi, Luca; Carroll, Patrick J.; Walsh, Patrick J.

2009-01-01

Highly enantio- and diastereoselective methods for the synthesis of a variety of cyclopropyl alcohols are reported. These methods represent the first one-pot approaches to syn-vinyl cyclopropyl alcohols, syn-cis-disubstituted cyclopropyl alcohols, and anti-cyclopropyl alcohols from achiral precursors. The methods begin with enantioselective C–C bond formations promoted by a MIB-based zinc catalyst to generate allylic alkoxide intermediates. The intermediates are then subjected to in situ alkoxide-directed cyclopropanation to provide cyclopropyl alcohols. In the synthesis of vinyl cyclopropyl alcohols, hydroboration of enynes is followed by transmetalation of the resulting dienylborane to zinc to provide dienylzinc reagents. Enantioselective addition to aldehydes generates the requisite dienyl zinc alkoxides, which are then subjected to in situ cyclopropanation to furnish vinyl cyclopropyl alcohols. Cyclopropanation occurs at the double bond allylic to the alkoxide. Using this method, syn-vinylcyclopropyl alcohols are obtained in 65–85% yield, 76–93% ee, and >19:1 dr. To prepare anti-cyclopropanols, enantioselective addition of alkylzinc reagents to conjugated enals provides allylic zinc alkoxides. Because direct cyclopropanation provides syn-cyclopropyl alcohols, the intermediate allylic alkoxides were treated with TMSCl/Et3N to generate intermediate silyl ethers. In situ cyclopropanation of the allylic silyl ether resulted in cyclopropanation to form the anti-cyclopropyl silyl ether. Workup with TBAF affords the anti-cyclopropyl alcohols in one-pot in 60–82% yield, 89–99% ee, and ≥10:1 dr. For the synthesis of cis-disubstituted cyclopropyl alcohols, in situ generated (Z)-vinyl zinc reagents were employed in asymmetric addition to aldehydes to generate (Z)-allylic zinc alkoxides. In situ cyclopropanation provides syn-cis-disubstituted cyclopropyl alcohols in 42–70% yield, 88–97% ee, and >19:1 dr. These one-pot procedures enable the synthesis of a diverse array of cyclopropyl alcohol building blocks with high enantio- and diastereoselectivities. PMID:19954146

Speciation analysis and leaching behaviors of selected trace elements in spent SCR catalyst.

PubMed

Dai, Zejun; Wang, Lele; Tang, Hao; Sun, Zhijun; Liu, Wei; Sun, Yi; Su, Sheng; Hu, Song; Wang, Yi; Xu, Kai; Liu, Liang; Ling, Peng; Xiang, Jun

2018-09-01

This study investigated heavy metal chemical speciation and leaching behavior from a board-type spent selective catalytic reduction (SCR) catalyst containing high concentrations of vanadium, chromium, nickel, copper, zinc, and lead. A three-step sequential extraction method, standard toxicity characteristic leaching procedure (TCLP), and leaching characteristic tests have been performed. It was found that the mobility of six heavy metals in the spent SCR catalyst was significantly different. The mobility of the six heavy metals exhibited the following order: Ni > Zn > V > Cr > As > Cu. Meanwhile, TCLP test results revealed relatively high Zn and Cr leaching rate of 83.20% and 10.35%, respectively. It was found that leaching rate was positively correlated with available contents (sum of acid soluble, reducible and oxidizable fractions). Leaching characteristics tests indicated that pH substantially affected the leaching of these heavy metals. In particular, the leaching of Cr, Ni, Cu, and Zn was positively influenced by strong acid, while V and As were easily released in the presence of strong acid and strong alkali (pH < 3 or pH > 11). In terms of kinetics, the leaching of Cr, Ni, Cu, Zn, and As within the spent catalyst was dominated by erosion and dissolution processes, which were rapid reaction processes. V was released in large amounts within 1 h, but its leaching amount sharply decreased with time due to readsorption. Copyright © 2018 Elsevier Ltd. All rights reserved.

Cobalt doped lanthanum chromite material suitable for high temperature use

DOEpatents

Ruka, R.J.

1986-12-23

A high temperature, solid electrolyte electrochemical cell, subject to thermal cycling temperatures of between about 25 C and about 1,200 C, capable of electronic interconnection to at least one other electrochemical cell and capable of operating in an environment containing oxygen and a fuel, is made; where the cell has a first and second electrode with solid electrolyte between them, where an improved interconnect material is applied along a portion of a supporting electrode; where the interconnect is made of a chemically modified lanthanum chromite, containing cobalt as the important additive, which interconnect allows for adjustment of the thermal expansion of the interconnect material to more nearly match that of other cell components, such as zirconia electrolyte, and is stable in oxygen containing atmospheres such as air and in fuel environments. 2 figs.

Orthopyroxene oikocrysts in the MG1 chromitite layer of the Bushveld Complex: implications for cumulate formation and recrystallisation

NASA Astrophysics Data System (ADS)

Kaufmann, Felix E. D.; Vukmanovic, Zoja; Holness, Marian B.; Hecht, Lutz

2018-02-01

Two typical mineral textures of the MG 1 chromitite of the Bushveld Complex, South Africa, were observed; one characterised by abundant orthopyroxene oikocrysts, and the other by coarse-grained granular chromitite with only minor amounts of interstitial material. Oikocrysts form elongate clusters of several crystals aligned parallel to the layering, and typically have subhedral, almost chromite-free, core zones containing remnants of olivine. The core zones are surrounded by poikilitic aureoles overgrowing euhedral to subhedral chromite chadacrysts. Chromite grains show no preferred crystal orientation, whereas orthopyroxene grains forming clusters commonly share the same crystallographic orientation. Oikocryst core zones have lower Mg# and higher concentrations of incompatible trace elements compared to their poikilitic aureoles. Core zones are relatively enriched in REE compared to a postulated parental magma (B1) and did not crystallise in equilibrium with the surrounding minerals, whereas the composition of the poikilitic orthopyroxene is consistent with growth from the B1 magma. These observations cannot be explained by the classic cumulus and post-cumulus models of oikocryst formation. Instead, we suggest that the oikocryst core zones in the MG1 chromitite layer formed by peritectic replacement of olivine primocrysts by reaction with an upwards-percolating melt enriched in incompatible trace elements. Poikilitic overgrowth on oikocryst core zones occurred in equilibrium with a basaltic melt of B1 composition near the magma-crystal mush interface. Finally, adcumulus crystallisation followed by grain growth resulted in the surrounding granular chromitite.

Chemical and mineralogical characterization of chromite ore processing residue from two recent Indian disposal sites.

PubMed

Matern, Katrin; Kletti, Holger; Mansfeldt, Tim

2016-07-01

Chromite ore processing residue (COPR) is a hazardous waste. Nevertheless, deposition of COPR in uncontrolled surface landfills is still common practice in some countries. Whereas old (between at least 40 and 180 years) COPR from the temperate zone has been intensively investigated, information on COPR in other regions is restricted. Relatively young (<25 years) COPR samples obtained from two abandoned landfill sites in India were investigated by a modified total microwave digestion method, X-ray powder diffraction (XRPD), and scanning electron microscopy (SEM) in order to determine their chemical and mineralogical nature. By the use of microwave digestion with acid mixtures of HNO3, H3PO4, and HBF4 (5:3:2 vol), COPR was completely dissolved and element contents similar to those obtained by X-ray fluorescence were found. Total Cr contents of the two COPR accounted for 81 and 74 g kg(-1), of which 20 and 13% were present in the carcinogenic hexavalent form (CrVI). Apart from the common major mineral phases present in COPR reported earlier, a further Cr host mineral, grimaldiite [CrO(OH)], could be identified by XRPD and SEM. Additionally, well soluble Na2CrO4 was present. Improving the effectiveness of chromite ore processing and preventing the migration of Cr(VI) into water bodies are the main challenges when dealing with these COPR. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metal-Organic Framework-Derived Reduced Graphene Oxide-Supported ZnO/ZnCo2O4/C Hollow Nanocages as Cathode Catalysts for Aluminum-O2 Batteries.

PubMed

Liu, Yisi; Jiang, Hao; Hao, Jiayu; Liu, Yulong; Shen, Haibo; Li, Wenzhang; Li, Jie

2017-09-20

Aluminum-air battery is a promising candidate for large-scale energy applications because of its low cost and high energy density. Remarkably, tremendous efforts have been concentrated on developing efficient and stable cathode electrocatalysts toward the oxygen reduction reaction. In this work, a hydrothermal-calcination approach was utilized to prepare novel reduced graphene oxide (rGO)-supported hollow ZnO/ZnCo 2 O 4 nanoparticle-embedded carbon nanocages (ZnO/ZnCo 2 O 4 /C@rGO) using a zeolitic imidazolate framework (ZIF-67)/graphene oxide/zinc nitrate composite as the precursor. The ZnO/ZnCo 2 O 4 /C@rGO hybrid exhibits remarkable electrocatalytic performance for oxygen reduction reaction under alkaline conditions and superior stability and methanol tolerance to those of the commercial Pt/C catalyst. Furthermore, novel and simple Al-air coin cells were first fabricated using the hybrid materials as cathode catalysts under ambient air conditions to further investigate their catalytic performance. The coin cell with the ZnO/ZnCo 2 O 4 /C@rGO cathode catalyst displays a higher open circuit voltage and discharge voltage and more sluggish potential drop than those of the cell with the ZnO/ZnCo 2 O 4 /C cathode catalyst, which confirms that rGO can enhance the electrocatalytic activity and stability of the catalyst system. The excellent electrocatalytic performance of the ZnO/ZnCo 2 O 4 /C@rGO hybrid is attributed to the prominent conductivity and high specific surface area resulting from rGO, the more accessible catalytic active sites induced by the unique porous hollow nanocage structure, and synergic covalent coupling between rGO sheets and ZnO/ZnCo 2 O 4 /C nanocages.

Synthesis of zinc aluminate with high surface area by microwave hydrothermal method applied in the transesterification of soybean oil (biodiesel)

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

Quirino, M.R.; Oliveira, M.J.C.; Keyson, D.

Highlights: • ZnAl{sub 2}O{sub 4} spinel was synthesized by the microwave hydrothermal method in only 15 or 30 min. • The powders show high specific surface area. • ZAT{sub b}15 showed activity of 52.22% for the conversion of soybean oil into biodiesel. - Abstract: Zinc aluminate is a material with high thermal stability and high mechanical strength that, owing to these properties, is used as a catalyst or support. In this work, zinc aluminate spinel was synthesized by the microwave hydrothermal method in only 15 or 30 min at a low temperature (150 °C) without templates, using only Al(NO{sub 3}){submore » 3}·9H{sub 2}O, Zn(NO{sub 3}){sub 2}·6H{sub 2}O, and urea as precursors and applied in the transesterification of soybean oil. X-ray diffraction analysis showed that ZnAl{sub 2}O{sub 4} had a cubic structure without secondary phases. The nitrogen adsorption measurements (BET) revealed a high surface area (266.57 m{sup 2} g{sup −1}) for the nanopowder synthesized in 15 min. This powder showed activity of 52.22% for the catalytic conversion of soybean oil into biodiesel by transesterification.« less

Transition metal-modified zinc oxides for UV and visible light photocatalysis.

PubMed

Bloh, J Z; Dillert, R; Bahnemann, D W

2012-11-01

In order to use photocatalysis with solar light, finding more active and especially visible light active photocatalysts is a very important challenge. Also, studies of these photocatalysts should employ a standardized test procedure so that their results can be accurately compared and evaluated with one another. A systematic study of transition metal-modified zinc oxide was conducted to determine whether they are suitable as visible light photocatalysts. The photocatalytic activity of ZnO modified with eight different transition metals (Cu, Co, Fe, Mn, Ni, Ru, Ti, Zr) in three different concentrations (0.01, 0.1, and 1 at.%) was investigated under irradiation with UV as well as with visible light. The employed activity test is the gas-phase degradation of acetaldehyde as described by the ISO standard 22197-2. The results suggest that the UV activity can be improved with almost any modification element and that there exists an optimal modification ratio at about 0.1 at.%. Additionally, Mn- and Ru-modified ZnO display visible light activity. Especially the Ru-modified ZnO is highly active and surpasses the visible light activity of all studied titania standards. These findings suggest that modified zinc oxides may be a viable alternative to titanium dioxide-based catalysts for visible light photocatalysis. Eventually, possible underlying mechanisms are proposed and discussed.

Catalytically active nanorotor reversibly self-assembled by chemical signaling within an eight-component network.

PubMed

Goswami, Abir; Pramanik, Susnata; Schmittel, Michael

2018-04-17

A catalytically active three-component nanorotor is reversibly self-assembled and disassembled by remote control. When zinc(ii) ions (2 equiv.) are added as an external chemical trigger to the mixture of transmitter [Cu(1)]+ and pre-rotor assembly [(S)·(R)], two equiv. of copper(i) ions translocate from [Cu(1)]+ to the two phenanthroline sites of [(S)·(R)]. As a result, [Zn(1)]2+ forms along with the three-component assembly [Cu2(S)(R)]2+, which is both a nanorotor (k298 = 46 kHz, ΔH‡ = 49.1 ± 0.4 kJ mol-1, ΔS‡ = 9.5 ± 1.7 J mol-1 K-1) and a catalyst for click reactions (catalysis ON: A + B→AB). Removal of zinc from the mixture reverts the translocation sequence and thus commands disassembly of the catalytically active rotor (catalysis OFF). The ON/OFF catalytic cycle was run twice in situ in the full network.

Hydrogenation of CO 2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis

DOE PAGES

Palomino, Robert M.; Ramirez, Pedro J.; Liu, Zongyuan; ...

2017-08-21

The results of kinetic tests and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) show the important role played by a ZnO–copper interface in the generation of CO and the synthesis of methanol from CO 2 hydrogenation. The deposition of nanoparticles of ZnO on Cu(100) and Cu(111), θ oxi < 0.3 monolayer, produces highly active catalysts. The catalytic activity of these systems increases in the sequence: Cu(111) < Cu(100) < ZnO/Cu(111) < ZnO/Cu(100). The structure of the copper substrate influences the catalytic performance of a ZnO–copper interface. Furthermore, size and metal–oxide interactions affect the chemical and catalytic properties of the oxide making themore » supported nanoparticles different from bulk ZnO. The formation of a ZnO–copper interface favors the binding and conversion of CO 2 into a formate intermediate that is stable on the catalyst surface up to temperatures above 500 K. Alloys of Zn with Cu(111) and Cu(100) were not stable at the elevated temperatures (500–600 K) used for the CO 2 hydrogenation reaction. However, reaction with CO 2 oxidized the zinc, enhancing its stability over the copper substrates.« less

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

PubMed

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

2017-11-01

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

Hydrogenation of CO 2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis

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

Palomino, Robert M.; Ramirez, Pedro J.; Liu, Zongyuan

The results of kinetic tests and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) show the important role played by a ZnO–copper interface in the generation of CO and the synthesis of methanol from CO 2 hydrogenation. The deposition of nanoparticles of ZnO on Cu(100) and Cu(111), θ oxi < 0.3 monolayer, produces highly active catalysts. The catalytic activity of these systems increases in the sequence: Cu(111) < Cu(100) < ZnO/Cu(111) < ZnO/Cu(100). The structure of the copper substrate influences the catalytic performance of a ZnO–copper interface. Furthermore, size and metal–oxide interactions affect the chemical and catalytic properties of the oxide making themore » supported nanoparticles different from bulk ZnO. The formation of a ZnO–copper interface favors the binding and conversion of CO 2 into a formate intermediate that is stable on the catalyst surface up to temperatures above 500 K. Alloys of Zn with Cu(111) and Cu(100) were not stable at the elevated temperatures (500–600 K) used for the CO 2 hydrogenation reaction. However, reaction with CO 2 oxidized the zinc, enhancing its stability over the copper substrates.« less

Amine-functionalized Zn(ii) MOF as an efficient multifunctional catalyst for CO2 utilization and sulfoxidation reaction.

PubMed

Patel, Parth; Parmar, Bhavesh; Kureshy, Rukhsana I; Khan, Noor-Ul H; Suresh, Eringathodi

2018-06-19

Herein, a zinc(ii)-based 3D mixed ligand metal organic framework (MOF) was synthesized via versatile routes including green mechanochemical synthesis. The MOF {[Zn(ATA)(L)·H2O]}n (ZnMOF-1-NH2) has been characterized by various physico-chemical techniques, including SCXRD, and composed of the bipyridyl-based Schiff base (E)-N'-(pyridin-4-ylmethylene)isonicotinohydrazide (L) and 2-aminoterephthalic acid (H2ATA) ligands as linkers. The MOF material has been explored as a multifunctional heterogeneous catalyst for the cycloaddition of alkyl and aryl epoxides with CO2 and sulfoxidation reactions of aryl sulfides. The influence of various reaction parameters is examined to optimize the performance of the catalytic reactions. It is found that solvent-free catalytic reaction conditions offer good catalytic conversion in the case of cyclic carbonates, and for sulfoxide, good conversion and selectivity are achieved in the presence of DCM as a solvent medium under ambient reaction conditions. The chemical and thermal stability of the catalyst are excellent and it is active for up to four catalytic cycles without significant loss in activity. Furthermore, based on the catalytic activity and structural evidence, a plausible mechanism for both catalytic reactions is proposed.

Self-sensitization of tetracycline degradation with simulated solar light catalyzed by ZnO@montmorillonite

NASA Astrophysics Data System (ADS)

Zyoud, Ahed; Jondi, Waheed; AlDaqqah, Najat; Asaad, Sara; Qamhieh, Naser; Hajamohideen, AbdulRazack; Helal, Muath H. S.; Kwon, Hansang; Hilal, Hikmat S.

2017-12-01

Zinc oxide (ZnO) nano-particles were chemically deposited onto montmorillonite (MONT) clay particles. The composite ZnO@MONT was then characterized and used as a catalyst for photo-degradation of aqueous tetracycline. Unlike earlier studies, solar simulated light can be effectively used in this work. The composite shows high efficiency as adsorbent and as a photo-degradation catalyst. Both adsorbed and dissolved tetracycline molecules undergo mineralization under the photo-catalytic conditions, and up to 94% of the contaminant gross amount is completely mineralized. Other forms of ZnO particles, commercial ZnO and synthetic ZnO particles were examined in separate experiments. The ZnO@MONT is superior to both pristine counterparts. The ability of tetracycline to sensitize the supported ZnO particles, to solar simulated light, before being photo-degraded itself, is discussed here for the first time. In addition to enhanced catalytic activity of the ZnO@MONT, the composite can be efficiently recovered and reused with no significant loss of efficiency.

Comparison of Cu2+ and Zn2+ thermalcatalyst in treating diazo dye

NASA Astrophysics Data System (ADS)

Lau, Y. Y.; Wong, Y. S.; Ong, S. A.; Lutpi, N. A.; Ho, L. N.

2018-05-01

This research demonstrates the comparison between copper (II) sulphate (CuSO4) and zinc oxide (ZnO) as thermalcatalysts in thermolysis process for the treatment of diazo reactive black 5 (RB 5) wastewater. CuSO4 was found to be the most effective thermalcatalyst in comparison to ZnO. The color removal efficiency of RB 5 catalysed by CuSO4 and ZnO were 91.55 % at pH 9.5 and 7.36 % at pH 2, respectively. From the UV-Vis wavelength scan, CuSO4 catalyst is able to cleave the molecular structure bonding more efficiently compared to ZnO. ZnO which only show a slight decay on the main chemical network strands: azo bond, naphthalene and benzene rings whereas CuSO4 catalyst is able to fragment azo bond and naphthalene more effectively. The degradation reactions of CuSO4 and ZnO as thermalcatalysts in thermolysis process were compared.

Aromatization of n-hexane over ZnO/H-ZSM-5 catalysts

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

Kanai, J.; Kawata, N.

The mechanism of transformation of n-hexane into aromatics over ZnO/H-ZSM-5 catalyst has been investigated. The yields of aromatics in the transformation of n-hexane over H-ZSM-5 are enhanced by mechanical mixing of ZnO as well as by ion exchange or impregnation of zinc cation. It is concluded that aromatization of n-hexane over ZnO/H-ZSM-5 is a bifunctional reaction, and that ZnO as well as H-ZSM-5 takes part both in the activation of n-hexane and in the aromatization of lower olefins. By contrasting the conversion of n-hexane with that of 1-hexane, it is found that aromatization of n-hexane over ZnO/H-ZSM-5 involves both themore » dehydrogenation of n-hexane into hexene and that of the oligomerized products into aromatics. It is proposed that ZnO catalyzes the dehydrogenation of n-hexane into hexene and of the oligomerized products into aromatics.« less

Synthesis of ZnO-CuO/MCM-48 photocatalyst for the degradation of organic pollutions.

PubMed

Duan, Yongzheng; Shen, Yulian

2017-07-01

The photocatalytic properties of ZnO-CuO catalysts supported on siliceous MCM-48 (Mobil Composition of Matter No. 48) for the degradation of organic pollutions such as methylene blue and salicylic acid under UV light irradiation were investigated. These catalysts were prepared by impregnation of MCM-48 with a mixed aqueous solution of copper acetate and zinc acetate. X-ray diffraction, N 2 -physisorption, high resolution transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and photoluminescence were used to characterize these samples. Results from characterizations showed that the addition of ZnO to CuO/MCM-48 could markedly improve the photocatalytic degradation properties. The enhanced photocatalytic behaviors of ZnO-CuO/MCM-48 may be due to the formation of p-n heterojunctions between ZnO and CuO, resulting in the effective separation of photogenerated electron-hole pairs. Moreover, the photocatalysts were easily recovered and reused for five cycles without considerable loss of activity.

Application of the radioisotope excited X-ray fluorescence technique in charge optimization during thermite smelting of Fe-Ni, Fe-cr, and Fe-Ti alloys

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

Sharma, I.G.; Joseph, D.; Lal, M.

1995-10-01

A wide range of ferroalloys are used to facilitate the addition of different alloying elements to molten steel. High-carbon ferroalloys are produced on a tonnage basis by carbothermic smelting in an electric furnace, and an aluminothermic route is generally adopted for small scale production of low-carbon varieties. The physicochemical principles of carbothermy and aluminothermy have been well documented in the literature. However, limited technical data are reported on the production of individual ferroalloys of low-carbon varieties from their selected resources. The authors demonstrate her the application of an energy dispersive X-ray fluorescence (EDXRF) technique in meeting the analytical requirements ofmore » a thermite smelting campaign, carried out with the aim of preparing low-carbon-low-nitrogen Fe-Ni, Fe-Cr, and Fe-Ti alloys from indigenously available nickel bearing spent catalyst, mineral chromite, and ilmenite/rutile, respectively. They have chosen the EDXRF technique to meet the analytical requirements because of its capability to analyze samples of ore, minerals, a metal, and alloys in different forms, such as powder, sponge, as-smelted, or as-cast, to obtain rapid multielement analyses with ease. Rapid analyses of thermite feed and product by this technique have aided in the appropriate alterations of the charge constitutents to obtain optimum charge consumption.« less

Complete zircon and chromite digestion by sintering of granite, rhyolite, andesite and harzburgite rock reference materials for geochronological purposes

NASA Astrophysics Data System (ADS)

Bokhari, Syed Nadeem H.; Meisel, Thomas

2014-05-01

Zircon (ZrSiO4) is a common accessory mineral in nature that occurs in a wide variety of sedimentary, igneous, and metamorphic rocks. Zircon has the ability to retain substantial chemical and isotopic information that are used in range of geochemical and geo- chronological investigations. Sample digestion of such rock types is a limiting factor due to the chemical inertness of zircon (ZrSiO4) tourmaline, chromite, barite, monazite, sphene, xenotime etc. as the accuracy of results relies mainly on recovery of analytes from these minerals. Dissolution by wet acid digestions are often incomplete and high blank and total dissolved solids (TDS) contents with alkali fusions lead to an underestimation of analyte concentrations. Hence an effective analytical procedure, that successfully dissolves refractory minerals such as zircon is needed to be employed for reliable analytical results. Na2O2 digestion [1] was applied in characterisation of granite (G-3), rhyolite (MRH), andesite (MGL-AND) and harzburgite (MUH-1) powdered reference material with solution based ICP-MS analysis. In this study we undertake a systematic evaluation of decomposition time and sample:Na2O2 ratio and test portion size after minimising effect of all other constraints that makes homogeneity ambiguous. In recovering zircon and chromite 100 mg test portion was mixed with different amounts of Na2O2 i.e. 100-600 mg. Impact of decomposition time was observed by systematically increasing heating time from 30-45 minutes to 90-120 minutes at 480°C. Different test portion sizes 100-500 mg of samples were digested to control variance of inhomogeneity. An improved recovery of zirconium in zircon in granite (G-3), rhyolite MRH), andesite (MGL-AND) and chromite in harzburgite (MUH-1) was obtained by increasing heating time (2h) at 480°C and by keeping (1:6) ratio of sample:Na2O2. Through this work it has been established that due to presence of zircon and chromite, decomposition time and sample:Na2O2 ratio has to be increased for an accurate content determination and complete release of analytes for geochronological studies. Larger test portion size reduces the heterogeneity issues in granites in particular [2]. No significant blanks issues were observed and interferences were controlled using QQQ MS mode of ICP-MS. References [1] Meisel, T., N. Schöner, et al. (2002). "Determination of Rare Earth Elements, Y, Th, Zr, Hf, Nb and Ta in Geological Reference Materials G-2, G-3, SCo-1 and WGB-1 by Sodium Peroxide Sintering and Inductively Coupled Plasma-Mass Spectrometry." Geostandards Newsletter 26(1): 53-61. [2] Bokhari SNH., Meisel T (2013) "The Determination of Homogeneity of Geological Reference Material" Mineralogical Magazine, 77(5): 731.

The Role of Spinel Minerals in Lunar Magma Evolution

NASA Astrophysics Data System (ADS)

Taylor, L. A.; Head, J. W.; Pieters, C. M.; Sunshine, J. M.; Staid, M.; Isaacson, P.; Petro, N. E.

2009-12-01

The Moon Mineralogy Mapper (M3), a NASA guest instrument on Chandrayaan-1, India’s first mission to the Moon, was designed to map the surface mineralogy of the Moon using reflected solar radiation at visible and near-infrared wavelengths, which contain highly diagnostic absorptions due to minerals. The M3 spectrometer has discovered several new and unexpected aspects of the geology and petrology of the Moon, some involving specific oxide phases. Spinel minerals, with the general formula, AB2O4, present clues as to the oxygen fugacity, the nature of magmatic systems, and their evolution, particularly during the early stages of crystallization. On the Moon, with its total lack of Fe3+ and minerals such as magnetite, observed spinels range between spinel, MgAl2O4; hercynite, FeAl2O4; Chromite, FeCr2O4; and ulvöspinel, Fe(FeTi)2O4. They manifest themselves in three distinctly different igneous rock types: highlands rocks of anorthosites/troctolites, gabbro-norites; mare basalts with various TiO2 contents; and basaltic pyroclastic volcanic glasses. Although spinels occur as minor minerals in the Apollo collection, unique rock types dominated by Mg-spinel (with olivine and pyroxene abundances below detection limits, assumed to be ~5%) have been identified by M3 on the Moon. Because the spinel-bearing rocks detected by M3 have no signature of a significant olivine component, they must be dominated by plagioclase and spinel. Pink Mg-spinels typically occur as a minor phase in troctolites (plagioclase + olivine), a highland rock formed after the initial Ferroan Anorthosite (FAN) crust, presumably by serial magmatism deep within the crust, with intrusion upward. FANs were formed by floatation of plagioclase in the lunar magma ocean (LMO), whereas spinels would sink due to their much higher density. Thus, a plagioclase-rich rock type with a strong Mg-spinel spectral signature would have to be part of later highland intrusives. The excess Mg-spinel could be the product of crystal settling in an anorthositic magma chamber, much like in anorthositic layered intrusives on Earth. On the Moon, this would be a cumulate spinel anorthosite, never before seen in remote sensing or in the lunar sample collection. Virtually all types of mare basalt melts have chromite at or near the liquidus, closely associated with olivine or low-Ca pyroxene. During crystallization, the chromite becomes more Ti-rich, typically with nearly continuous solid-solution zonation outward to ulvöspinel. Pyroclastic orange/black glass on the Moon typically contains dendritic crystallites of ilmenite and olivine, a product of the rich-TiO2 content of the fire-fountain melt. However, other pyroclastic melt compositions, with high-Cr and low-Ti contents, have chromite on the liquidus, which could result in dendrites of chromite and olivine in the volcanic glass. Here again, M3 is seeing spinel-dominated materials, this time in close association with pyroclastic deposits.

[Optimization of ethylene production from ethanol dehydration using Zn-Mn-Co/HZSM-5 by response surface methodology].

PubMed

Wang, Wei; Cheng, Keke; Xue, Jianwei; Zhang, Jian'an

2011-03-01

The effects of reaction temperature, ethanol concentration and weight hourly space velocity (WHSV) on the ethylene production from ethanol dehydration using zinc, manganese and cobalt modified HZSM-5 catalyst were investigated by response surface methodology (RSM). The results showed that the most significant effect among factors was reaction temperature and the factors had interaction. The optimum conditions were found as 34.4% ethanol concentration, 261.3 0 degrees C of reaction temperature and 1.18 h(-1) of WHSV, under these conditions the yield of ethylene achieved 98.69%.

Impact of lubricant additives on the physicochemical properties and activity of three-way catalysts

DOE PAGES

Toops, Todd J.; Lance, Michael J.; Qu, Jun; ...

2016-04-04

As alternative lubricant anti-wear additives are sought to reduce friction and improve overall fuel economy, it is important that these additives are also compatible with current emissions control catalysts. In the present work, an oil-miscible phosphorous-containing ionic liquid (IL), trihexyltetradecylphosphonium bis(2-ethylhexyl) phosphate ([P 66614][DEHP]), is evaluated for its impact on three-way catalysts (TWC) and benchmarked against the industry standard zinc-dialkyl-dithio-phosphate (ZDDP). The TWCs are aged in different scenarios: neat gasoline (no-additive, or NA), gasoline+ZDDP, and gasoline+IL. The aged samples, along with the as received TWC, are characterized through various analytical techniques including catalyst reactivity evaluation in a bench-flow reactor. Themore » temperatures of 50% conversion (T50) for the ZDDP-aged TWCs increased by 30, 24, and 25 °C for NO, CO, and C3H6, respectively, compared to the no-additive case. Although the IL-aged TWC also increased in T50 for CO and C3H6, it was notably less than ZDDP, 7 and 9 °C, respectively. Additionally, the IL-aged samples had higher water-gas-shift reactivity and oxygen storage capacity than the ZDDP-aged TWC. Characterization of the aged samples indicated the predominant presence of CePO 4 in the ZDDP-aged TWC aged by ZDDP, while its formation was retarded in the case of IL where higher levels of AlPO 4 is observed. Furthermore, the results in this work indicate that the phosphonium-phosphate IL potentially has less adverse impact on TWC than ZDDP.« less

Impact of lubricant additives on the physicochemical properties and activity of three-way catalysts

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

Toops, Todd J.; Lance, Michael J.; Qu, Jun

As alternative lubricant anti-wear additives are sought to reduce friction and improve overall fuel economy, it is important that these additives are also compatible with current emissions control catalysts. In the present work, an oil-miscible phosphorous-containing ionic liquid (IL), trihexyltetradecylphosphonium bis(2-ethylhexyl) phosphate ([P 66614][DEHP]), is evaluated for its impact on three-way catalysts (TWC) and benchmarked against the industry standard zinc-dialkyl-dithio-phosphate (ZDDP). The TWCs are aged in different scenarios: neat gasoline (no-additive, or NA), gasoline+ZDDP, and gasoline+IL. The aged samples, along with the as received TWC, are characterized through various analytical techniques including catalyst reactivity evaluation in a bench-flow reactor. Themore » temperatures of 50% conversion (T50) for the ZDDP-aged TWCs increased by 30, 24, and 25 °C for NO, CO, and C3H6, respectively, compared to the no-additive case. Although the IL-aged TWC also increased in T50 for CO and C3H6, it was notably less than ZDDP, 7 and 9 °C, respectively. Additionally, the IL-aged samples had higher water-gas-shift reactivity and oxygen storage capacity than the ZDDP-aged TWC. Characterization of the aged samples indicated the predominant presence of CePO 4 in the ZDDP-aged TWC aged by ZDDP, while its formation was retarded in the case of IL where higher levels of AlPO 4 is observed. Furthermore, the results in this work indicate that the phosphonium-phosphate IL potentially has less adverse impact on TWC than ZDDP.« less

The Preparation and Characterization of Materials.

ERIC Educational Resources Information Center

Wold, Aaron

1980-01-01

Presents several examples illustrating different aspects of materials problems, including problems associated with solid-solid reactions, sintering and crystal growth, characterization of materials, preparation and characterization of stoichiometric ferrites and chromites, copper-sulfur systems, growth of single crystals by chemical vapor…

Peridotite-suite dominated mineral inclusions in diamonds from Kelsey Lake Mine, Colorado U.S.A.

NASA Astrophysics Data System (ADS)

Schulze, D. J.; Coopersmith, H. G.

2005-12-01

Thirty silicate and oxide inclusions large enough for in situ WDS electron microprobe analysis were exposed by grinding/polishing of 16 diamonds from the Kelsey Lake Mine in the Colorado-Wyoming State Line kimberlite district. Three garnets in two stones belong to the eclogite (E) suite, and 18 olivines, three Mg-chromites and six Cr-pyropes in the other 14 stones belong to the peridotite (P) suite. The peridotite-dominated population is in stark contrast to the other suites studied in the State Line district. The reported inclusion population from George Creek is completely eclogitic and that of the Sloan pipe is overwhelmingly eclogitic, with only a minor, relatively Fe-rich peridotite component. Multiple inclusions are common in single stones, with 12 olivines (of uniform composition) exposed in one example. Kelsey Lake olivine inclusions are magnesian (17 of 18 grains in 9 stones are in the range Fo 92.7-93.1), typical of P-suite stones worldwide, but unlike the more Fe-rich Sloan olivine suite (13 of 14 in the range Fo 91.3-92.2). Mg-chromites (wt percent MgO = 12.8-13.8, wt percent Cr2O3 = 61.4-66.6) are in the lower MgO range of diamond inclusion chromites worldwide. Six Cr-pyropes in four stones have moderately low calcium contents (wt percent CaO = 3.5-4.5) but are very Cr-rich (wt percent Cr2O3 = 10.5-16.7). An olivine-garnet pair in one stone yields a Mg-Fe exchange temperature of 895 degrees C, possibly indicating disequilibrium, whereas an olivine-chromite pair yields an Mg-Fe exchange temperature of 1035 degrees C, cool but reasonable for equilibration within the diamond stability field. Comparison with diamond inclusion minerals worldwide reveals that the Kesley Lake suite is most similar to those from the Slave Craton in Canada, especially in terms of Cr-pyrope compositions. Both suites are somewhat less depleted than suites from southern Africa or Siberian kimberlites. By analogy with the Slave P-suite diamonds of Archean age and a Proterozoic eclogitic component in the Slave mantle, the mixed diamond inclusion populations from the State Line district may support models in which blocks of Archean mantle survive buried beneath Proterozoic continental crust, mixed with eclogitic regimes emplaced by Proterozoic subduction.

A regional-scale study of chromium and nickel in soils of northern California, USA

USGS Publications Warehouse

Morrison, J.M.; Goldhaber, M.B.; Lee, L.; Holloway, J.M.; Wanty, R.B.; Wolf, R.E.; Ranville, J.F.

2009-01-01

A soil geochemical survey was conducted in a 27,000-km2 study area of northern California that includes the Sierra Nevada Mountains, the Sacramento Valley, and the northern Coast Range. The results show that soil geochemistry in the Sacramento Valley is controlled primarily by the transport and weathering of parent material from the Coast Range to the west and the Sierra Nevada to the east. Chemically and mineralogically distinctive ultramafic (UM) rocks (e.g. serpentinite) outcrop extensively in the Coast Range and Sierra Nevada. These rocks and the soils derived from them have elevated concentrations of Cr and Ni. Surface soil samples derived from UM rocks of the Sierra Nevada and Coast Range contain 1700-10,000 mg/kg Cr and 1300-3900 mg/kg Ni. Valley soils west of the Sacramento River contain 80-1420 mg/kg Cr and 65-224 mg/kg Ni, reflecting significant contributions from UM sources in the Coast Range. Valley soils on the east side contain 30-370 mg/kg Cr and 16-110 mg/kg Ni. Lower Cr and Ni concentrations on the east side of the valley are the result of greater dilution by granitic sources of the Sierra Nevada. Chromium occurs naturally in the Cr(III) and Cr(VI) oxidation states. Trivalent Cr is a non-toxic micronutrient, but Cr(VI) is a highly soluble toxin and carcinogen. X-ray diffraction and scanning electron microscopy of soils with an UM parent show Cr primarily occurs within chromite and other mixed-composition spinels (Al, Mg, Fe, Cr). Chromite contains Cr(III) and is highly refractory with respect to weathering. Comparison of a 4-acid digestion (HNO3, HCl, HF, HClO4), which only partially dissolves chromite, and total digestion by lithium metaborate (LiBO3) fusion, indicates a lower proportion of chromite-bound Cr in valley soils relative to UM source soils. Groundwater on the west side of the Sacramento Valley has particularly high concentrations of dissolved Cr ranging up to 50 ??g L-1 and averaging 16.4 ??g L-1. This suggests redistribution of Cr during weathering and oxidation of Cr(III)-bearing minerals. It is concluded that regional-scale transport and weathering of ultramafic-derived constituents have resulted in enrichment of Cr and Ni in the Sacramento Valley and a partial change in the residence of Cr.

Recycling of crustal materials through study of ultrahigh-pressure minerals in collisional orogens, ophiolites, and mantle xenoliths: A review

NASA Astrophysics Data System (ADS)

Liou, Juhn G.; Tsujimori, Tatsuki; Yang, Jingsui; Zhang, R. Y.; Ernst, W. G.

2014-12-01

Newly recognized occurrences of ultrahigh-pressure (UHP) minerals including diamonds in ultrahigh-temperature (UHT) felsic granulites of orogenic belts, in chromitites associated with ophiolitic complexes, and in mantle xenoliths suggest the recycling of crustal materials through deep subduction, mantle upwelling, and return to the Earth's surface. This circulation process is supported by crust-derived mineral inclusions in deep-seated zircons, chromites, and diamonds from collision-type orogens, from eclogitic xenoliths in kimberlites, and from chromitities of several Alpine-Himalayan and Polar Ural ophiolites; some of these minerals contain low-atomic number elements typified by crustal isotopic signatures. Ophiolite-type diamonds in placer deposits and as inclusions in chromitites together with numerous highly reduced minerals and alloys appear to have formed near the mantle transition zone. In addition to ringwoodite and inferred stishovite, a number of nanometric minerals have been identified as inclusions employing state-of-the-art analytical tools. Reconstitution of now-exsolved precursor UHP phases and recognition of subtle decompression microstructures produced during exhumation reflect earlier UHP conditions. For example, Tibetan chromites containing exsolution lamellae of coesite + diopside suggest that the original chromitites formed at P > 9-10 GPa at depths of >250-300 km. The precursor phase most likely had a Ca-ferrite or a Ca-titanite structure; both are polymorphs of chromite and (at 2000 °C) would have formed at minimum pressures of P > 12.5 or 20 GPa respectively. Some podiform chromitites and host peridotites contain rare minerals of undoubted crustal origin, including zircon, feldspars, garnet, kyanite, andalusite, quartz, and rutile; the zircons possess much older U-Pb ages than the time of ophiolite formation. These UHP mineral-bearing chromitite hosts evidently had a deep-seated evolution prior to extensional mantle upwelling and partial melting at shallow depths to form the overlying ophiolite complexes. These new findings together with stable isotopic and inclusion characteristics of diamonds provide compelling evidence for profound underflow of both oceanic and continental lithosphere, recycling of surface 'organic' carbon into the lower mantle, and ascent to the Earth's surface through mantle upwelling. Intensified study of UHP granulite-facies lower crustal basement and ophiolitic chromitites should allow a better understanding of the geodynamics of subduction and crustal cycling.

ZnxCd1-xSe alloy nanowires covering the entire compositional range grown by metalorganic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Shan, C. X.; Liu, Z.; Ng, C. M.; Hark, S. K.

2005-07-01

We show that preferentially oriented, single-crystalline ZnxCd1-xSe alloy nanowires can be grown on GaAs (100) surface using Au as a catalyst over the entire compositional range in a metalorganic chemical vapor deposition system. The composition of the alloy nanowires can be simply adjusted through the ratio of the flow rates of group-II precursors. Electron microscopy shows that the nanowires are smooth and uniform in shape; their diameters range from 20 to 80 nm and lengths exceed a few micrometers. Nanowires containing more than 13% Zn are zinc blende structured and grow along the ⟨110⟩ direction. Those containing less Zn are wurtzite structured and grow along the ⟨210⟩ direction. Compared with the bulk alloy, the change from zinc blende to wurtzite structure in nanowires occurs at far smaller x. The preferred orientation and the persistence of the zinc blende structure both reflect the influence of the substrate on the growth of the nanowires. Photoluminescence measurements identify a strong near-band-edge emission for all samples and show that its peak energy tracks the band gap of ZnxCd1-xSe epilayer for x>0.13. The growth of alloy nanowires at many compositions opens up the possibility of realizing quasi-one-dimensional heterojunctions.

The Role of Phosphorus and Soot on the Deactivation of Diesel Oxidation Catalysts

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

Eaton, Scott J; Nguyen, Ke; Bunting, Bruce G

The deactivation of diesel oxidation catalysts (DOCs) by soot contamination and lube-oil derived phosphorus poisoning is investigated. Pt/CeO2/-Al2O3 DOCs aged using three different protocols developed by the authors and six high mileage field-returned DOCs of similar formulation are evaluated for THC and CO oxidation performance using a bench-flow reactor. Collectively, these catalysts exhibit a variety of phosphorus and soot morphologies contributing to performance deactivation. To isolate and examine the contribution of each deactivation mechanism, performance evaluations are carried out for each DOC ''as received'' and after removal of surface carbon in a high-temperature oxidizing environment. In such a manner themore » deactivation contribution of soot contamination is de-convoluted from that of phosphorus poisoning. It will be shown that this is accomplished while preserving phosphorus (and to a lesser degree sulfur, calcium and zinc) chemistries and concentrations within the washcoat. Washcoat contaminant information and materials changes are characterized using electron-probe microanalysis (EPMA), X-ray diffraction (XRD), scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS), BET surface area, oxygen storage capacity (OSC), X-ray fluorescence (XRF) and inductively coupled plasma (ICP) analysis, from which the relative severity of each mechanism can be quantified. Results show that soot contamination from diesel exhaust severely degrades THC and CO oxidation performance by acting as a catalyst surface diffusion barrier. This results in a considerable increase of light-off temperatures. In contrast, phosphorus poisoning, which is considered a significant deactivation mechanism in three-way catalysts, is shown to have minimal effect on DOC oxidation performance for the conditions studied here. Material changes include the formation of both Ce(III-IV) and aluminum phosphates which do not significantly hinder the THC and CO oxidation in lean exhaust. In addition, thermal aging and sulfur poisoning are shown to produce minimal contributions to the overall deactivation. Consequently, performance of aged DOCs after soot removal is observed to be comparable to that of a fresh catalyst under our testing conditions.« less

Warm Cleanup of Coal-Derived Syngas: Multicontaminant Removal Process Demonstration

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

Spies, Kurt A.; Rainbolt, James E.; Li, Xiaohong S.

Warm cleanup of coal- or biomass-derived syngas requires sorbent and catalytic beds to protect downstream processes and catalysts from fouling. Sulfur is particularly harmful because even parts-per-million amounts are sufficient to poison downstream synthesis catalysts. Zinc oxide (ZnO) is a conventional sorbent for sulfur removal; however, its operational performance using real gasifier-derived syngas and in an integrated warm cleanup process is not well reported. In this paper, we report the optimal temperature for bulk desulfurization to be 450oC, while removal of sulfur to parts-per-billion levels requires a lower temperature of approximately 350oC. Under these conditions, we found that sulfur inmore » the form of both hydrogen sulfide and carbonyl sulfide could be absorbed equally well using ZnO. For long-term operation, sorbent regeneration is desirable to minimize process costs. Over the course of five sulfidation and regeneration cycles, a ZnO bed lost about a third of its initial sulfur capacity, however sorbent capacity stabilized. Here, we also demonstrate, at the bench-scale, a process and materials used for warm cleanup of coal-derived syngas using five operations: 1) Na2CO3 for HCl removal, 2) regenerable ZnO beds for bulk sulfur removal, 3) a second ZnO bed for trace sulfur removal, 4) a Ni-Cu/C sorbent for multi-contaminant inorganic removal, and 5) a Ir-Ni/MgAl2O4 catalyst employed for ammonia decomposition and tar and light hydrocarbon steam reforming. Syngas cleanup was demonstrated through successful long-term performance of a poison-sensitive, Cu-based, water-gas-shift catalyst placed downstream of the cleanup process train. The tar reformer is an important and necessary operation with this particular gasification system; its inclusion was the difference between deactivating the water-gas catalyst with carbon deposition and successful 100-hour testing using 1 LPM of coal-derived syngas.« less

Assessment of heavy metal contamination in sediment at Sukinda ultramafic complex using HAADF-STEM analysis.

PubMed

Equeenuddin, Sk Md; Pattnaik, Binaya Kumar

2017-10-01

The Sukinda ultramafic complex in Odisha has the largest chromite reserve in India. Sediment derived from ultramafic rocks has been enriched with various metals. Further, mining activities enhance the influx of metals into sediment by dumping mine overburden and tailings in the open area. Metal concentration in sediment is found in order of Cr Total (Cr) > Mn > Ni > Co > Zn > Cu with average concentration 26,778 mg/kg, 3098 mg/kg, 1813 mg/kg, 184 mg/kg, 116 mg/kg and 44 mg/kg respectively. Concentration of Cr(VI) varies from 5.25 to 26.47 mg/L with an average of 12.27 mg/L. Based on various pollution indices, it is confirmed that the area is severely contaminated. Nano-scale goethite, kaolinite, clinochlore and chromite have been identified and have high concentration of Cr, Co and Ni. Goethite has shown maximum metal retention potential as deciphered by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The HAADF-STEM mapping and principal component analysis indicate that Cr and Co mostly derived from chromite whereas Ni and Zn are derived from serpentine. Later, these metals co-precipitate and/or adsorbed onto the goethite and clay minerals. Fractionation study of metals confirms that Cu is the most mobile element followed by Zn. However, at low pH condition Ni is mobilized and likely to be bioavailable. Though Cr mostly occurs in residual fraction but as its concentration is very high, a small proportion of exchangeable fraction contributes significantly in terms of its bioavailability. Thus bioavailable Cr can pose severe threat to the environment in the Sukinda ultramafic complex. Copyright © 2017 Elsevier Ltd. All rights reserved.

Health risk assessment from contaminated foodstuffs: a field study in chromite mining-affected areas northern Pakistan.

PubMed

Nawab, Javed; Li, Gang; Khan, Sardar; Sher, Hassan; Aamir, Muhammad; Shamshad, Isha; Khan, Anwarzeb; Khan, Muhammad Amjad

2016-06-01

This study aimed to investigate the potential health risk associated with toxic metals in contaminated foodstuffs (fruits, vegetables, and cereals) collected from various agriculture fields present in chromite mining-affected areas of mafic and ultramafic terrains (northern Pakistan). The concentrations of Cr, Ni, Zn, Cd, and Pb were quantified in both soil and food samples. The soil samples were highly contaminated with Cr (320 mg/kg), Ni (108 mg/kg), and Cd (2.55 mg/kg), which exceeded their respective safe limits set by FAO/WHO. Heavy metal concentrations in soil were found in the order of Cr>Ni>Pb>Zn>Cd and showed significantly (p < 0.001) higher concentrations as compared to reference soil. The integrated pollution load index (PLI) value was observed greater than three indicating high level of contamination in the study area. The concentrations of Cr (1.80-6.99 mg/kg) and Cd (0.21-0.90 mg/kg) in foodstuffs exceeded their safe limits, while Zn, Pb, and Ni concentrations were observed within their safe limits. In all foodstuffs, the selected heavy metal concentrations were accumulated significantly (p < 0.001) higher as compared to the reference, while some heavy metals were observed higher but not significant like Zn in pear, persimmon, white mulberry, and date-plum; Cd in pear, fig and white mulberry; and Pb in walnut, fig, and pumpkin. The health risk assessment revealed no potential risk for both adults and children for the majority of heavy metals, except Cd, which showed health risk index (HRI) >1 for children and can pose potential health threats for local inhabitants. Graphical Abstract Heavy metals released from chromite mining lead to soil and foodstuff contamination and human health risk.

Spade: An H Chondrite Impact-melt Breccia that Experienced Post-shock Annealing

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Jones, Rhian H.

2006-01-01

The low modal abundances of relict chondrules (1.8 Vol%) and of coarse (i.e. >= 2200 micron-size) isolated mafic silicate grains (1.8 Vol%) in Spade relative to mean H6 chondrites (11.4 and 9.8 vol%, respectively) show Spade to be a rock that has experienced a significant degree of melting. Various petrographic features (e.g., chromite-plagioclase assemblages, chromite veinlets, silicate darkening) indicate that melting was caused by shock. Plagioclase was melted during the shock event and flowed so that it partially to completely surrounded nearby mafic silicate grains. During crystallization, plagioclase developed igneous zoning. Low-Ca pyroxene that crystallized from the melt (or equilibrated with the melt at high temperatures) acquired relatively high amounts of CaO. Metallic Fe-Ni cooled rapidly below the Fe-Ni solws and transformed into martensite. Subsequent reheating of the rock caused transformation of martensite into abundant duplex plessite. Ambiguities exist in the shock stage assignment of Spade. The extensive silicate darkening, the occurrence of chromite-plagioclase assemblages, and the impact-melted characteristics of Spade are consistent with shock stage S6. Low shock (stage S2) is indicated by the undulose extinction and lack of planar fractures in olivine. This suggests that Spade reached a maximum prior shock level equivalent to stage S6 and then experienced post-shock annealing (probably to stage Sl). These events were followed by a less intense impact that produced the undulose extinction in the olivine, characteristic of shock stage S2. Annealing could have occurred if Spade were emplaced near impact melts beneath the crater floor or deposited in close proximity to hot debris within an ejecta blanket. Spade firmly establishes the case for post-shock annealing. This may have been a common process on ordinary chondrites (OC) asteroids.

High- and low-Cr chromitite and dunite in a Tibetan ophiolite: evolution from mature subduction system to incipient forearc in the Neo-Tethyan Ocean

NASA Astrophysics Data System (ADS)

Xiong, Qing; Henry, Hadrien; Griffin, William L.; Zheng, Jian-Ping; Satsukawa, Takako; Pearson, Norman J.; O'Reilly, Suzanne Y.

2017-06-01

The microstructures, major- and trace-element compositions of minerals and electron backscattered diffraction (EBSD) maps of high- and low-Cr# [spinel Cr# = Cr3+/(Cr3+ + Al3+)] chromitites and dunites from the Zedang ophiolite in the Yarlung Zangbo Suture (South Tibet) have been used to reveal their genesis and the related geodynamic processes in the Neo-Tethyan Ocean. The high-Cr# (0.77-0.80) chromitites (with or without diopside exsolution) have chromite compositions consistent with initial crystallization by interaction between boninitic magmas, harzburgite and reaction-produced magmas in a shallow, mature mantle wedge. Some high-Cr# chromitites show crystal-plastic deformation and grain growth on previous chromite relics that have exsolved needles of diopside. These features are similar to those of the Luobusa high-Cr# chromitites, possibly recycled from the deep upper mantle in a mature subduction system. In contrast, mineralogical, chemical and EBSD features of the Zedang low-Cr# (0.49-0.67) chromitites and dunites and the silicate inclusions in chromite indicate that they formed by rapid interaction between forearc basaltic magmas (MORB-like but with rare subduction input) and the Zedang harzburgites in a dynamically extended, incipient forearc lithosphere. The evidence implies that the high-Cr# chromitites were produced or emplaced in an earlier mature arc (possibly Jurassic), while the low-Cr# associations formed in an incipient forearc during the initiation of a new episode of Neo-Tethyan subduction at 130-120 Ma. This two-episode subduction model can provide a new explanation for the coexistence of high- and low-Cr# chromitites in the same volume of ophiolitic mantle.

Mössbauer study of Cu1-xZnxFe2O4 catalytic materials

NASA Astrophysics Data System (ADS)

Koleva, K.; Velinov, N.; Tsoncheva, T.; Mitov, I.

2014-04-01

Copper zinc ferrites (Cu1-xZnxFe2O4) with different composition (x = 1; 0.2; 0.5; 0.8) were prepared by conventional thermal method. Formation of well crystallized ferrite phase with cubic structure and crystallites size of about 19.08-24.39 nm was observed by Powder X-ray diffraction and Mössbauer spectroscopy. The ferrite materials were tested as catalysts in methanol decomposition to CO and H2. A strong dependence of the catalytic behaviour of Cu1-xZnxFe2O4 ferrites of their composition and the phase transformations which occurred under the reaction medium was established.

Process for the conversion of lower alcohols to higher branched oxygenates

DOEpatents

Barger, Paul T.

1996-01-01

A process is provided for the production of branched C.sub.4+ oxygenates from lower alcohols such as methanol, ethanol, propanol and mixtures thereof. The process comprises contacting the lower alcohols with a solid catalyst comprising a mixed metal oxide support having components selected from the group consisting of oxides of zinc, magnesium, zirconia, titanium, manganese, chromium, and lanthanides, and an activation metal selected from the group consisting of Group VIII metal, Group IB metals, and mixtures thereof. The advantage of the process is improved yields and selectivity to isobutanol which can subsequently be employed in the production of high octane motor gasoline.

Process for the conversion of lower alcohols to higher branched oxygenates

DOEpatents

Barger, P.T.

1996-09-24

A process is provided for the production of branched C{sub x} oxygenates from lower alcohols such as methanol, ethanol, propanol and mixtures thereof. The process comprises contacting the lower alcohols with a solid catalyst comprising a mixed metal oxide support having components selected from the group consisting of oxides of zinc, magnesium, zirconia, titanium, manganese, chromium, and lanthanides, and an activation metal selected from the group consisting of Group VIII metal, Group IB metals, and mixtures thereof. The advantage of the process is improved yields and selectivity to isobutanol which can subsequently be employed in the production of high octane motor gasoline.

Preparation and Characterization of Soybean Oil-Based Polyurethanes for Digital Doming Applications

PubMed Central

Pantone, Vincenzo; Laurenza, Amelita Grazia; Annese, Cosimo; Fracassi, Francesco; Fini, Paola; Nacci, Angelo; Russo, Antonella; Fusco, Caterina

2017-01-01

Polyurethane-resin doming is currently one of the fastest growing markets in the field of industrial graphics and product identification. Semi-rigid bio-based polyurethanes were prepared deriving from soybean oil as a valuable alternative to fossil materials for digital doming and applied to digital mosaic technology. Bio-resins produced can favorably compete with the analogous fossil polymers, giving high-quality surface coatings (ascertained by SEM analyses). In addition, polyurethane synthesis was accomplished by using a mercury- and tin-free catalyst (the commercially available zinc derivative K22) bringing significant benefits in terms of cost efficiency and eco-sustainability. PMID:28773208

Recent Progress in Photocatalysis Mediated by Colloidal II-VI Nanocrystals

PubMed Central

Wilker, Molly B; Schnitzenbaumer, Kyle J; Dukovic, Gordana

2012-01-01

The use of photoexcited electrons and holes in semiconductor nanocrystals as reduction and oxidation reagents is an intriguing way of harvesting photon energy to drive chemical reactions. This review focuses on recent research efforts to understand and control the photocatalytic processes mediated by colloidal II-VI nanocrystalline materials, such as cadmium and zinc chalcogenides. First, we highlight how nanocrystal properties govern the rates and efficiencies of charge-transfer processes relevant to photocatalysis. We then describe the use of nanocrystal catalyst heterostructures for fuel-forming reactions, most commonly H2 generation. Finally, we review the use of nanocrystal photocatalysis as a synthetic tool for metal–semiconductor nano-heterostructures. PMID:24115781

On two alternative mechanisms of ethane activation over ZSM-5 zeolite modified by Zn2+ and Ga1+ cations.

PubMed

Kazansky, V B; Subbotina, I R; Rane, N; van Santen, R A; Hensen, E J M

2005-08-21

The activation of ethane over zinc- and gallium-modified HZSM-5 dehydrogenation catalysts was studied by diffuse reflectance infrared spectroscopy. Hydrocarbon activation on HZSM-5 modified by bivalent Zn and univalent Ga cations proceeds via two distinctly different mechanisms. The stronger molecular adsorption of ethane by the acid-base pairs formed by distantly separated cationic Zn2+ and basic oxygen sites results already at room temperature in strong polarizability of adsorbed ethane and subsequent heterolytic dissociative adsorption at moderate temperatures. In contrast, molecular adsorption of ethane on Ga+ cations is weak. At high temperatures dissociative hydrocarbon adsorption takes place, resulting in the formation of ethyl and hydride fragments coordinating to the cationic gallium species. Whereas in the zinc case a Brønsted acid proton is formed upon ethane dissociation, decomposition of the ethyl fragment on gallium results in gallium dihydride species and does not lead to Brønsted acid protons. This difference in alkane activation has direct consequences for hydrocarbon conversions involving dehydrogenation.

Overall water splitting on (Ga(1-x)Zn(x))(N(1-x)O(x)) solid solution photocatalyst: relationship between physical properties and photocatalytic activity.

PubMed

Maeda, Kazuhiko; Teramura, Kentaro; Takata, Tsuyoshi; Hara, Michikazu; Saito, Nobuo; Toda, Kenji; Inoue, Yasunobu; Kobayashi, Hisayoshi; Domen, Kazunari

2005-11-03

The physical and photocatalytic properties of a novel solid solution between GaN and ZnO, (Ga(1-x)Zn(x))(N(1-x)O(x)), are investigated. Nitridation of a mixture of Ga(2)O(3) and ZnO at 1123 K for 5-30 h under NH(3) flow results in the formation of a (Ga(1-x)Zn(x))(N(1-x)O(x)) solid solution with x = 0.05-0.22. With increasing nitridation time, the zinc and oxygen concentrations decrease due to reduction of ZnO and volatilization of zinc, and the crystallinity and band gap energy of the product increase. The highest activity for overall water splitting is obtained for (Ga(1-x)Zn(x))(N(1-x)O(x)) with x = 0.12 after nitridation for 15 h. The crystallinity of the catalyst is also found to increase with increasing the ratio of ZnO to Ga(2)O(3) in the starting material, resulting in an increase in activity.

Zinc oxide nanostructured layers for gas sensing applications

NASA Astrophysics Data System (ADS)

Caricato, A. P.; Cretí, A.; Luches, A.; Lomascolo, M.; Martino, M.; Rella, R.; Valerini, D.

2011-03-01

Various kinds of zinc oxide (ZnO) nanostructures, such as columns, pencils, hexagonal pyramids, hexagonal hierarchical structures, as well as smooth and rough films, were grown by pulsed laser deposition using KrF and ArF excimer lasers, without use of any catalyst. ZnO films were deposited at substrate temperatures from 500 to 700°C and oxygen background pressures of 1, 5, 50, and 100 Pa. Quite different morphologies of the deposited films were observed using scanning electron microscopy when different laser wavelengths (248 or 193 nm) were used to ablate the bulk ZnO target. Photoluminescence studies were performed at different temperatures (down to 7 K). The gas sensing properties of the different nanostructures were tested against low concentrations of NO2. The variation in the photoluminescence emission of the films when exposed to NO2 was used as transduction mechanism to reveal the presence of the gas. The nanostructured films with higher surface-to-volume ratio and higher total surface available for gas adsorption presented higher responses, detecting NO2 concentrations down to 3 ppm at room temperature.

Nanoporosity studies of novel catalysts through positronium annihilation

NASA Astrophysics Data System (ADS)

Félix, M. V.; Rodríguez-Rojas, R. A.; Castañeda-Contreras, J.; Nava, R.; Consolati, G.; Castaño, V. M.

2006-10-01

Eight novel hybrid silica gel-succinic acid-zinc acetate samples were analyzed through Positron annihilation lifetime spectroscopy in order to study average free volume quantities and free volume distributions. The aim of this work was to understand the type of porosity within these species and its relationship with surface textural properties (tested by the BET method) and catalytic activity. We found a noticeable dependence of o-Ps lifetimes on the nature of each modifier agent (succinic acid, Zn acetate, succinic acid-Zn acetate) fixed on the surface of SiO 2 and SiO 2-Al 2O 3 particles. We observed the trend of the Zinc acetate to create mesopores among silica particles, while succinic acid acts as a positronium quencher and a nanoporosity performer. Long o-Ps lifetimes were decomposed into two components accounting for the existence of interparticle and intraparticle holes, however discrepancies beyond elementary facts between the BET method measurements and our positronium calculations were found. A discussion of the kind of open spaces analysis necessary to fully understand the porosity in these hybrid materials is also presented.

Nickel oxide decorated zinc oxide composite nanorods: Excellent catalyst for photoreduction of hexavalent chromium.

PubMed

Singh, Simranjeet; Ahmed, Imtiaz; Haldar, Krishna Kanta

2018-08-01

In light of the growing interest and ability to search for new materials, we have synthesized Nickel oxide (NiO) nanoparticles decorated Zinc (ZnO) nanorods composite (NiO/ZnO) nanostructure. The NiO/ZnO heterostructure formation was confirmed by X-ray powder diffraction and high-resolution transmission electron microscopy (HRTEM). The fabricated environmental friendly NiO/ZnO composite nanostructure shows a well-defined photoreduction characteristic of hexavalent Chromium (Cr) (VI) to tri-valent Chromium (Cr) (III) under UV-light. Such an enhanced photoreduction property is attributed due to the decreased electron-hole recombination process which was proved by photoluminescence (PL) spectroscopy, photocurrent study, and electrochemical impedance spectroscopy. Furthermore, the photocatalytic activity rate of the NiO decorated ZnO nanorods was much higher than that of bare ZnO nanorods for the reduction of chromium (VI) and the rate is found to be 0.306 min -1 . These results have demonstrates that suitable surface engineering may open up new opportunities in the development of high-performance photocatalyst. Copyright © 2018 Elsevier Inc. All rights reserved.

How to polymerize ethylene in a highly controlled fashion?

PubMed

Kempe, Rhett

2007-01-01

Very fast, reversible, polyethylene (PE) chain transfer or complex-catalysed "Aufbaureaktion" describes a "living" chain-growing process on a main-group metal or zinc atom; this process is catalysed by an organo-transition-metal or lanthanide complex. PE chains are transferred very fast between the two metal sites and chain growth takes place through ethylene insertion into the transition-metal- or lanthanide-carbon bond-coordinative chain-transfer polymerisation (CCTP). The transferred chains "rest" at the main-group or zinc centre, at which chain-termination processes like beta-H transfer/elimination are of low significance. Such protocols can be used to synthesise very narrowly distributed PE materials (M(w)/M(n)<1.1 up to a molecular weight of about 4000 g mol(-1)) with differently functionalised end groups. Higher molecular-weight polymers can be obtained with a slightly increased M(w)/M(n), since diffusion control and precipitation of the polymers influences the chain-transfer process. Recently, a few transition-metal- or lanthanide-based catalyst systems that catalyse such a highly reversible chain-growing process have been described. They are summarised and compared within this contribution.

High-Efficiency Co/CoxSy@S,N-Codoped Porous Carbon Electrocatalysts Fabricated from Controllably Grown Sulfur- and Nitrogen-Including Cobalt-Based MOFs for Rechargeable Zinc-Air Batteries.

PubMed

Liu, Shengwen; Zhang, Xian; Wang, Guozhong; Zhang, Yunxia; Zhang, Haimin

2017-10-04

Developing bifunctional oxygen electrocatalysts with superior catalytic activities of oxygen reduction reaction (ORR) and oxygen revolution reaction (OER) is crucial to their practical energy storage and conversion applications. In this work, we report the fabrication of Co/Co x S y @S,N-codoped porous carbon structures with various morphologies, specific surface areas, and pore structures, derived from controllably grown Co-based metal-organic frameworks with S- and N-containing organic ligands (thiophene-2,5-dicarboxylate, Tdc; and 4,4'-bipyridine, bpy) utilizing solvent effect (e.g., water and methanol) under room temperature and hydrothermal conditions. The results demonstrate that Co/Co x S y @S,N-codoped carbon fibers fabricated at a pyrolytic temperature of 800 °C (Co/Co x S y @SNCF-800) from Co-MOFs fibers fabricated in methanol under hydrothermal conditions as electrocatalysts exhibit superior bifunctional ORR and OER activities in alkaline media, endowing them as air cathodic catalysts in rechargeable zinc-air batteries with high power density and good durability.

Carbon Dioxide Utilization by the Five-Membered Ring Products of Cyclometalation Reactions

PubMed Central

Omae, Iwao

2016-01-01

In carbon dioxide utilization by cyclometalated five-membered ring products, the following compounds are used in four types of applications: 1. 2-Phenylpyrazole iridium compounds, pincer phosphine iridium compounds and 2-phenylimidazoline iridium compounds are used as catalysts for both formic acid production from CO2 and H2, and hydrogen production from the formic acid. This formic acid can be a useful agent for H2 production and storage for fuel cell electric vehicles. 2. Other chemicals, e.g., dimethyl carbonate, methane, methanol and CO, are produced with dimethylaminomethylphenyltin compounds, pincer phosphine iridium compounds, pincer phosphine nickel compound and ruthenium carbene compound or 2-phenylpyridine iridium compounds, and phenylbenzothiazole iridium compounds as the catalysts for the reactions with CO2. 3. The five-membered ring intermediates of cyclometalation reactions with the conventional substrates react with carbon dioxide to afford their many types of carboxylic acid derivatives. 4. Carbon dioxide is easily immobilized at room temperature with immobilizing agents such as pincer phosphine nickel compounds, pincer phosphine palladium compounds, pincer N,N-dimethylaminomethyltin compounds and tris(2-pyridylthio)methane zinc compounds. PMID:28503084

Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

DOEpatents

Nicholas, Christpher P; Boldingh, Edwin P

2013-12-17

A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and show to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hyrdocarbons into hydrocarbons removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

DOEpatents

Nicholas, Christopher P; Boldingh, Edwin P

2014-10-07

A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and shown to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub.1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

Seed/catalyst-free vertical growth of high-density electrodeposited zinc oxide nanostructures on a single-layer graphene

NASA Astrophysics Data System (ADS)

Aziz, Nur Suhaili Abd; Mahmood, Mohamad Rusop; Yasui, Kanji; Hashim, Abdul Manaf

2014-02-01

We report the seed/catalyst-free vertical growth of high-density electrodeposited ZnO nanostructures on a single-layer graphene. The absence of hexamethylenetetramine (HMTA) and heat has resulted in the formation of nanoflake-like ZnO structure. The results show that HMTA and heat are needed to promote the formation of hexagonal ZnO nanostructures. The applied current density plays important role in inducing the growth of ZnO on graphene as well as in controlling the shape, size, and density of ZnO nanostructures. High density of vertically aligned ZnO nanorods comparable to other methods was obtained. The quality of the ZnO nanostructures also depended strongly on the applied current density. The growth mechanism was proposed. According to the growth timing chart, the growth seems to involve two stages which are the formation of ZnO nucleation and the enhancement of the vertical growth of nanorods. ZnO/graphene hybrid structure provides several potential applications in electronics and optoelectronics such as photovoltaic devices, sensing devices, optical devices, and photodetectors.

Sonocatalytic removal of naproxen by synthesized zinc oxide nanoparticles on montmorillonite.

PubMed

Karaca, Melike; Kıranşan, Murat; Karaca, Semra; Khataee, Alireza; Karimi, Atefeh

2016-07-01

ZnO/MMT nanocomposite as sonocatalyst was prepared by immobilizing synthesized ZnO on the montmorillonite surface. The characteristics of as-prepared nanocomposite were studied by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD) techniques. The synthesized samples were used as a catalyst for sonocatalytic degradation of naproxen. ZnO/MMT catalyst in the presence of ultrasound irradiation was more effective compared to pure ZnO nanoparticles and MMT particles in the sonocatalysis of naproxen. The effect of different operational parameters on the sonocatalytic degradation of naproxen including initial drug concentration, sonocatalyst dosage, solution pH, ultrasonic power and the presence of organic and inorganic scavengers were evaluated. It was found that the presence of the scavengers suppressed the sonocatalytic degradation efficiency. The reusability of the nanocomposite was examined in several consecutive runs, and the degradation efficiency decreased only 2% after 5 repeated runs. The main intermediates of naproxen degradation were determined by gas chromatography-mass spectrometry (GC-Mass). Copyright © 2016 Elsevier B.V. All rights reserved.

Carbon Dioxide Utilization by the Five-Membered Ring Products of Cyclometalation Reactions.

PubMed

Omae, Iwao

2016-04-01

In carbon dioxide utilization by cyclometalated five-membered ring products, the following compounds are used in four types of applications: 1. 2-Phenylpyrazole iridium compounds, pincer phosphine iridium compounds and 2-phenylimidazoline iridium compounds are used as catalysts for both formic acid production from CO 2 and H 2 , and hydrogen production from the formic acid. This formic acid can be a useful agent for H 2 production and storage for fuel cell electric vehicles. 2. Other chemicals, e.g. , dimethyl carbonate, methane, methanol and CO, are produced with dimethylaminomethylphenyltin compounds, pincer phosphine iridium compounds, pincer phosphine nickel compound and ruthenium carbene compound or 2-phenylpyridine iridium compounds, and phenylbenzothiazole iridium compounds as the catalysts for the reactions with CO 2 . 3. The five-membered ring intermediates of cyclometalation reactions with the conventional substrates react with carbon dioxide to afford their many types of carboxylic acid derivatives. 4. Carbon dioxide is easily immobilized at room temperature with immobilizing agents such as pincer phosphine nickel compounds, pincer phosphine palladium compounds, pincer N , N -dimethylaminomethyltin compounds and tris(2-pyridylthio)methane zinc compounds.

Synthesis of Fe3O4@P4VP@ZIF-8 core-shell microspheres and their application in a Knoevenagel condensation reaction

NASA Astrophysics Data System (ADS)

Miao, Zongcheng; Yang, Fengxia; Luan, Yi; Shu, Xin; Ramella, Daniele

2017-12-01

In this work, a core-shell magnetic composite Fe3O4@P4VP@ZIF-8 microspheres were successfully designed and synthesized. A polymerization approach on the surface of pre-made Fe3O4 microspheres was employed for the synthesis of Fe3O4@P4VP. The zinc-derived Zeolite Imidazolate Framework (ZIF) shell was introduced through a layer-by-layer strategy. The obtained Fe3O4@P4VP@ZIF-8 core-shell structure was employed as an efficient Knoevenagel condensation catalyst for a variety of aldehydes. Furthermore, the inner P4VP layer also served as a basic additive in the condensation reaction process, while much less homogeneous basic additive was used. High catalytic reaction efficiency was achieved when the P4VP layer was utilized in combination with a Lewis acidity bearing ZIF-8 layer. The Fe3O4@P4VP@ZIF-8 catalyst was tested for recyclability and no drop in the catalytic activity was observed after more than five cycles.

2-Piperidino-1,1,2-triphenylethanol: a highly effective catalyst for the enantioselective arylation of aldehydes.

PubMed

Fontes, Montserrat; Verdaguer, Xavier; Solà, Lluís; Pericàs, Miquel A; Riera, Antoni

2004-04-02

Here we report the use of 2-piperidino-1,2,2-triphenylethanol (5) as an outstanding catalyst for the ligand-catalyzed arylation of aldehydes. The use of 5 and a 2/1 mixture of Et(2)Zn/Ph(2)Zn provided the corresponding chiral diarylcarbinols with enantiomeric excess of up to 99% ee. The effect of temperature on the reaction enantioselectivity was studied and the inversion temperature (T(inv)) was determined to be 10 degrees C for reaction with p-tolylaldehyde. Most remarkably, lowering the amount of catalyst (5) to 0.5 mol % still afforded excellent levels of enantiocontrol (93.7% ee). Kinetics of the catalyzed and uncatalyzed arylation of aldehydes was studied by means of in situ FT-IR. The background uncatalyzed addition rates to p-tolylaldehyde when using pure Ph(2)Zn and Et(2)Zn/Ph(2)Zn (2/1) suggest that in the latter case a mixed zinc species forms (EtPhZn) minimizing the undesired nonselective addition. Formation of EtPhZn was modeled at the DFT calculation level. A four-center TS (TS-V) corresponding to the Et/Ph scrambling was localized along with two dimers (D-IV and D-VI). The model supports the hypothesis that Et/Ph exchange is a kinetically facile process. Gas evolution experiments during the formation of the active catalyst showed that the formation of an active site with a ONZn-Et (10) moiety is kinetically favored over ONZn-Ph (11). Finally, the phenyl transfer to benzaldehyde was modeled at the PM3(tm) level through anti and syn 5/4/4 tricyclic TS structures for both 10 and 11. The model could correctly predict the sense and selectivity of the overall process and predicted that 11 should be more selective than 10.

Cobalt Ferrite Bearing Nitrogen-Doped Reduced Graphene Oxide Layers Spatially Separated with Microporous Carbon as Efficient Oxygen Reduction Electrocatalyst.

PubMed

Kashyap, Varchaswal; Singh, Santosh K; Kurungot, Sreekumar

2016-08-17

The present work discloses how high-quality dispersion of fine particles of cobalt ferrite (CF) could be attained on nitrogen-doped reduced graphene oxide (CF/N-rGO) and how this material in association with a microporous carbon phase could deliver significantly enhanced activity toward electrochemical oxygen reduction reaction (ORR). Our study indicates that the microporous carbon phase plays a critical role in spatially separating the layers of CF/N-rGO and in creating a favorable atmosphere to ensure the seamless distribution of the reactants to the active sites located on CF/N-rGO. In terms of the ORR current density, the heat-treated hybrid catalyst at 150 °C (CF/N-rGO-150) is found to be clearly outperforming (7.4 ± 0.5 mA/cm(2)) the state-of-the-art 20 wt % Pt-supported carbon catalyst (PtC) (5.4 ± 0.5 mA/cm(2)). The mass activity and stability of CF-N-rGO-150 are distinctly superior to PtC even after 5000 electrochemical cycles. As a realistic system level exploration of the catalyst, testing of a primary zinc-air battery could be demonstrated using CF/N-rGO-150 as the cathode catalyst. The battery is giving a galvanostatic discharge time of 15 h at a discharge current density of 20 mA/cm(2) and a specific capacity of ∼630 mAh g(-1) in 6 M KOH by using a Zn foil as the anode. Distinctly, the battery performance of this system is found to be superior to that of PtC in less concentrated KOH solution as the electrolyte.

Nanocrystalline semiconductor doped rare earth oxide for the photocatalytic degradation studies on Acid Blue 113: A di-azo compound under UV slurry photoreactor.

PubMed

Suganya Josephine, G A; Mary Nisha, U; Meenakshi, G; Sivasamy, A

2015-11-01

Preventive measures for the control of environmental pollution and its remediation has received much interest in recent years due to the world-wide increase in the contamination of water bodies. Contributions of these harmful effluents are caused by the leather processing, pharmaceutical, cosmetic, textile, agricultural and other chemical industries. Nowadays, advanced oxidation processes considered to be better option for the complete destruction of organic contaminants in water and wastewater. Acid Blue 113 is a most widely used di-azo compound in leather, textile, dying and food industry as a color rending compound. In the present study, we have reported the photo catalytic degradation of Acid Blue 113 using a nanocrystalline semiconductor doped rare earth oxide as a photo catalyst under UV light irradiation. The photocatalyst was prepared by a simple precipitation technique and were characterized by XRD, FT-IR, UV-DRS and FE-SEM analysis. The experimental results proved that the prepared photo catalyst was nanocrystalline and highly active in the UV region. The UV-DRS results showed the band gap energy was 3.15eV for the prepared photo catalyst. The photodegradation efficiency was analyzed by various experimental parameters such as pH, catalyst dosage, variation of substrate concentration and effect of electrolyte addition. The photo degradation process followed a pseudo first order kinetics and was continuously monitored by UV-visible spectrophotometer. The experimental results proved the efficacy of the nanocrystalline zinc oxide doped dysprosium oxide which are highly active under UV light irradiations. It is also suggested that the prepared material would find wider applications in environmental remediation technologies to remove the carcinogenic and toxic moieties present in the industrial effluents. Copyright © 2015 Elsevier Inc. All rights reserved.

Converting solid wastes into liquid fuel using a novel methanolysis process.

PubMed

Xiao, Ye; He, Peng; Cheng, Wei; Liu, Jacqueline; Shan, Wenpo; Song, Hua

2016-03-01

Biomass fast pyrolysis followed by hydrodeoxygenation upgrading is the most popular way to produce upgraded bio-oil from biomass. This process requires large quantities of expensive hydrogen and operates under high pressure condition (70-140 atm). Therefore, a novel methanolysis (i.e., biomass pyrolysis under methane environment) process is developed in this study, which is effective in upgraded bio-oil formation at atmospheric pressure and at about 400-600°C. Instead of using pure methane, simulated biogas (60% CH4+40% CO2) was used to test the feasibility of this novel methanolysis process for the conversion of different solid wastes. The bio-oil obtained from canola straw is slightly less than that from sawdust in term of quantity, but the oil quality from canola straw is better in terms of lower acidity, lower Bromine Number, higher H/C atomic ratio and lower O/C atomic ratio. The municipal solid waste and newspaper can also obtain relatively high oil yields, but the oil qualities of them are both lower than those from sawdust and canola straw. Compared with catalysts of 5%Zn/ZSM-5 and 1%Ag/ZSM-5, the 5%Zn-1%Ag/ZSM-5 catalyst performed much better in terms of upgraded bio-oil yield as well as oil quality. During the methanolysis process, the metal silver may be used to reduce the total acid number of the oil while the metal zinc might act to decrease the bromine number of the oil. The highly dispersed Zn and Ag species on/in the catalyst benefit the achievement of better upgrading performance and make it be a very promising catalyst for bio-oil upgrading by biogas. Copyright © 2015 Elsevier Ltd. All rights reserved.

Preliminary Assessment of Non-Fuel Mineral Resources of Afghanistan, 2007

USGS Publications Warehouse

,

2007-01-01

Introduction Afghanistan has abundant mineral resources, including known deposits of copper, iron, barite, sulfur, talc, chromium, magnesium, salt, mica, marble, rubies, emeralds, lapis lazuli, asbestos, nickel, mercury, gold and silver, lead, zinc, fluorspar, bauxite, beryllium, and lithium (fig. 1). Between 2005 and 2007, the U.S. Agency for International Development (USAID) funded a cooperative study by the U.S. Geological Survey (USGS) and the Afghanistan Geological Survey (AGS) to assess the non-fuel mineral resources of Afghanistan as part of the effort to aid in the reconstruction of that country. An assessment is an estimation or evaluation, in this instance of undiscovered non-fuel mineral resources. Mineral resources are materials that are in such form that economic extraction of a commodity is currently or potentially feasible. In this assessment, teams of scientists from the USGS and the AGS compiled information about known mineral deposits and then evaluated the possible occurrence of undiscovered deposits of all types. Quantitative probabilistic estimates were made for undiscovered deposits of copper, mercury, rare-earth elements, sulfur, chromite, asbestos, potash, graphite, and sand and gravel. These estimates were made for undiscovered deposits at depths less than a kilometer. Other deposit types were considered and discussed in the assessment, but quantitative estimates of numbers of undiscovered deposits were not made. In addition, the assessment resulted in the delineation of 20 mineralized areas for further study, of which several may contain resources amenable to rapid development.

Effect of dissimilatory Fe(III) reducers on bio-reduction and nickel-cobalt recovery from Sukinda chromite-overburden.

PubMed

Esther, Jacintha; Panda, Sandeep; Behera, Sunil K; Sukla, Lala B; Pradhan, Nilotpala; Mishra, Barada K

2013-10-01

The effect of an adapted dissimilatory iron reducing bacterial consortium (DIRB) towards bio-reduction of Sukinda chromite overburden (COB) with enhanced recovery of nickel and cobalt is being reported for the first time. The remarkable ability of DIRB to utilize Fe(III) as terminal electron acceptor reducing it to Fe(II) proved beneficial for treatment of COB as compared to previous reports for nickel leaching. XRD studies showed goethite as the major iron-bearing phase in COB. Under facultative anaerobic conditions, goethite was reduced to hematite and magnetite with the exposure of nickel oxide. FESEM studies showed DIRB to be associated with COB through biofilm formation with secondary mineral precipitates of magnetite deposited as tiny globular clusters on the extra polymeric substances. The morphological and mineralogical changes in COB, post DIRB application, yielded a maximum of 68.5% nickel and 80.98% cobalt in 10 days using 8M H2SO4. Copyright © 2013 Elsevier Ltd. All rights reserved.

Preparation of a Bimetal Using Mechanical Alloying for Environmental or Industrial Use

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline; Geiger, Cherie; Clausen, Christian

2013-01-01

Following the 1976 Toxic Substances Control Act ban on their manufacture, PCBs remain an environmental threat. PCBs are known to bio-accumulate and concentrate in fatty tissues. Further complications arise from the potential for contamination of commercial mixtures with other more toxic chlorinated compounds such as polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Until recently, only one option was available for the treatment of PCB-contaminated materials: incineration. This may prove to be more detrimental to the environment than the PCBs themselves due to the potential for formation of PCDDs. Metals have been used for the past ten years for the remediation of halogenated solvents and other contaminants in the environment; however, zero-valent metals alone do not possess the activity required to dehalogenate PCBs. Palladium has been shown to act as an excellent catalyst for the dechlorination of PCBs with active metals. This invention is a method for the production of a palladium/magnesium bimetal capable of dechlorinating PCBs using mechanical milling/mechanical alloying. Other base metals and catalysts may also be alloyed together (e.g., nickel or zinc) to create a similarly functioning catalyst system. Several bimetal catalyst systems currently can be used for processes such as hydrogen peroxide synthesis, oxidation of ethane, selective oxidation, hydrogenation, and production of syngas for further conversion to clean fuels. The processes for making these bimetal catalysts often involve vapor deposition. This technology provides an alternative to vapor deposition that may provide equally active catalysts. A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts. Preferably, the hydrogenation catalyst is a bimetallic particle formed from a zero-valent iron or zero-valent magnesium particle coated with palladium that is impregnated onto a high-surface-area graphite support. The zero-valent metal particles should be microscale or nanoscale zero-valent magnesium or zero-valent iron particles. Other zero-valent metal particles and combinations may be used. Additionally, the base material may be selected from a variety of minerals including, but not limited to, alumina and zeolites. The catalytic metal is preferably selected from the group consisting of noble metals and transition metals, preferably palladium. The mechanical milling process includes milling the base material with a catalytic metal impregnated into a high-surface-area support to form the hydrogenation catalyst. In a preferred mechanical milling process, a zero-valent metal particle is provided as the base material, preferably having a particle size of less than about 10 microns, preferably 0.1 to 10 microns or smaller, prior to milling. The catalytic metal is supported on a conductive carbon support structure prior to milling. For example, palladium may be impregnated on a graphite support. Other support structures such as semiconductive metal oxides may also be used.

IN-SITU CR(VI) SOURCE AND PLUME TREATMENT USING A FERROUS IRON BASED REDUCTANT

EPA Science Inventory

A large volume of chromite ore processing residue (COPR) generated from ferrochrome production operations is present at the Macalloy Corporation Superfund site in Charleston, S.C. Groundwater hexavalent chromium (Cr(VI)) concentrations in the approximately 20 acre-foot COPR satu...

IN-SITU CR(VI) SOURCE AND PLUME TREATMENT USING A FERROUS IRON-BASED REDUCTANT

EPA Science Inventory

A large volume of chromite ore processing residue (COPR) generated from ferrochrome production operations is present at the Macalloy Corporation Superfund site in Charleston, S.C. Groundwater hexavalent chromium (Cr(VI)) concentrations in the approximately 20 acre-foot COPR sat...

Hearing Threshold, Loss, Noise Levels and Worker’s Profiles of an Open Cast Chromite Mines in Odisha, India

PubMed Central

Kerketta, Sunamani; Gartia, Rajendra; Bagh, Somanath

2012-01-01

Objectives: The aims of the study were to describe the noise levels at an open cast chromite mine in Odisha, India, and the hearing threshold of its workers and to associate their hearing loss with their age, work station and length of employment at the mine. Methods: We performed a cross-sectional study of the hearing threshold of chromite mine workers. Audiometric data from 500 subjects was collected at the mines’ hospital in the Sukinda Valley of Jajpur, Odisha, India. The latest audiometry data available for the period 2002 to 2008 was used in the analysis. Audiometric screening was performed using an audiometer (TRIVENI TAM-25 6025A) in a quiet environment by qualified technicians, audiologists or physicians. Tests were conducted on the subjects after they had completely rested for 16 hours or more after their day shift. Results: A maximum of 262 subjects (52.4%) were employed in the work zone area and a minimum of 2 subjects (0.4%) had less than 5 years working experience. The age of the subjects ranged from 29 to 59 years and their working experience ranged from 4 to 37 years. The subjects’ average mean hearing thresholds at 4, 6 and 8 kHz were 21.53 dBA, 23.40 dBA and 21.90 dBA, respectively. The maximum Leq and L90 levels exceeded the prescribed limits for commercial, residential and silence zones. The maximum Leq levels exceeded 95 dBA for large and medium heavy earth moving machineries (HEMMs), both outside and at the operator’s position. Hearing loss due to the subjects’ work experience was found to be greater than that attributable to age and workstation. Conclusion: In our study population, the maximum noise levels for large and medium HEMMs and inside the cabins of HEMMs were found to be more than 95 dBA. This indicates that operators in this particular chromite mine at Odisha, India were exposed to noise levels exceeding 95 dBA for more than 10% of the monitoring time. The subjects’ hearing loss was also found to increase for every 10-year age interval and that for every 5 years of work experience at high fence. The subjects’ age and experience are significantly associated with hearing loss at all levels for frequencies of 4.0, 6.0, and 8.0 kHz, with older and more experienced workers having a higher incidence of hearing loss. PMID:23613650

Hearing Threshold, Loss, Noise Levels and Worker's Profiles of an Open Cast Chromite Mines in Odisha, India.

PubMed

Kerketta, Sunamani; Gartia, Rajendra; Bagh, Somanath

2012-10-01

The aims of the study were to describe the noise levels at an open cast chromite mine in Odisha, India, and the hearing threshold of its workers and to associate their hearing loss with their age, work station and length of employment at the mine. We performed a cross-sectional study of the hearing threshold of chromite mine workers. Audiometric data from 500 subjects was collected at the mines' hospital in the Sukinda Valley of Jajpur, Odisha, India. The latest audiometry data available for the period 2002 to 2008 was used in the analysis. Audiometric screening was performed using an audiometer (TRIVENI TAM-25 6025A) in a quiet environment by qualified technicians, audiologists or physicians. Tests were conducted on the subjects after they had completely rested for 16 hours or more after their day shift. A maximum of 262 subjects (52.4%) were employed in the work zone area and a minimum of 2 subjects (0.4%) had less than 5 years working experience. The age of the subjects ranged from 29 to 59 years and their working experience ranged from 4 to 37 years. The subjects' average mean hearing thresholds at 4, 6 and 8 kHz were 21.53 dBA, 23.40 dBA and 21.90 dBA, respectively. The maximum Leq and L90 levels exceeded the prescribed limits for commercial, residential and silence zones. The maximum Leq levels exceeded 95 dBA for large and medium heavy earth moving machineries (HEMMs), both outside and at the operator's position. Hearing loss due to the subjects' work experience was found to be greater than that attributable to age and workstation. In our study population, the maximum noise levels for large and medium HEMMs and inside the cabins of HEMMs were found to be more than 95 dBA. This indicates that operators in this particular chromite mine at Odisha, India were exposed to noise levels exceeding 95 dBA for more than 10% of the monitoring time. The subjects' hearing loss was also found to increase for every 10-year age interval and that for every 5 years of work experience at high fence. The subjects' age and experience are significantly associated with hearing loss at all levels for frequencies of 4.0, 6.0, and 8.0 kHz, with older and more experienced workers having a higher incidence of hearing loss.

Copper(II) and zinc(II) dinuclear enzymes model compounds: The nature of the metal ion in the biological function

NASA Astrophysics Data System (ADS)

Ferraresso, L. G.; de Arruda, E. G. R.; de Moraes, T. P. L.; Fazzi, R. B.; Da Costa Ferreira, A. M.; Abbehausen, C.

2017-12-01

First series transition metals are used abundantly by nature to perform catalytic transformations of several substrates. Furthermore, the cooperative activity of two proximal metal ions is common and represents a highly efficient catalytic system in living organisms. In this work three dinuclear μ-phenolate bridged metal complexes were prepared with copper(II) and zinc(II), resulting in a ZnZn, CuCu and CuZn with the ligand 2-ethylaminodimethylamino phenol (saldman) as model compounds of superoxide dismutase (CuCu and CuZn) and metallo-β-lactamases (ZnZn). Metals are coordinated in a μ-phenolate bridged symmetric system. Cu(II) presents a more distorted structure, while zinc is very symmetric. For this reason, [CuCu(saldman)] shows higher water solubility and also higher lability of the bridge. The antioxidant and hydrolytic beta-lactamase-like activity of the complexes were evaluated. The lability of the bridge seems to be important for the antioxidant activity and is suggested to because of [CuCu(saldman)] presents a lower antioxidant capacity than [CuZn(saldman)], which showed to present a more stable bridge in solution. The hydrolytic activity of the bimetallic complexes was assayed using nitrocefin as substrate and showed [ZnZn(saldman)] as a better catalyst than the Cu(II) analog. The series demonstrates the importance of the nature of the metal center for the biological function and how the reactivity of the model complex can be modulated by coordination chemistry.

Distribution and PGE mineralization in the formation of chromitite in ophiolite complexes (Ospina-Kitoi Kharanur and ultrabasic massifs of Eastern Sayan, Sousern Siberia)

NASA Astrophysics Data System (ADS)

Kiseleva, Olga; Zhmodik, Sergei

2015-04-01

New study of PGE in restitic ultrabasic (Kharanur and Ospin-Kitoi) massifs from North and South branches (Dobretsov et al., 1985) of the ophiolite complexes in south-eastern part of the Eastern Sayan show their presence in chromitites of both branches belonging to the different geodynamic settings. Modern concepts model includes several mechanisms of podiform chromitite origin reflected in the chemistry of Cr-spinels (Arai, Yurimoto, 1994; Ballhaus, 1998; Uysal et al., 2009 et al.): 1) partial melting of upper mantle rocks, 2) mixing of primitive melts with melts enriched in SiO2, 3) melt-rock interaction. We estimated the types of interaction of mafic melts with mantle peridotites, with the formation of chromite bodies. For ore chrome spinelides from northern branch (Al2O3) melt = 8 - 14 wt%, (TiO2) melt = 0 - 0,4 wt%, (Fe/Mg) melt = 0,5 - 2,4; Southern branch (Al2O3) melt = 10 - 13 wt%, (TiO2) melt = 0,1 wt%, (Fe/Mg) melt = 0,3 - 1 (Kiseleva, 2014). There are two types of PGE distribution Os-Ir-Ru (I) and Pt-Pd (II). Type I chromitites (mid-Al#Cr-spinels) revealed only Os-Ir-Ru distributions; type II (low-Al#Cr spinelides) show both Os-Ir-Ru and (Pt-Pd) distributions (Kiseleva et al., 2012, 2014). PGE distribution in ultramafic peridotites and chromitites reflects PGE fractionation during partial melting (Barnes et al., 1985; Rehkämper et al., 1997). Processes bringing to extreme fractionation of PGE, may be associated with fluid-saturated supra subduction environment where melting degree near 20% and above is sufficient for the release of PGE from the mantle source (Dick, Bullen, 1984; Naldrett, 2010). Enrichment in PPGE together with a high content of IPGE in same chromite bodies is attributed to the second step of melting, and formation of S-enriched and saturated in PGE melts (Hamlyn, Keays, 1986; Prichard et al., 1996). For type I chromitites platinum group minerals (PGM) are presented by Os-Ir-Ru system. In type II chromitites PGM are represented by Os-Ir-Ru-Rh-Pt system. Solid solutions Os-Ir-Ru and formed in the upper mantle RuS2 conditions together with chromite. The (Os-Ir-Ru)AsS minerals are forming on postmagmatic stage under the influence of S, As-containing fluids Under the influence of mantle reduced fluids the remobilization of PGE during desulfurization and deserpentinization early of "primary" PGM takes place. Changes of the redox environment from reducing to oxidizing condition is followed by creation of PGE together with As, Sb, Sn, and nickel arsenides, ferrichromie, chrommagnetite. The latter association reflects the redistribution of chromite and platinum group metals and formation of new mineral associations within the ultramafic substrate in crustal conditions (Kiseleva, 2014). Kiseleva O.N. Chromitite and PGE mineralization in ophiolites south-eastern part of the East Sayan (Ospina-Kitoi and Kharanur massifs), Thesis of PHD dissertation, Novosibirsk, 2014 IPGG SB RAS, 15p. Kiseleva O.N., Zhmodik SM, Damdinov BB, Agafonov LV, Belyanin D.K. 2014 The composition and evolution of platinum group mineralization in chromite ores Ilchir ophiolite complex (Ospin-Kitoi and Kharanur massifs, Eastern Sayan). Geology and Geophysics 55, 333 - 349.

The Compaction of Ultramafic Cumulates in Layered Intrusions - Time and Length Scales (Invited)

NASA Astrophysics Data System (ADS)

Schmidt, M. W.; Manoochehri, S.

2013-12-01

Many large mafic intrusions have thick series of mostly ultramafic cumulates composed of dense cumulus minerals (chromite, olivine, pyroxenes) precipitated from low viscosity (roughly basaltic) liquids. To understand the time and length scales involved, the crystal settling and compaction process was simulated through centrifuge-assisted experiments of olivine or chromite in basaltic melt. Experiments were performed in a centrifuging piston cylinder at 200-1500 g, 1200-1300 C, 0.5-1.1 GPa on previously annealed and texturally equilibrated samples. The mechanical settling of the dense olivine or chromite suspensions occurs at 1/6 and 1/2 the speed of simple Stokes settling. The porosity (φm ) of orthocumulates resulting from gravitational settling is 50-55 %, pile up times for natural grain sizes result to 0.1-10 m/day. Hence, gravitational deposition (including re-deposition) of crystals may take place within years, i.e. almost instantaneously with progressing crystallization. After (re-)deposition, grains rest on each other. Further (chemical) compaction occurs through pressure dissolution at grain contacts, olivine or chromite re-precipitates where in contact with melt. Concomitantly excess liquid is expulsed from the cumulate layer. Centrifugation let to porosities as low as 30.3 vol% for olivine. The crystal content at the bottom of the experimentally compacted cumulate is 1-φm ~ log(Δρ h a t), where Δρ = crystal-melt density difference, h = crystal layer thickness, a = acceleration and t = time. Compaction is hence proportional to effective stress integrated over time indicating that pressure dissolution is the dominant mechanism. Notably, chromite crystals compact only about half as fast as olivine crystals. The compaction limit, i.e. the lowermost porosity to be reached, is calculated by equating the lithostatic and hydraulic pressure gradients in the cumulate and results to 3-5 % porosity for the experiments. Crystal size distribution curves and a growth exponent n of 3.1(3) (for olivine) indicate that diffusion controlled Ostwald ripening is the dominant crystal growth mechanism. The experimentally calibrated compaction relationship, combined with a linear scaling for grain size as appropriate for reaction-controlled pressure solution creep, allows calculation of formation times of natural adcumulates. A single layer of olivine adcumulate of 1/2 m thickness with 70-75 vol% olivine at the base (as observed in Rhum), would have typical formation times of 0.4-3 yrs for grain sizes of 2-10 mm, comparing favourably with characteristic cooling times of sills. If a >20 m thick series of cumulate layers pressurizes a base layer with the porosity still filled by a melt, then compaction proceeds to the compaction limit within a few years. To understand the thickness of a simultaneously compacting (layered) crystal pile, (paleo)-porosity gradients determined from incompatible trace elements can be employed when combined with modelled characteristic cooling times. In layered mafic intrusions where cumulates are deposited from a large magma chamber, compaction zones of several tens to hundreds of meter may form adcumulates with porosities in the order of 5%. In conclusion, gravitation driven chemical compaction is feasible for dense mafic minerals in basaltic magmas, in particular in large layered intrusions. The limiting factor appears to be rather the supply of crystals then the time necessary for compaction.

Chromium isotope variations (δ53/52Cr) in mantle-derived sources and their weathering products: Implications for environmental studies and the evolution of δ53/52Cr in the Earth’s mantle over geologic time

NASA Astrophysics Data System (ADS)

Farkaš, Juraj; Chrastný, Vladislav; Novák, Martin; Čadkova, Eva; Pašava, Jan; Chakrabarti, Ramananda; Jacobsen, Stein B.; Ackerman, Lukáš; Bullen, Thomas D.

2013-12-01

Here we report chromium isotope compositions, expressed as δ53/52Cr in per mil (‰) relative to NIST 979, measured in selected Cr-rich minerals and rocks formed by the primary magmatic as well as the secondary metamorphic and weathering processes. The main objectives of this study were: (i) to further constrain the isotope composition of the Earth’s mantle Cr inventory and its possible variation during geological history, based on the analysis of globally distributed and stratigraphically constrained mantle-derived chromites; and (ii) to investigate the magnitude and systematics of Cr isotope fractionation during oxidative weathering and secondary alteration (i.e., hydration, serpentinization) of the magmatic Cr sources. Specifically, we analyzed δ53/52Cr in a set of globally distributed mantle-derived chromites (FeMgCr2O4, n = 30) collected from various locations in Europe, Asia, Africa and South America, and our results confirm that a chromite-hosted Earth’s mantle Cr inventory is uniform at -0.079 ± 0.129‰ (2SD), which we named here as a ‘canonical’ mantle δ53/52Cr signature. Furthermore our dataset of stratigraphically constrained chromites, whose crystallization ages cover most of the Earth’s geological history, indicate that the bulk Cr isotope composition of the chromite-hosted mantle inventory has remained uniform, within about ±0.100‰, since at least the Early Archean times (∼3500 million years ago, Ma). To investigate the systematics of Cr isotope fractionation associated with alteration processes we analyzed a number of secondary Cr-rich minerals and variably altered ultramafic rocks (i.e., serpentinized harzburgites, lherzolites) that revealed large positive δ53/52Cr anomalies that are systematically shifted to higher values with an increasing degree of alteration and serpentinization. The degree of aqueous alteration and serpentinization was quantified by the abundances of fluid-mobile (Rb, K) elements, and by the Loss On Ignition (LOI) parameter, which determines the amount of structurally bound water (OH/H2O) present in secondary hydrated minerals like serpentine. Overall, we observed that altered ultramafic rocks that yielded the highest LOI values, and the lowest amounts of fluid mobile elements, also yielded the heaviest δ53/52Cr signatures. Therefore, we conclude that secondary alteration (i.e., hydration, serpentinization) of ultramafic rocks in near-surface oxidative environments tend to shift the bulk Cr isotope composition of the weathered products to isotopically heavier values, pointing to a dynamic redox cycling of Cr in the Earth’s crustal and near-surface environments. Hence, if validated by future studies, this would suggest that Cr isotopes could be used to trace the recycling of altered oceanic lithosphere through subduction zones, and to detect the sources of dehydrated and previously serpentinized oceanic crust carrying ‘heavy’ δ53/52Cr signatures in island arc systems. Finally, the fact that the geogenic Cr sources may locally exhibit anomalous (non-canonical) δ53/52Cr signatures has also implications for environmental studies that use δ53/52Cr as a tracer to quantify the amount of the hexavalent Cr reduction in waters.

Synthesis and biological evaluation of chalcone derivatives (mini review).

PubMed

Bukhari, Syed Nasir Abbas; Jasamai, Malina; Jantan, Ibrahim

2012-11-01

Chalcones are the principal precursors for the biosynthesis of flavonoids and isoflavonoids. A three carbon α, β-unsaturated carbonyl system constitutes chalcones. Chalcones are the condensation products of aromatic aldehyde with acetophenones in attendance of catalyst. They go through an assortment of chemical reactions and are found advantageous in synthesis of pyrazoline, isoxazole and a variety of heterocyclic compounds. In synthesizing a range of therapeutic compounds, chalcones impart key role. They have showed worth mentioning therapeutic efficacy for the treatment of various diseases. Chalcone based derivatives have gained heed since they own simple structures, and diverse pharmacological actions. A lot of methods and schemes have been reported for the synthesis of these compounds. Amongst all, Aldol condensation and Claisen-Schmidt condensation still grasp high up position. Other distinguished techniques include Suzuki reaction, Witting reaction, Friedel-Crafts acylation with cinnamoyl chloride, Photo-Fries rearrangement of phenyl cinnamates etc. These inventive techniques utilize various catalysts and reagents including SOCl(2) natural phosphate, lithium nitrate, amino grafted zeolites, zinc oxide, water, Na(2)CO(3), PEG400, silicasulfuric acid, ZrCl(4) and ionic liquid etc. The development of better techniques for the synthesis of α, β- unsaturated carbonyl compounds is still in high demand. In brief, we have explained the methods and catalysts used in the synthesis of chalcones along with their biological activities in a review form to provide information for the development of new-fangled processes targeting better yield, less reaction time and least side effects with utmost pharmacological properties.

Porphyrin-Sensitized Evolution of Hydrogen using Dawson and Keplerate Polyoxometalate Photocatalysts.

PubMed

Panagiotopoulos, Athanassios; Douvas, Antonios M; Argitis, Panagiotis; Coutsolelos, Athanassios G

2016-11-23

Hydrogen evolution using photocatalytic systems based on artificial photosynthesis is a major approach toward solar energy conversion and storage. In the polyoxometalate-based photocatalytic systems proposed in the past, middle/near UV light irradiation and noble-metal catalysts were mainly used. Although recently polyoxometalates were sensitized in visible light, photosensitizers or catalysts based on noble metals, and/or poor activity of polyoxometalates were generally obtained. Here we show the highly efficient [turnover number (TON)=215] hydrogen evolution induced by the zinc(II) mesotetrakis(N-methyl-pyridinium-4-yl)porphyrin (ZnTMPyP 4+ ) sensitization of a series of polyoxometalate catalysts (two Dawson type, P 2 Mo 18 O 62 6- and P 2 W 18 O 62 6- anions, and one Keplerate {Mo 132 } cluster) in a visible-light-driven, noble-metal-free, and fully water-soluble system. We attributed the high efficiency for hydrogen evolution to the multi-electron reduction of polyoxometalates and found that: (a) both Dawson polyoxometalates exhibit higher hydrogen evolution efficiency upon ZnTMPyP 4+ sensitization in relation to the direct photoreduction of those compounds; (b) the P 2 Mo 18 O 62 6- anion is more efficient (TON=65 vs. 38, respectively) for hydrogen evolution than the P 2 W 18 O 62 6- anion; and (c) the high nuclearity Keplerate {Mo 132 } cluster exhibits the highest efficiency (TON=215) for hydrogen evolution compared with the polyoxometalates studied. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nitrogen Isotopic Disequilibrium in the Cape York III A Iron

NASA Astrophysics Data System (ADS)

Zipfel, J.; Kim, Y.; Marti, K.

1995-09-01

Cape York is a medium octahedrite of the class III A, which is presumed to have been formed by fractional crystallization of an asteroidal metal core (1). Within the Cape York kamacite-taenite matrix abundant troilite nodules are found. From their elongated form it has been suggested that immiscible S-rich liquids were trapped under the influence of a gravity field. Some of these nodules contain chromite grains, preferentially at the bottom of the troilite/metal boundary (2,3). Minor phases within the troilite are sulfides, phosphates, silica and copper. Carlsbergite (CrN) is exclusively found within the metal matrix. The nitrogen isotopic composition in metal of Cape York was analyzed by several workers and found to be enriched in 14N (delta^(15)N -32.3 to -94.8 per mil) with concentrations varying from 7 to 37 ppm. The large range of N concentrations may reflect artifacts due to experimental difficulties (4), but also might be attributed to varying amounts of CrN within the metal separates. The N in troilite (delta^(15)N -3.8+/-1.2 per mil) was found to be heavier than that observed in metal (4). In one temperature step (1100 degrees C) during stepwise release, nitrogen with a delta^(15)N of -32 per mil was measured, indicating inclusions of an isotopically distinct phase in troilite. In order to trace the nature of the inclusion we determined the N isotopic composition first in a small pilot sample and then in a larger (23.93mg) chromite separate. The latter was stepwise heated at temperatures between 400 and 1000 degrees C, and the release of sample N started at 700 degrees C (delta^(15)N -9.6+/-2.4 per mil). The lightest N component was measured in the 1000 degrees C step with delta^(15)N -56.4+/-13.0 per mil and the average N composition is obtained as delta^(15)N -25.8 per mil. This result supports earlier evidence that nitrogen is isotopically not equilibrated between chromite, surrounding troilite and metal matrix. Possible processes which could lead to a disequilibrium as observed in Cape York include (a) survival of primary isotopic heterogeneities; (b) N loss during secondary processes, e.g., metamorphic heating and shock deformation: (a) Graphite grains within metal of the Acapulco meteorite were identified as carrier of isotopically distinct N and C components and were interpreted as surviving (possibly presolar) grains unaffected by the igneous alteration of the bulk meteorite (5). Obviously such grains exchanged N isotopically with metal and chromite, but not with sulfides and silicates, as these do not carry the light N of metal and chromite (6). The mechanism of this exchange is, however, unclear. No graphite has been observed so far in Cape York. Yet, isotopic heterogeneities in the precursor material of Cape York can not be excluded. During melting of the parent asteroid one would expect homogenization of the nitrogen isotopes. Since chromite and metal crystallize at high temperatures, a probable exchange of N between the S-rich melt and a distinct N reservoir at lower temperature might explain the disequilibrium. (b) Troilite nodules in Cape York indicate a small degree of shock deformation (2,3,5). One might argue that some N was lost and the residue fractionated during this event. However, 107Ag/109Ag ratios from metal and troilite correlate with Pd/Ag ratios, which is not the case in severely shocked magmatic irons (7). In addition, similar isotopic N fractionations are found in the "magmatic" Acapulco meteorite, which shows no indication of shock deformation. Therefore, secondary loss of N preferentially from troilite can be excluded. References: [1] Haak H. and Scott E. (1993) GCA, 57, 3457-3472. [2] Buchwald V. (1975) Handbook of Iron Meteorites, Vols. 1_3, Univ. of California and Arizona State Univ., Berkeley. [3] Kracher A et al. (1977) Geochem. J., 11, 207-217. [4] Murty S. and Marti K. (1994) GCA, 58, 1841-1848. [5] El Goresy A. et al. (1995) Nature, 373, 496-499. [6] Kim Y. et al. (1992) LPS XXIII, 691-692. [7] Teshima J. et al. (1986) GCA, 50, 2073-2087.

Photo-induced electron transfer method

DOEpatents

Wohlgemuth, R.; Calvin, M.

1984-01-24

The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospholipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transferring electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

Rh(II)-catalyzed Reactions of Diazoesters with Organozinc Reagents

PubMed Central

Panish, Robert; Selvaraj, Ramajeyam; Fox, Joseph M.

2015-01-01

Rh(II)-catalyzed reactions of diazoesters with organozinc reagents are described. Diorganozinc reagents participate in reactions with diazo compounds by two distinct, catalyst-dependent mechanisms. With bulky diisopropylethylacetate ligands, the reaction mechanism is proposed to involve initial formation of a Rh-carbene and subsequent carbozincation to give a zinc enolate. With Rh2(OAc)4, it is proposed that initial formation of an azine precedes 1,2-addition by an organozinc reagent. This straightforward route to the hydrazone products provides a useful method for preparing chiral quaternary α-aminoesters or pyrazoles via the Paul-Knorr condensation with 1,3-diketones. Crossover and deuterium labeling experiments provide evidence for the mechanisms proposed. PMID:26241081

Rh(II)-Catalyzed Reactions of Diazoesters with Organozinc Reagents.

PubMed

Panish, Robert; Selvaraj, Ramajeyam; Fox, Joseph M

2015-08-21

Rh(II)-catalyzed reactions of diazoesters with organozinc reagents are described. Diorganozinc reagents participate in reactions with diazo compounds by two distinct, catalyst-dependent mechanisms. With bulky diisopropylethyl acetate ligands, the reaction mechanism is proposed to involve initial formation of a Rh-carbene and subsequent carbozincation to give a zinc enolate. With Rh2(OAc)4, it is proposed that initial formation of an azine precedes 1,2-addition by an organozinc reagent. This straightforward route to the hydrazone products provides a useful method for preparing chiral quaternary α-aminoesters or pyrazoles via the Paul-Knorr condensation with 1,3-diketones. Crossover and deuterium labeling experiments provide evidence for the mechanisms proposed.

Quadrupolar magic angle spinning NMR spectra fitted using the Pearson IV function.

PubMed

Mironenko, Roman M; Belskaya, Olga B; Talsi, Valentin P; Likholobov, Vladimir A

2014-01-01

The Pearson IV function was used to fit the asymmetric solid-state (27)Al NMR spectra of alumina based catalysts. A high convergence (correlation coefficient is no less than 0.997) between experimental and simulated spectra was achieved. The decomposition of the (27)Al NMR spectra of zinc/aluminum mixed oxides with different Zn/Al molar ratio revealed an increased fraction (6-9%) of pentacoordinated aluminum atoms in these oxides as compared to γ-Al2O3. As the Zn/Al ratio is raised, the fraction of [AlO6] octahedral units decreases, while the fraction of [AlO4] tetrahedra increases. Copyright © 2014 Elsevier Inc. All rights reserved.

The first data on breithauptite in chromitite from the northern part of the Voykar-Synya ultramafic massif (Polar Urals)

NASA Astrophysics Data System (ADS)

Shaibekov, R. I.; Gaikovich, M. M.; Isaenko, S. I.; Shevchuk, S. S.

2017-11-01

This work presents the results of studying the mineral composition of chromite ores of the Khoila area. For the first time, nickel antimonide (breithauptite), including an Au-bearing type (with intergrowths and microinclusions of auricuprides) was found in the paragenesis with chromespinelides.

Using Vanadium in Spinel as a Sensor of Oxygen Fugacity in Meteorites: Applications to Mars, Vesta, and Other Asteroids

NASA Technical Reports Server (NTRS)

Righter, K.; Sutton, S.; Danielson, L.; Le, L.; Newville, M.; Pando, K.

2009-01-01

Igneous and metamorphic rocks commonly contain a mineral assemblage that allows oxygen fugacity to be calculated or constrained such as FeTi oxides, olivine-opx-spinel, or some other oxybarometer [1]. Some rocks, however, contain a limited mineral assemblage and do not provide constraints on fO2 using mineral equilibria. Good examples of the latter are orthopyroxenites or dunites, such as diogenites, ALH 84001, chassignites, or brachinites. In fact it is no surprise that the fO2 of many of these samples is not well known, other than being "reduced" and below the metal saturation value. In order to bridge this gap in our understanding, we have initiated a study of V in chromites in natural meteorite samples. Because the V pre-edge peak intensity and energy in chromites varies with fO2 (Fig. 1) [2], and this has been calibrated over a large fO 2 range, we can apply this relation to rocks for which we otherwise have no fO2 constraints.

Solidification/stabilization of chromite ore processing residue using alkali-activated composite cementitious materials.

PubMed

Huang, Xiao; Zhuang, RanLiang; Muhammad, Faheem; Yu, Lin; Shiau, YanChyuan; Li, Dongwei

2017-02-01

Chromite Ore Processing Residue (COPR) produced in chromium salt production process causes a great health and environmental risk with Cr(VI) leaching. The solidification/stabilization (S/S) of COPR using alkali-activated blast furnace slag (BFS) and fly ash (FA) based cementitious material was investigated in this study. The optimum percentage of BFS and FA for preparing the alkali-activated BFS-FA binder had been studied. COPR was used to replace the amount of BFS-FA or ordinary Portland cement (OPC) for the preparation of the cementitious materials, respectively. The immobilization effect of the alkali-activated BFS-FA binder on COPR was much better than that of OPC based cementitious material. The potential for reusing the final treatment product as a readily available construction material was evaluated. X-ray diffraction (XRD), Fourier transform infrared spectrometry (FTIR) and scanning electron microscope with energy dispersive spectrometer (SEM-EDS) analysis indicated that COPR had been effectively immobilized. The solidification mechanism is the combined effect of reduction, ion exchange, precipitation, adsorption and physical fixation in the alkali-activated composite cementitious material. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of interlayer cations of montmorillonite on the biodegradation and adsorption of crude oil polycyclic aromatic compounds.

PubMed

Ugochukwu, Uzochukwu C; Manning, David A C; Fialips, Claire I

2014-09-01

Cation exchange capacity, surface acidity and specific surface area are surface properties of clay minerals that make them act as catalysts or supports in most biogeochemical processes hence making them play important roles in environmental control. However, the role of homoionic clay minerals during the biodegradation of polycyclic aromatic compounds is not well reported. In this study, the effect of interlayer cations of montmorillonites in the removal of some crude oil polycyclic aromatic compounds during biodegradation was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. The homoionic montmorillonites were prepared via cation exchange reactions by treating the unmodified montmorillonite with the relevant metallic chloride. The study indicated that potassium-montmorillonite and zinc-montmorillonite did not enhance the biodegradation of the polycyclic aromatic hydrocarbons whereas calcium-montmorillonite, and ferric-montmorillonite enhanced their biodegradation significantly. Adsorption of polycyclic aromatic hydrocarbons was significant during biodegradation with potassium- and zinc-montmorillonite where there was about 45% removal of the polycyclic aromatic compounds by adsorption in the experimental microcosm containing 5:1 ratio (w/w) of clay to oil. Copyright © 2014 Elsevier Ltd. All rights reserved.

All zinc-blende GaAs/(Ga,Mn)As core-shell nanowires with ferromagnetic ordering.

PubMed

Yu, Xuezhe; Wang, Hailong; Pan, Dong; Zhao, Jianhua; Misuraca, Jennifer; von Molnár, Stephan; Xiong, Peng

2013-04-10

Combining self-catalyzed vapor-liquid-solid growth of GaAs nanowires and low-temperature molecular-beam epitaxy of (Ga,Mn)As, we successfully synthesized all zinc-blende (ZB) GaAs/(Ga,Mn)As core-shell nanowires on Si(111) substrates. The ZB GaAs nanowire cores are first fabricated at high temperature by utilizing the Ga droplets as the catalyst and controlling the triple phase line nucleation, then the (Ga,Mn)As shells are epitaxially grown on the side facets of the GaAs core at low temperature. The growth window for the pure phase GaAs/(Ga,Mn)As core-shell nanowires is found to be very narrow. Both high-resolution transmission electron microscopy and scanning electron microscopy observations confirm that all-ZB GaAs/(Ga,Mn)As core-shell nanowires with smooth side surface are obtained when the Mn concentration is not more than 2% and the growth temperature is 245 °C or below. Magnetic measurements with different applied field directions provide strong evidence for ferromagnetic ordering in the all-ZB GaAs/(Ga,Mn)As nanowires. The hybrid nanowires offer an attractive platform to explore spin transport and device concepts in fully epitaxial all-semiconductor nanospintronic structures.

Preparation of ZnO Photocatalyst for the Efficient and Rapid Photocatalytic Degradation of Azo Dyes.

PubMed

Chen, Xiaoqing; Wu, Zhansheng; Liu, Dandan; Gao, Zhenzhen

2017-12-01

Zinc oxide (ZnO) photocatalysts were synthesized by sol-gel method using zinc acetate as precursor for degradation of azo dyes under UV irradiation. The resultant samples were characterized by different techniques, such as XRD, SEM, and EDX. The influence of preparation conditions such as calcination temperature and composite ratio on the degradation of methyl orange (MO) was investigated. ZnO prepared with a composite ratio of 4:1 and calcination temperature of 400 °C exhibited 99.70% removal rate for MO. The effect of operation parameters on the degradation was also studied. Results showed that the removal rate of azo dyes increased with the increased dosage of catalyst and decreased initial concentration of azo dyes and the acidic condition is favorable for degradation. Furthermore, the kinetics and scavengers of the reactive species during the degradation were also investigated. It was found that the degradation of azo dyes fitted the first-order kinetics and superoxide ions were the main species. The proposed photocatalyst can efficiently and rapidly degrade azo dyes; thus, this economical and environment-friendly photocatalyst can be applied to the treatment of wastewater contaminated with synthetic dyes.

Photocatalytic degradation of sunscreen active ingredients mediated by nanostructured materials

NASA Astrophysics Data System (ADS)

Soto-Vazquez, Loraine

Water scarcity and pollution are environmental issues with terrible consequences. In recent years several pharmaceutical and personal care products, such as sunscreen active ingredients, have been detected in different water matrices. Its recalcitrant behavior in the environment has caused controversies and generated countless questions about its safety. During this research, we employed an advanced oxidation process (photocatalysis) to degrade sunscreen active ingredients. For this study, we used a 3x3 system, evaluating three photocatalysts and three different contaminants. From the three catalysts employed, two of them were synthesized. ZnO nanoparticles were obtained using zinc acetate dihydrated as the precursor, and TiO2 nanowires were synthesized from titanium tetrachloride precursor. The third catalyst employed (namely, P25) was obtained commercially. The synthesized photocatalysts were characterized in terms of the morphology, elemental composition, crystalline structure, elemental oxidation states, vibrational modes and surface area, using SEM-EDS, XRD, XPS, Raman spectroscopy and BET measurements, respectively. The photocatalysts were employed during the study of the degradation of p-aminobenzoic acid, phenylbenzimidazole sulfonic acid, and benzophenone-4. In all the cases, at least 50% degradation was achieved. P25 showed degradation efficiencies above 90%, and from the nine systems, 7 of them degraded at least 86%.

Co@Co3 O4 @PPD Core@bishell Nanoparticle-Based Composite as an Efficient Electrocatalyst for Oxygen Reduction Reaction.

PubMed

Wang, Zhijuan; Li, Bing; Ge, Xiaoming; Goh, F W Thomas; Zhang, Xiao; Du, Guojun; Wuu, Delvin; Liu, Zhaolin; Andy Hor, T S; Zhang, Hua; Zong, Yun

2016-05-01

Durable electrocatalysts with high catalytic activity toward oxygen reduction reaction (ORR) are crucial to high-performance primary zinc-air batteries (ZnABs) and direct methanol fuel cells (DMFCs). An efficient composite electrocatalyst, Co@Co3 O4 core@shell nanoparticles (NPs) embedded in pyrolyzed polydopamine (PPD) is reported, i.e., in Co@Co3 O4 @PPD core@bishell structure, obtained via a three-step sequential process involving hydrothermal synthesis, high temperature calcination under nitrogen atmosphere, and gentle heating in air. With Co@Co3 O4 NPs encapsulated by ultrathin highly graphitized N-doped carbon, the catalyst exhibits excellent stability in aqueous alkaline solution over extended period and good tolerance to methanol crossover effect. The integration of N-doped graphitic carbon outer shell and ultrathin nanocrystalline Co3 O4 inner shell enable high ORR activity of the core@bishell NPs, as evidenced by ZnABs using catalyst of Co@Co3 O4 @PPD in air-cathode which delivers a stable voltage profile over 40 h at a discharge current density of as high as 20 mA cm(-2) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Porous LaCo1-xNixO3-δ Nanostructures as an Efficient Electrocatalyst for Water Oxidation and for a Zinc-Air Battery.

PubMed

Vignesh, Ahilan; Prabu, Moni; Shanmugam, Sangaraju

2016-03-09

Perovskites have emerged as promising earth-abundant alternatives to precious metals for catalyzing the oxygen evolution reaction (OER). Herein, we report the synthesis of a series of porous perovskite nanostructures, LaCo0.97O3-δ, with systematic Ni substitution in Co octahedral sites. Their electrocatalytic activity during the water oxidation reaction was studied in alkaline electrolytes. The electrocatalytic OER activity and stability of the perovskite nanostructure was evaluated using the rotating disk electrode technique. We show that the progressive replacement of Co by Ni in the LaCo0.97O3-δ perovskite structure greatly altered the electrocatalytic activity and that the La(Co0.71Ni0.25)0.96O3-δ composition exhibited the lowest OER overpotential of 324 and 265 mV at 10 mA cm(-2) in 0.1 M KOH and 1 M KOH, respectively. This value was much lower than that of the noble metal catalysts, IrO2, Ru/C, and Pt/C. Furthermore, the La(Co0.71Ni0.25)0.96O3-δ nanostructure showed outstanding electrode stability, with no observable decrease in performance up to 114th cycle in the auxiliary linear sweep voltammetry that lasted for 10 h in chronoamperometry studies. The excellent oxygen evolution activity of the La(Co0.71Ni0.25)0.96O3-δ perovskite nanostructure can be attributed to its intrinsic structure, interconnected particle arrangement, and unique redox characteristics. The enhanced intrinsic electrocatalytic activity of the La(Co0.71Ni0.25)0.96O3-δ catalyst was correlated with several parameters, such as the electrochemical surface area, the roughness factor, and the turnover frequency, with respect to variation in the transition metals of the perovskite structure. Subsequently, La(Co0.71Ni0.25)0.96O3-δ was utilized as the air cathode in a zinc-air battery application.

Multi-scale analysis of the occurrence of Pb, Cr and Mn in the NIST standards: Urban dust (SRM 1649a) and indoor dust (SRM 2584)

NASA Astrophysics Data System (ADS)

Jiang, Mingyu; Nakamatsu, Yuki; Jensen, Keld A.; Utsunomiya, Satoshi

2014-01-01

Adverse health effects of ambient particulate matters are closely related to the speciation of the constituting organic matters and toxic metals. To determine multi-parameters of the metal speciation in urban and indoor dusts, we have performed systematic bulk- to nano-scale (“multi-scale”) analysis on the speciation of Pb, Mn, and Cr in two National Institute of Standards and Technology (NIST) standard reference materials (SRMs): urban dust (SRM 1649a) and indoor dust (SRM 2584), utilizing X-ray absorption near-edge structure, powder X-ray diffraction analysis, electron microprobe analysis, scanning electron microscopy, and transmission electron microscopy. Major crystalline phases are quartz, gypsum, kaolinite, and muscovite in SRM 1649a, while quartz, gypsum, calcite, and possibly muscovite (or chabazite) in SRM 2584. A number of Pb sulfate nanoparticles (50-200 nm) occur in SRM 1649a, whereas micron-sized Pb carbonate is present containing various concentrations of Zn and Ti in the complex texture in SRM 2584. Relatively soluble Mn(II) sulfate is the bulk-averaged Mn speciation in SRM 1649a, although discrete Mn sulfate particles are not characterized by individual particle analysis, implying the diluted Mn distribution within other sulfate. In SRM 2584, Mn speciation includes a mixture of oxides and carbonates, and trace Mn in chromite. Chromite (FeCr2O4) is the major Cr speciation in SRM1694a, while unidentified Cr(III) phases with minor chromite and Pb chromate are present in SRM 2584, among which the Pb chromate is composed of Cr(VI). A significant number of the metal-bearing particles are distributed to the submicron-size fraction in the urban dust, SRM 1649a, suggesting that these metal nanoparticles can potentially penetrate into the deep respiratory system. This study demonstrates that multi-scale analysis combining nano and bulk analytical techniques is a powerful approach to investigate the multi-parameters of metal-bearing nanoparticles in heterogeneous PM samples.

Pressure increases, the for­mation of chromite seams, and the development of the ultramafic series in the Stillwater Complex, Montana

USGS Publications Warehouse

Lipin, Bruce R.

1993-01-01

This paper explores the hypothesis that chromite seams in the Stillwater Complex formed in response to periodic increases in total pressure in the chamber. Total pressure increased because of the positive δV of nucleation of CO2 bubbles in the melt and their subsequent rise through the magma chamber, during which the bubbles increased in volume by a factor of 4–6. By analogy with the pressure changes in the summit chambers of Kilauea and Krafla volcanoes, the maximum variation was 0⋅2–0⋅25 kbar, or 5–10% of the total pressure in the Stillwater chamber. An evaluation of the likelihood of fountaining and mixing of a new, primitive liquid that entered the chamber with the somewhat more evolved liquid already in the chamber is based upon calculations using observed and inferred velocities and flow rates of basaltic magmas moving through volcanic fissures. The calculations indicate that hot, dense magma would have oozed, rather than fountained into the chamber, and early mixing of the new and residual magmas that could have resulted in chromite crystallizing alone did not take place.Mixing was an important process in the Stillwater magma chamber, however. After the new magma in the chamber underwent ˜5% fractional crystallization, its composition, temperature, and density approached those of the overlying liquid in the chamber and the liquids then mixed. If this process occurred many times over the course of the development of the Ultramafic series, a thick column of magma with orthopyroxene on its liquidus would have been the result. Thus, the sequence of multiple injections, fractionation, and mixing with previously fractionated magma could have been the mechanism that produced the thick bronzite cumulate layer (the Bronzitite zone) above the cyclic units.

Relict chondrules in primitive achondrites: Remnants from their precursor parent bodies

NASA Astrophysics Data System (ADS)

Schrader, Devin L.; McCoy, Timothy J.; Gardner-Vandy, Kathryn

2017-05-01

We studied the petrography, analyzed the chemical compositions, constrained the closure temperatures (via geothermometry), and determined the oxidation states of relict chondrules in Campo del Cielo (IAB iron meteorite), Graves Nunataks (GRA) 98028 (acapulcoite), and Netschaëvo (IIE iron meteorite) to constrain their formation conditions and investigate links to known meteorite groups. Despite having been thermally metamorphosed, mineral phases within relict chondrules retain information about their precursor compositions. The sizes and textures of relict chondrules, and silicate and chromite compositions indicate that Campo del Cielo, GRA 98028, and Netschaëvo had distinct parent bodies that were similar to, but different from, known chondrite groups. To determine the utility of relict chondrule sizes in thermally metamorphosed meteorites, we determined the chondrule size distributions in the LL chondrites Semarkona (LL3.00), Soko-Banja (LL4), Siena (LL5), and Saint-Séverin (LL6), and the H chondrites Clovis (No. 1) (H3.6), Kesen (H4), Arbol Solo (H5), and Estacado (H6). As expected, mean chondrule diameters increase with degree of thermal metamorphism. We find that Campo del Cielo and GRA 98028 were reduced during thermal metamorphism, consistent with previous studies, indicating that their precursors were initially more FeO-rich than their current compositions. In contrast to previous studies, we find no evidence for reduction of silicates in Netschaëvo. Normal zoning of olivine in Netschaëvo is consistent with crystallization and suggests its silicates are near their primary FeO-contents. The presence of elongated chromite grains along olivine grain boundaries in Netschaëvo indicates formation during thermal metamorphism under oxidizing conditions. Due to the absence of reduction and the composition of chromite being distinct from that of metamorphosed H chondrites, we conclude that Netschaëvo, and by extension the IIE iron meteorites, are not from the H chondrite parent body.

Diamond exploration and regional prospectivity of Western Australia

NASA Astrophysics Data System (ADS)

Hutchison, Mark T.

2018-06-01

Pre-1.6 Ga rocks comprise around 45% of the onshore area of Western Australia (WA), constituting the West Australian Craton (WAC) (including the Archean Yilgarn and Pilbara Cratons) and the western part of the North Australian Craton (NAC). These areas provide the conditions suitable for diamond formation at depth, and numerous diamondiferous lamproite and kimberlite fields are known. As emplacement ages span close to 2500 Ma, there are significant opportunities for diamond-affinity rocks being present near-surface in much of the State, including amongst Phanerozoic rocks. WA's size, terrain, infrastructure and climate, mean that many areas remain underexplored. However, continuous diamond exploration since the 1970s has resulted in abundant data. In order to advance future exploration, a comprehensive database of results of diamond exploration sampling (Geological Survey of Western Australia 2018) has been assessed. The Yilgarn and Pilbara Cratons have spinel indicators almost exclusively dominated by chromite (>90% of grains), whereas (Mg,Fe,Ti)-bearing Al-chromites account for more of the indicator spinels in the NAC, up to 50% of grains at the Northern Territory (NT) border. Increasing dominance of Al in chromites is interpreted as a sign of weathering or a shallower source than Al-depleted Mg-chromites. Garnet compositions across the State also correlate with geological subdivisions, with lherzolitic garnets showing more prospective compositions (Ca-depleted) in WAC samples compared to the NAC. WAC samples also show a much broader scatter into strongly diamond-prospective G10 and G10D compositions. Ilmenites from the NAC show Mg-enriched compositions (consistent with kimberlites), over and above those present in NT data. However, ilmenites from the WAC again show the most diamond-prospective trends. Numerous indicator mineral concentrations throughout the State have unknown sources. Due in part to the presence of diamondiferous lamproites, it is cautioned that some accepted indicator mineral criteria do not apply in parts of WA. For example Ca-depleted garnets, Mg-depleted ilmenites and Cr-depleted and Al-absent clinopyroxenes are all sometimes associated with strongly diamondiferous localities. Quantitative prospectivity analysis has also been carried out based on the extent and results of sampling, age of surface rocks relative to ages of diamond-prospective rocks, and the underlying mantle structure. Results show that locations within the NAC and with proximity to WA's diamond mines score well. However, results point to parts of the WAC being more prospective, consistent with mineral chemical data. Most notable are the Hamersley Basin, Eastern Goldfields Superterrane and the Goodin Inlier of the Yilgarn Craton. Despite prolific diamond exploration, WA is considerably underexplored and the ageing Argyle mine and recent closure of operations at Ellendale warrant a re-evaluation of diamond potential. Results of mineral chemistry and prospectivity analysis make a compelling case for renewed exploration.

Surface-Tuned Co3O4 Nanoparticles Dispersed on Nitrogen-Doped Graphene as an Efficient Cathode Electrocatalyst for Mechanical Rechargeable Zinc-Air Battery Application.

PubMed

Singh, Santosh K; Dhavale, Vishal M; Kurungot, Sreekumar

2015-09-30

The most vital component of the fuel cells and metal-air batteries is the electrocatalyst, which can facilitate the oxygen reduction reaction (ORR) at a significantly reduced overpotential. The present work deals with the development of surface-tuned cobalt oxide (Co3O4) nanoparticles dispersed on nitrogen-doped graphene as a potential ORR electrocatalyst possessing some unique advantages. The thermally reduced nitrogen-doped graphene (NGr) was decorated with three different morphologies of Co3O4 nanoparticles, viz., cubic, blunt edged cubic, and spherical, by using a simple hydrothermal method. We found that the spherical Co3O4 nanoparticle supported NGr catalyst (Co3O4-SP/NGr-24h) has acquired a significant activity makeover to display the ORR activity closely matching with the state-of-the-art Pt supported carbon (PtC) catalyst in alkaline medium. Subsequently, the Co3O4-SP/NGr-24h catalyst has been utilized as the air electrode in a Zn-air battery, which was found to show comparable performance to the system derived from PtC. Co3O4-SP/NGr-24h catalyst has shown several hours of flat discharge profile at the discharge rates of 10, 20, and 50 mA/cm(2) with a specific capacity and energy density of ~590 mAh/g-Zn and ~840 Wh/kg-Zn, respectively, in the primary Zn-air battery system. In conjunction, Co3O4-SP/NGr-24h has outperformed as an air electrode in mechanical rechargeable Zn-air battery as well, which has shown consistent flat discharge profile with minimal voltage loss at a discharge rate of 50 mA/cm(2). The present results, thus demonstrate that the proper combination of the tuned morphology of Co3O4 with NGr will be a promising and inexpensive material for efficient and ecofriendly cathodes for Zn-air batteries.

Synthesis and characterization of phytochemical fabricated zinc oxide nanoparticles with enhanced antibacterial and catalytic applications.

PubMed

Ali, Jawad; Irshad, Rabia; Li, Baoshan; Tahir, Kamran; Ahmad, Aftab; Shakeel, Muhammad; Khan, Naeem Ullah; Khan, Zia Ul Haq

2018-06-01

A "green route" to fabricate nanoparticles has emerged as a revolutionary approach. The reported work presents a green approach to synthesize ZnO nanoparticles using Conyza canadensis plant leaves extract. The synthesis of ZnO was conducted at two different temperatures i.e. 30 °C and 80 °C. ZnO nanoparticles prepared at 80 °C were smaller in size and exhibited spherical morphology. The prepared nanomaterials were examined for the reduction of organic dyes i.e. methylene blue and methyl orange. The fabricated ZnO nanoparticles synthesized at 80 °C were found to be highly active for the reduction of aforementioned dyes with 94.5% reduction of MO and 85.3% reduction of MB in 45 min and 20 min respectively. The rate constant (k) for this reduction of MO was found to be 5.781 × 10 -3  s -1 in the absence of a catalyst and 5.843 × 10 -2  s -1 in the presence of ZnO NPs catalyst. The rate constant (k) for the reduction of MB was found to be 4.7 × 10 -3  s -1 in the absence of a catalyst and 9.936 × 10 -3  s -1 in the presence of ZnO NPs catalyst. ZnO nanoparticles synthesized at 80 °C were examined for their antibacterial activity. The biogenic ZnO nanoparticles exhibited strong antibacterial activity against E. coli and S. aureus with a zone of inhibition (16 mm) and (14 mm) respectively. This high antibacterial and catalytic activity of biogenic ZnO nanoparticles can be attributed to its small size, good dispersion, and well-defined morphology. Copyright © 2018 Elsevier B.V. All rights reserved.

Synthesis and Reactivity of Tripodal Complexes Containing Pendant Bases

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

Blacquiere, Johanna M.; Pegis, Michael L.; Raugei, Simone

2014-09-02

The synthesis of a new tripodal ligand family is reported, with tertiary-amine groups in the second-coordination sphere. The ligands are tris(amido)amine derivatives, with the pendant amines attached via a peptide coupling strategy. They were designed to be used in new catalysts for the oxygen reduction reaction (ORR), in which the pendant acid/base group could improve catalyst performance. Two members of the new ligand family were each metallated with Co(II) and Zn(II) to afford trigonal monopyramidal complexes. Reaction of the cobalt complexes, [Co(L)]-, with dioxygen reversibly generates a small amount of a Co(III)-superoxo species, which was characterized by EPR. Protonation ofmore » the zinc complex Zn[N{CH2CH2NC(O)CH2N(CH2Ph)2}3)-– ([Zn(TNBn)]-) with one equivalent of acid occurs with displacement and dissociation of an amide ligand. Addition of excess acid to the any of the complexes [M(L)]- results in complete proteolysis and formation of the ligands H3L. This decomposition limits the use of these complexes as catalysts for the ORR. An alternative ligand with two pyridyl arms was also prepared but could not be metallated. These studies highlight the importance of stability of the primary-coordination sphere of ORR electrocatalysts to both oxidative and acidic conditions. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

Photo-induced electron transfer method

DOEpatents

Wohlgemuth, Roland; Calvin, Melvin

1984-01-01

The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospho-lipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transfering electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

Direct Growth of Feather-Like ZnO Structures by a Facile Solution Technique for Photo-Detecting Application

NASA Astrophysics Data System (ADS)

Jiang, Yurong; Liu, Xingbing; Cai, Fangmin; Liu, Hairui

2017-08-01

The feather-like hierarchical zinc oxide (ZnO) was synthesized via successive ionic layer adsorption and reaction without any seed layer or metal catalyst. A possible growth mechanism is proposed to explain the forming process of ZnO feather-like structures. Meanwhile, the photo-electronic performances of the feather-like ZnO have been investigated with the UV-vis-NIR spectroscopy, I-V and I-tmeasurements. The results indicate that feather-like ZnO hierarchical structures have good anti-reflection and excellent photo-sensitivity. All results suggest that the direct growth processing of novel feather-like ZnO is envisaged to have promising application in the field of photo-detector devices.

Study of the zinc-silver oxide battery system

NASA Technical Reports Server (NTRS)

Nanis, L.

1973-01-01

Theoretical and experimental models for the evaluation of current distribution in flooded, porous electrodes are discussed. An approximation for the local current distribution function was derived for conditions of a linear overpotential, a uniform concentration, and a very conductive matrix. By considering the porous electrode to be an analog of chemical catalyst structures, a dimensionless performance parameter was derived from the approximated current distribution function. In this manner the electrode behavior was characterized in terms of an electrochemical Thiele parameter and an effectiveness factor. It was shown that the electrochemical engineering approach makes possible the organizations of theoretical descriptions and of practical experience in the form of dimensionless parameters, such as the electrochemical Thiele parameters, and hence provides useful information for the design of new electrochemical systems.

Stability of solid oxide fuel cell materials

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

Armstrong, T.R.; Bates, J.L.; Chick, L.A.

1996-04-01

Interconnection materials in a solid oxide fuel cell are exposed to both highly oxidizing conditions at the cathode and to highly reducing conditions at the anode. The thermal expansion characteristics of substituted lanthanum and yttrium chromite interconnect materials were evaluated by dilatometry as a function of oxygen partial pressures from 1 atm to 10{sup -18} atm, controlled using a carbon dioxide/hydrogen buffer.

Feature level fusion for enhanced geological mapping of ophiolile complex using ASTER and Landsat TM data

NASA Astrophysics Data System (ADS)

Pournamdari, M.; Hashim, M.

2014-02-01

Chromite ore deposit occurrence is related to ophiolite complexes as a part of the oceanic crust and provides a good opportunity for lithological mapping using remote sensing data. The main contribution of this paper is a novel approaches to discriminate different rock units associated with ophiolite complex using the Feature Level Fusion technique on ASTER and Landsat TM satellite data at regional scale. In addition this study has applied spectral transform approaches, consisting of Spectral Angle Mapper (SAM) to distinguish the concentration of high-potential areas of chromite and also for determining the boundary between different rock units. Results indicated both approaches show superior outputs compared to other methods and can produce a geological map for ophiolite complex rock units in the arid and the semi-arid region. The novel technique including feature level fusion and Spectral Angle Mapper (SAM) discriminated ophiolitic rock units and produced detailed geological maps of the study area. As a case study, Sikhoran ophiolite complex located in SE, Iran has been selected for image processing techniques. In conclusion, a suitable approach for lithological mapping of ophiolite complexes is demonstrated, this technique contributes meaningfully towards economic geology in terms of identifying new prospects.

Spectral transformation of ASTER and Landsat TM bands for lithological mapping of Soghan ophiolite complex, south Iran

NASA Astrophysics Data System (ADS)

Pournamdari, Mohsen; Hashim, Mazlan; Pour, Amin Beiranvand

2014-08-01

Spectral transformation methods, including correlation coefficient (CC) and Optimum Index Factor (OIF), band ratio (BR) and principal component analysis (PCA) were applied to ASTER and Landsat TM bands for lithological mapping of Soghan ophiolitic complex in south of Iran. The results indicated that the methods used evidently showed superior outputs for detecting lithological units in ophiolitic complexes. CC and OIF methods were used to establish enhanced Red-Green-Blue (RGB) color combination bands for discriminating lithological units. A specialized band ratio (4/1, 4/5, 4/7 in RGB) was developed using ASTER bands to differentiate lithological units in ophiolitic complexes. The band ratio effectively detected serpentinite dunite as host rock of chromite ore deposits from surrounding lithological units in the study area. Principal component images derived from first three bands of ASTER and Landsat TM produced well results for lithological mapping applications. ASTER bands contain improved spectral characteristics and higher spatial resolution for detecting serpentinite dunite in ophiolitic complexes. The developed approach used in this study offers great potential for lithological mapping using ASTER and Landsat TM bands, which contributes in economic geology for prospecting chromite ore deposits associated with ophiolitic complexes.

Method of making highly sinterable lanthanum chromite powder

DOEpatents

Richards, Von L.; Singhal, Subhash C.

1992-01-01

A highly sinterable powder consisting essentially of LaCrO.sub.3, containing from 5 weight % to 20 weight % of a chromite of dopant Ca, Sr, Co, Ba, or Mg and a coating of a chromate of dopant Ca, Sr, Co, Ba, or Mg; is made by (1) forming a solution of La, Cr, and dopant; (2) heating their solutions; (3) forming a combined solution having a desired ratio of La, Cr, and dopant and heating to reduce solvent; (4) forming a foamed mass under vacuum; (5) burning off organic components and forming a charred material; (6) grinding the charred material; (7) heating the char at from 590.degree. C. to 950 C. in inert gas containing up to 50,000 ppm O.sub.2 to provide high specific surface area particles; (8) adding that material to a mixture of a nitrate of Cr and dopant to form a slurry; (9) grinding the particles in the slurry; (10) freeze or spray drying the slurry to provide a coating of nitrates on the particles; and (11) heating the coated particles to convert the nitrate coating to a chromate coating and provide a highly sinterable material having a high specific surface area of over 7 m.sup.2 /g.

Pressure increases, the formation of chromite seams, and the development of the ultramafic series in the Stillwater Complex, Montana

USGS Publications Warehouse

Lipin, B.R.

1993-01-01

This paper explores the hypothesis that chromate seams in the Stillwater Complex formed in response to periodic increases in total pressure in the chamber. Total pressure increased because of the positive ??V of nucleation of CO2 bubbles in the melt and their subsequent rise through the magma chamber, during which the bubbles increased in volume by a factor of 4-6. By analogy with the pressure changes in the summit chambers of Kilauea and Krafla volcanoes, the maximum variation was 0.2-0.25 kbar, or 5-10% of the total pressure in the Stillwater chamber. An evaluation of the likelihood of fountaining and mixing of a new, primitive liquid that entered the chamber with the somewhat more evolved liquid already in the chamber is based upon calculations using observed and inferred velocities and flow rates of basaltic magmas moving through volcanic fissures. The calculations indicate that hot, dense magma would have oozed, rather than fountained into the chamber, and early mixing of the new and residual magmas that could have resulted in chromite crystallizing alone did not take place. -from Author

V Xanes in Spinels as an Oxy-Barometer in Meteorites with Implications for Redox Variations in the Inner Solar System

NASA Technical Reports Server (NTRS)

Righter, K.; Sutton, S.; Danielson, L.; Pando, K.; Le, L.; Newville, M.

2015-01-01

The variation of oxygen fugacity within inner solar system materials spans a range of nearly 15 orders of magnitude. Igneous and metamorphic rocks commonly contain a mineral assemblage that allows oxygen fugacity to be calculated or con-strained such as FeTi oxides, olivine-opx-spinel, or some other oxy-barometer. Some rocks, however, contain a limited mineral assemblage and do not provide constraints on fO2 using mineral equilibria. Good examples of the latter are orthopyroxenites or dunites, such as diogenites, ALH 84001, chassignites, or brachinites. In fact it is no surprise that the fO2 of many of these achondrites is not well known, other than being "reduced" and below the metal saturation value. In order to bridge this gap in our understanding, we have initiated a study of V in chromites in achondrite. Because the V pre-edge peak intensity and energy in chromites varies with fO2, and this has been calibrated over a large fO2 range, we can apply this relation to rocks for which we otherwise have no fO2 constraints.

Structural and Dielectric Study of (Dy,Er,Ho) CrO 3 Biferroic Compounds

NASA Astrophysics Data System (ADS)

Meza, Cesar; Siqueiros, Jesus; Duran, Alejandro

2011-03-01

Technological progress, especially in electronic applications, demands increasingly advanced substances, capable of performing a variety of tasks while simultaneously occupying less space than their predecessors. An answer to this demand lies within the realm of multiferroics. Multiferroic materials are defined as those single phase compounds where more than one ferroic order coexists; they generally belong to the perovskite group. One manifestation of multiferroicity, magnetoelectricity, requires the coexistence of spontaneous electric polarization and magnetic ordering. It is for this reason that rare-earth chromites have been selected as suitable candidates. This work is concerned with synthesis, characterization and dielectric response of the DyCr O3 , ErCr O3 and HoCr O3 ceramic compounds. The samples were synthesized by both the traditional solid state ceramic method, and the self-propagating combustion method. The resultant chromites were characterized by TG, DTA and XRD, which confirms the Pbnm space group. Additionally, conductivity analysis was performed and the associated activation energy determined for each system using experimental values and Arrhenius law. Thanks are due to DGAPA-UNAM for financial support through projects no. IN112909 and IN105711.

Pyrolysis Treatment of Chromite Ore Processing Residue by Biomass: Cellulose Pyrolysis and Cr(VI) Reduction Behavior.

PubMed

Zhang, Da-Lei; Zhang, Mei-Yi; Zhang, Chu-Hui; Sun, Ying-Jie; Sun, Xiao; Yuan, Xian-Zheng

2016-03-15

The pyrolysis treatment with biomass is a promising technology for the remediation of chromite-ore-processing residue (COPR). However, the mechanism of this process is still unclear. In this study, the behavior of pyrolysis reduction of Cr(VI) by cellulose, the main component of biomass, was elucidated. The results showed that the volatile fraction (VF) of cellulose, ie. gas and tar, was responsible for Cr(VI) reduction. All organic compounds, as well as CO and H2 in VF, potentially reduced Cr(VI). X-ray absorption near-edge structure (XANES) spectroscopy and extended X-ray absorption fine-structure (EXAFS) spectroscopy confirmed the reduction of Cr(VI) to Cr(III) and the formation of amorphous Cr2O3. The remnant Cr(VI) content in COPR can be reduced below the detection limit (2 mg/kg) by the reduction of COPR particle and extension of reaction time between VF and COPR. This study provided a deep insight on the co-pyrolysis of cellulose with Cr(VI) in COPR and an ideal approach by which to characterize and optimize the pyrolysis treatment for COPR by other organics.

Preparation of C60(O)n-ZnO nanocomposite under electric furnace and photocatalytic degradation of organic dyes.

PubMed

Cho, Bum Hwi; Oh, Youn Jun; Mun, Sang Mi; Ko, Weon Bae

2012-07-01

Zinc oxide (ZnO) nanoparticles were synthesized sonochemically by applying ultrasonic irradiation to a mixed aqueous-alcoholic solution of zinc nitrate with sodium hydroxide at room temperature. The morphology and optical properties of the ZnO nanoparticles were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV-vis spectroscopy. The C60(O)n nanoparticles were synthesized by heating a mixture of C60 and 3-chloroperoxybenzoic acid in a benzene solvent under the reflux system. The heated C60(O)n-ZnO nanocomposite was synthesized in an electric furnace at 700 degrees C for two hours. The heated C60(O)n-ZnO nanocomposite was characterized by XRD, SEM, and TEM, and examined as a catalyst in the photocatalytic degradation of organic dyes by UV-vis spectroscopy. The photocatalytic effect of the heated C60(O)n-ZnO nanocomposite was evaluated by a comparison with that of unheated C60(O)n nanoparticles, heated C60(O)n nanoparticles, and unheated C60(O)n-ZnO in organic dyes, such as methylene blue (MB), methyl orange (MO), and rhodamine B (RhB) under ultraviolet light at 365 nm.

Cu-Doped ZnO Thin Films Deposited by a Sol-Gel Process Using Two Copper Precursors: Gas-Sensing Performance in a Propane Atmosphere.

PubMed

Gómez-Pozos, Heberto; Arredondo, Emma Julia Luna; Maldonado Álvarez, Arturo; Biswal, Rajesh; Kudriavtsev, Yuriy; Pérez, Jaime Vega; Casallas-Moreno, Yenny Lucero; Olvera Amador, María de la Luz

2016-01-29

A study on the propane gas-sensing properties of Cu-doped ZnO thin films is presented in this work. The films were deposited on glass substrates by sol-gel and dip coating methods, using zinc acetate as a zinc precursor, copper acetate and copper chloride as precursors for doping. For higher sensitivity values, two film thickness values are controlled by the six and eight dippings, whereas for doping, three dippings were used, irrespective of the Cu precursor. The film structure was analyzed by X-ray diffractometry, and the analysis of the surface morphology and film composition was made through scanning electron microscopy (SEM) and secondary ion mass spectroscopy (SIMS), respectively. The sensing properties of Cu-doped ZnO thin films were then characterized in a propane atmosphere, C₃H₈, at different concentration levels and different operation temperatures of 100, 200 and 300 °C. Cu-doped ZnO films doped with copper chloride presented the highest sensitivity of approximately 6 × 10⁴, confirming a strong dependence on the dopant precursor type. The results obtained in this work show that the use of Cu as a dopant in ZnO films processed by sol-gel produces excellent catalysts for sensing C₃H₈ gas.

Deep seated inclusions in kimberlites from Kharamai field and some kimberlite fields of Prianabarie.

NASA Astrophysics Data System (ADS)

Ashchepkov, I. V.; Kuligin, S. S.; Afanasiev, V. P.; Vladykin, N. V.; Kostrovitsky, S. I.; Lelyukh, M. I.; Vavilov, M. A.; Nigmatulina, E. N.; Palessky, S. V.

2012-04-01

The problem of the thickness of the lithospheric keel in the northern part of Yakutia is critical for the diamond grade. Reported delamination of the SCLM (Griffin et al., 2005)which is not supported by the geophysical methods (Koulakov et al ., 2011) was checked in number of localities in circum Anabar region. Pyropes, chrome-diopside, omphacites, enstatite, chromites and ilmenites from concentrate three kimberlitic pipes of the Kharamai field revealed compositional variations typical for thick SCLM: pyropes to 13% Of cr2O3 in the association with chromites (to 60% Of cr2O3.) low- Al - Cr diopsides and enstatite, omphacites, Cr-pargasite and K-Na richterite and picroilmenites (to 20% Of MgO). The pyropes belong to lherzolite filed (Sobolev et al., 1973) as those published only in the low-chromium part relate to Ca- Fe to pyroxenite magmatic trend (Tychkov et al., 2008) which is typical for the majority of Mesozoic (especially Jurassic) kimberlitic pipes in Prianabarie and other northern parts of Yakutia. Thermo-barometric reconstructions using four methods of monomineral thermobarometry reveal the thickness of lithospheric keel not less than 200 km which coinsides with the determined thickness of the SCLM beneath nearest Ary- Mastakh filed (Khardakh pipe). Straya Rechka and Kuranakh fields (Universitetskaya, Tudovaya , Los kimberlites etc). But the pipes in Evenkiyskaya kimberlite group (including Malysh and Tuzic pipes) carry material dominantly from the upper part of the SCLM, sub-calcium garnets are rare. Relatively high oxidation state, determined according to chromite, pyroxenes and pyropes are in accord with the rather low diamond grades. However some other Jurassic pipes in northern part of the Siberian craton reveal sufficiently deep mantle roots evidencing about lack of the delamination of mantle keel after Siberian PT superplume. The trace elements determined for the pyropes show variations and belong to the melt metasomatized groups I the middle and lower part of the SCLM But those from upper part correspond to the LREE and LILE enriched melts. The chrome diopsides show dominantly the signs of the refertillization. The influence of the superplume melts for the SCLM in Kharamai field is higher then for the internal part of the Anabar region affected to the low Jurassic kimberlite magmatism. The Cretaceous pipes show the location of the magma derrivatio level near 130 km (Taylor et al ., 2003) Alluvial diamonds in the northern part of Siberian craton can be associated with undiscovered kimberlite II or lamproites which, were carried from the mantle sections of those saturated by eclogite. The relatively small portion of pyropes from thee deep part of the mantle sections in Prianabarie and surroundings is explained by the general exhaustion of mantle peridotite substratum in this region (Griffin et al., 1998). Rare Cr rich pyropes, chromites, orange pyropes referred to the deep eclogitic associations support this idea.

Platinum-group minerals in the LG and MG chromitites of the eastern Bushveld Complex, South Africa

NASA Astrophysics Data System (ADS)

Oberthür, Thomas; Junge, Malte; Rudashevsky, Nikolay; de Meyer, Eveline; Gutter, Paul

2016-01-01

The chromitites of the Bushveld Complex in South Africa contain vast resources of platinum-group elements (PGE); however, except for the economic upper group (UG)-2 chromitite seam, information on the distribution of the PGE in the ores and on the mineralogical nature, assemblages, and proportions of platinum-group minerals (PGM) is essentially missing. In the present geochemical and mineralogical study, PGE concentrates originating from the lower group (LG)-6 and middle group (MG)-1/2 chromitites were investigated with the intention to fill this gap of knowledge. Chondrite-normalized PGE patterns of bulk rock and concentrates are characterized by a positive slope from Os to Rh, a slight drop to Pt, and an increase to Pd again. The pronounced similarities of the PGE patterns indicate similar primary processes of PGE concentration in the chromitites, namely "sulfide control" of the PGE mineralization, i.e., co-precipitation of chromite and sulfide. Further, the primary control of PGE concentration in chromitites appears to be dual in character: (i) base-level concentrations of IPGE (up to ˜500 ppb) hosted within chromite and (ii) co-precipitation of chromite and sulfide, the latter containing virtually the entire remaining PGE budget. Sulfides (chalcopyrite, pentlandite, and pyrite; pyrrhotite is largely missing) are scarce within the chromitites and occur mainly interstitial to chromite grains. Pd and Rh contents in pentlandite are low and erratic. Essentially, the whole PGE inventory of the ores occurs in the form of discrete PGM. The PGM are almost always associated with sulfides. The dominant PGM are various Pt-Pd-Rh sulfides (cooperite/braggite [(Pt,Pd)S] and malanite/cuprorhodsite [CuPt2S4]/[CuRh2S4]), laurite [RuS2], the main carrier of the IPGE (Os, Ir, Ru), sulfarsenides [(Rh,Pt,Ir)AsS], sperrylite [PtAs2], Pt-Fe alloys, and a large variety of mainly Pd-rich PGM. The LG and MG chromitites have many characteristics in common and define a general, "typical" PGM spectrum of Bushveld chromitites. This PGM assemblage is characterized by the predominance of PGE-sulfides including elevated proportions of malanite, variable proportions of (sulf) arsenides, and Pt-Fe alloys in conjunction with a paucity of (bismutho)tellurides. The formation of this specific PGM spectrum is related to the distinct chromitite environment and its depositional and post-depositional history, whereby desulfurization reactions have probably played an important role. The LG-6 samples have higher contents of PGE-sulfides, including extraordinary high proportions of malanite but low PGE-arsenide and PGE-sulfarsenide contents compared to the MG-1/2 samples. This indicates a higher availability of arsenic either in the stratigraphically higher MG-1/2 samples (compared to the LG-6) or regionally in the chromitites south of the Steelpoort lineament.

Pulsed laser synthesis in liquid of efficient visible-light-active ZnO/rGO nanocomposites for improved photo-catalytic activity

NASA Astrophysics Data System (ADS)

Moqbel, Redhwan A.; Gondal, Mohammed A.; Qahtan, Talal F.; Dastageer, Mohamed A.

2018-03-01

In this work the synthesis of visible light active zinc oxide/reduced graphene oxide (ZnO/rGO) nanocomposite by laser induced fragmentation of particulates in liquid, its morphological/optical characterizations, and its application in the process of photo-catalytic degradation of toxic Rhodamine B (RhB) dye under visible radiation were studied. It is observed from the optical and morphological characterization that the anchoring of ZnO on the rGO sheets in ZnO/rGO nanocomposite considerably reduced the aggregation of ZnO (increased surface area), reduced the recombination of photo-induced charge carriers, promoted more adsorption of reactants on the catalytic surface and also enhanced and extended the light absorption in the visible spectral region. With all these improved characteristics of ZnO/rGO nanocomposite, it was found that this material as a photo-catalyst yielded an RhB degradation efficiency of 86%, as compared to the 40% degradation with pure ZnO NPs under the same experimental conditions. In the ZnO/rGO nanocomposite, rGO functions as an electron acceptor to promote charge separation, an aggregation inhibitor to enhance the active surface area, a co-catalyst, a good dye adsorber and also as a supporting matrix for ZnO.

Hydride VPE: the unexpected process for the fast growth of GaAs and GaN nanowires with record aspect ratio and polytypism-free crystalline structure

NASA Astrophysics Data System (ADS)

André, Yamina; Trassoudaine, Agnès.; Avit, Geoffrey; Lekhal, Kaddour; Ramdani, Mohammed R.; Leroux, Christine; Monier, Guillaume; Varenne, Christelle; Hoggan, Philip; Castelluci, Dominique; Bougerol, Catherine; Réveret, François; Leymarie, Joël.; Petit, Elodie; Dubrovskii, Vladimir G.; Gil, Evelyne

2013-12-01

Hydride Vapor Phase Epitaxy (HVPE) makes use of chloride III-Cl and hydride V-H3 gaseous growth precursors. It is known as a near-equilibrium process, providing the widest range of growth rates from 1 to more than 100 μm/h. When it comes to metal catalyst-assisted VLS (vapor-liquid-solid) growth, the physics of HVPE growth is maintained: high dechlorination frequency, high axial growth rate of nanowires (NWs) up to 170 μm/h. The remarkable features of NWs grown by HVPE are the untapered morphology with constant diameter and the stacking fault-free crystalline phase. Record pure zinc blende cubic phase for 20 μm long GaAs NWs with radii of 10 and 5 nm is shown. The absence of wurtzite phase in GaAs NWs grown by HVPE whatever the diameter is discussed with respect to surface energetic grounds and kinetics. Ni assisted, Ni-Au assisted and catalyst-free HVPE growth of wurtzite GaN NWs is also addressed. Micro-photoluminescence spectroscopy analysis revealed GaN nanowires of great optical quality, with a FWHM of 1 meV at 10 K for the neutral donor bound exciton transition.

Temperature dependence of stacking faults in catalyst-free GaAs nanopillars.

PubMed

Shapiro, Joshua N; Lin, Andrew; Ratsch, Christian; Huffaker, D L

2013-11-29

Impressive opto-electronic devices and transistors have recently been fabricated from GaAs nanopillars grown by catalyst-free selective-area epitaxy, but this growth technique has always resulted in high densities of stacking faults. A stacking fault occurs when atoms on the growing (111) surface occupy the sites of a hexagonal-close-pack (hcp) lattice instead of the normal face-centered-cubic (fcc) lattice sites. When stacking faults occur consecutively, the crystal structure is locally wurtzite instead of zinc-blende, and the resulting band offsets are known to negatively impact device performance. Here we present experimental and theoretical evidence that indicate stacking fault formation is related to the size of the critical nucleus, which is temperature dependent. The difference in energy between the hcp and fcc orientation of small nuclei is computed using density-function theory. The minimum energy difference of 0.22 eV is calculated for a nucleus with 21 atoms, so the population of nuclei in the hcp orientation is expected to decrease as the nucleus grows larger. The experiment shows that stacking fault occurrence is dramatically reduced from 22% to 3% by raising the growth temperature from 730 to 790 ° C. These data are interpreted using classical nucleation theory which dictates a larger critical nucleus at higher growth temperature.

Extended vapor-liquid-solid growth of silicon carbide nanowires.

PubMed

Rajesh, John Anthuvan; Pandurangan, Arumugam

2014-04-01

We developed an alloy catalytic method to explain extended vapor-liquid-solid (VLS) growth of silicon carbide nanowires (SiC NWs) by a simple thermal evaporation of silicon and activated carbon mixture using lanthanum nickel (LaNi5) alloy as catalyst in a chemical vapor deposition process. The LaNi5 alloy binary phase diagram and the phase relationships in the La-Ni-Si ternary system were play a key role to determine the growth parameters in this VLS mechanism. Different reaction temperatures (1300, 1350 and 1400 degrees C) were applied to prove the established growth process by experimentally. Scanning electron microscopy and transmission electron microscopy studies show that the crystalline quality of the SiC NWs increases with the temperature at which they have been synthesized. La-Ni alloyed catalyst particles observed on the top of the SiC NWs confirms that the growth process follows this extended VLS mechanism. The X-ray diffraction and confocal Raman spectroscopy analyses demonstrate that the crystalline structure of the SiC NWs was zinc blende 3C-SiC. Optical property of the SiC NWs was investigated by photoluminescence technique at room temperature. Such a new alloy catalytic method may be extended to synthesis other one-dimensional nanostructures.

The nature of iron deposits differs between symptomatic and asymptomatic carotid atherosclerotic plaques

DOE PAGES

Kopriva, David; Kisheev, Anastasye; Meena, Deiter; ...

2015-11-25

Iron within atherosclerotic plaque has been implicated as a catalyst of oxidative stress that causes progression of plaque, and plaque rupture. Iron is believed to accumulate within plaque by incorporation of erythrocytes following plaque rupture and hemorrhage. There is only indirect evidence to support this hypothesis. Plaque specimens were obtained from ten symptomatic and fifteen asymptomatic patients undergoing carotid endarterectomy at a single institution. Plaques were sectioned for study using synchrotron radiation induced X-ray fluorescence the study the distribution of zinc, calcium and iron. Histologic staining was carried out with Prussian Blue, and immunohistochemical staining was done to localize macrophagesmore » with CD68. Data were compared against patient clinical variables. Ten symptomatic (15 ± 10 days between index symptoms and surgery) and fifteen asymptomatic carotid plaques were studied. Zinc and calcium co-localized in mineralized areas of symptomatic and asymptomatic plaque. Iron was identified away from zinc and calcium in both symptomatic and asymptomatic plaques. Within the symptomatic plaques, iron was found within the thrombus associated with plaque rupture and hemorrhage. It did not stain with Prussian Blue, but was found in association with CD68 positive macrophages. In symptomatic plaques, the abundance of iron showed an association with the source patient’s LDL cholesterol (R 2 = 0.39, Significance F = 0.05). Iron in asymptomatic plaque was present as hemosiderin/ferritin that stained positive with Prussian Blue, and was observed in association with CD68 positive macrophages. Iron in acutely symptomatic plaques is found within thrombus, in the presence of macrophages. Moreover, the abundance of iron in symptomatic plaques is associated with the source patient’s LDL cholesterol. Within asymptomatic plaques, iron is found in association with macrophages, as hemosiderin/ferritin.« less

Sonocatalytic degradation of malachite green oxalate by a semiconductor metal oxide nanocatalyst.

PubMed

Bhavani, R; Sivasamy, A

2016-12-01

Advanced Oxidation Process (AOP) technologies are considered to be better technique for the degradation or mineralization of many recalcitrant compounds and pollutants. In the present study heterogeneous sonocatalytic degradation of a model organic compound such as Malachite green oxalate (MGO) was carried out in the aqueous phase. Zinc oxide nanorods were prepared by precipitation method employing zinc acetates as precursors and were characterized by FT-IR, XRD, FE-SEM and EDAX analysis. Degradation of MGO in the aqueous phase was studied in detail under the sonocatalytic process. Effects of pH, dye concentration, oxidant concentration, kinetics and effect of electrolytes on dye degradation were carried out to check the efficiency of the sonocatalyst. Effect of energy input on the degradation processes was also investigated. The degradation of dye molecules were monitored by UV-visible spectrophotometer and Chemical Oxygen demand (COD). The dye molecules were readily degraded at above 90% in the pH range 5.0-7.0 under ultrasound with zinc oxide nanorods. The interference of electrolytes like NaCl, KCl, Na 2 CO 3 , NaHCO 3 and MgSO 4 on the degradation of dye molecules were also studied on the sonocatalytic degradation of MGO. From the kinetic studies it was observed that at lower initial concentration of dye molecules the degradation efficiency was above 90%. The rate of the reaction decreased on increasing the initial dye concentrations of the dye molecules. It was observed that the complete mineralization of dye molecules was achieved without the formation of toxic by-products. The reusability of the catalyst also showed the effective degradation of the dye molecules up to five cycles without loss of the catalytic activities. Copyright © 2015 Elsevier Inc. All rights reserved.

The Nature of Iron Deposits Differs between Symptomatic and Asymptomatic Carotid Atherosclerotic Plaques

PubMed Central

Kopriva, David; Kisheev, Anastasye; Meena, Deiter; Pelle, Shaneen; Karnitsky, Max; Lavoie, Andrea; Buttigieg, Josef

2015-01-01

Iron within atherosclerotic plaque has been implicated as a catalyst of oxidative stress that causes progression of plaque, and plaque rupture. Iron is believed to accumulate within plaque by incorporation of erythrocytes following plaque rupture and hemorrhage. There is only indirect evidence to support this hypothesis. Plaque specimens were obtained from ten symptomatic and fifteen asymptomatic patients undergoing carotid endarterectomy at a single institution. Plaques were sectioned for study using synchrotron radiation induced X-ray fluorescence the study the distribution of zinc, calcium and iron. Histologic staining was carried out with Prussian Blue, and immunohistochemical staining was done to localize macrophages with CD68. Data were compared against patient clinical variables. Ten symptomatic (15 ± 10 days between index symptoms and surgery) and fifteen asymptomatic carotid plaques were studied. Zinc and calcium co-localized in mineralized areas of symptomatic and asymptomatic plaque. Iron was identified away from zinc and calcium in both symptomatic and asymptomatic plaques. Within the symptomatic plaques, iron was found within the thrombus associated with plaque rupture and hemorrhage. It did not stain with Prussian Blue, but was found in association with CD68 positive macrophages. In symptomatic plaques, the abundance of iron showed an association with the source patient’s LDL cholesterol (R2 = 0.39, Significance F = 0.05). Iron in asymptomatic plaque was present as hemosiderin/ferritin that stained positive with Prussian Blue, and was observed in association with CD68 positive macrophages. Iron in acutely symptomatic plaques is found within thrombus, in the presence of macrophages. The abundance of iron in symptomatic plaques is associated with the source patient’s LDL cholesterol. Within asymptomatic plaques, iron is found in association with macrophages, as hemosiderin/ferritin. PMID:26606178

The nature of iron deposits differs between symptomatic and asymptomatic carotid atherosclerotic plaques

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

Kopriva, David; Kisheev, Anastasye; Meena, Deiter

Iron within atherosclerotic plaque has been implicated as a catalyst of oxidative stress that causes progression of plaque, and plaque rupture. Iron is believed to accumulate within plaque by incorporation of erythrocytes following plaque rupture and hemorrhage. There is only indirect evidence to support this hypothesis. Plaque specimens were obtained from ten symptomatic and fifteen asymptomatic patients undergoing carotid endarterectomy at a single institution. Plaques were sectioned for study using synchrotron radiation induced X-ray fluorescence the study the distribution of zinc, calcium and iron. Histologic staining was carried out with Prussian Blue, and immunohistochemical staining was done to localize macrophagesmore » with CD68. Data were compared against patient clinical variables. Ten symptomatic (15 ± 10 days between index symptoms and surgery) and fifteen asymptomatic carotid plaques were studied. Zinc and calcium co-localized in mineralized areas of symptomatic and asymptomatic plaque. Iron was identified away from zinc and calcium in both symptomatic and asymptomatic plaques. Within the symptomatic plaques, iron was found within the thrombus associated with plaque rupture and hemorrhage. It did not stain with Prussian Blue, but was found in association with CD68 positive macrophages. In symptomatic plaques, the abundance of iron showed an association with the source patient’s LDL cholesterol (R 2 = 0.39, Significance F = 0.05). Iron in asymptomatic plaque was present as hemosiderin/ferritin that stained positive with Prussian Blue, and was observed in association with CD68 positive macrophages. Iron in acutely symptomatic plaques is found within thrombus, in the presence of macrophages. Moreover, the abundance of iron in symptomatic plaques is associated with the source patient’s LDL cholesterol. Within asymptomatic plaques, iron is found in association with macrophages, as hemosiderin/ferritin.« less

Nitrogen-doped graphene anchored with mixed growth patterns of CuPt alloy nanoparticles as a highly efficient and durable electrocatalyst for the oxygen reduction reaction in an alkaline medium.

PubMed

Illathvalappil, Rajith; Dhavale, Vishal M; Bhange, Siddheshwar N; Kurungot, Sreekumar

2017-07-06

A highly active and durable CuPt alloy catalyst with trigonal bipyramidal and truncated cube-type mixed morphologies, anchored on the nitrogen-doped graphene (NGr) surface (CuPt-TBTC/NGr), was prepared by a simple and fast method. The obtained CuPt alloy showed improved oxygen reduction reaction (ORR) activity, with a 30 mV positive shift in the half-wave potential value, as compared to the state-of-the-art Pt/C catalyst in a 0.1 M KOH solution. The CuPt alloy with the trigonal bipyramidal morphology possesses porous type inter-connected sides, which help to achieve improved mass transport of oxygen during the ORR. The exposure of the (111) plane of the CuPt alloy further improved the catalytic activity towards the dioxygen reduction in alkaline media. The ORR activity of the NGr-supported CuPt alloy was found to be dependent on the reaction time, and improved activity was obtained on the material derived at a reaction time of 90 min (CuPt-TBTC/NGr-90). The material synthesized at a lower or higher reaction time than 90 min resulted in a partially formed trigonal bipyramidal morphology with more truncated cubes or agglomerated trigonal bipyramidal and truncated cubes with closed type structures, respectively. Along with the high intrinsic ORR activity, CuPt-TBTC/NGr-90 displayed excellent electrochemical stability. Even after repeated 1000 potential cycling in a window ranging from 0.10 to 1.0 V (vs. RHE), the system clearly outperformed the state-of-the-art Pt/C catalyst with 15 and 60 mV positive shifts in the onset and half-wave potentials, respectively. CuPt-TBTC/NGr-90 also exhibited 2.1 times higher mass activity and 2.2 times higher specific activity, compared to Pt/C at 0.90 V (vs. RHE). Finally, a zinc-air battery fabricated with the alloy catalyst as the air electrode displayed a peak power density of 300 mW cm -2 , which is much higher than the peak power density of 253 mW cm -2 obtained for the state-of-the-art Pt/C catalyst as the air electrode.

Investigation of the growth and in situ heating transmission electron microscopy analysis of Ag2S-catalyzed ZnS nanowires

NASA Astrophysics Data System (ADS)

Kim, Jung Han; Kim, Jong Gu; Song, Junghyun; Bae, Tae-Sung; Kim, Kyou-Hyun; Lee, Young-Seak; Pang, Yoonsoo; Oh, Kyu Hwan; Chung, Hee-Suk

2018-04-01

We investigated the semiconductor-catalyzed formation of semiconductor nanowires (NWs) - silver sulfide (Ag2S)-catalyzed zinc sulfide (ZnS) NWs - based on a vapor-liquid-solid (VLS) growth mechanism through metal-organic chemical vapor deposition (MOCVD) with a Ag thin film. The Ag2S-catalyzed ZnS NWs were confirmed to have a wurtzite structure with a width and length in the range of ∼30 nm to ∼80 nm and ∼1 μm, respectively. Using extensive transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS) analyses from plane and cross-sectional viewpoints, the ZnS NWs were determined to have a c-axis, [0001] growth direction. In addition, the catalyst at the top of the ZnS NWs was determined to consist of a Ag2S phase. To support the Ag2S-catalyzed growth of the ZnS NWs by a VLS reaction, an in situ heating TEM experiment was conducted from room temperature to 840 °C. During the experiment, the melting of the Ag2S catalyst in the direction of the ZnS NWs was first observed at approximately 480 °C along with the formation of a carbon (C) shell. Subsequently, the Ag2S catalyst melted completely into the ZnS NWs at approximately 825 °C. As the temperature further increased, the Ag2S and ZnS NWs continuously melted and vaporized up to 840 °C, leaving only the C shell behind. Finally, a possible growth mechanism was proposed based on the structural and chemical investigations.

Gomez, Terry County, Texas - A new meteorite find

NASA Technical Reports Server (NTRS)

Sipiera, P. P.; Tarter, J.; Moore, C. B.; Dod, B. D.; Johnston, R. A.

1980-01-01

The Gomez meteorite, weighing slightly over 47 kg, was found near the town of Gomez, Terry County, Texas (33 deg 10 min 53 sec N, 102 deg 24 min 5 sec W) prior to 1974. It is a highly weathered, equilibrated L-6 chondrite of composition Fa 26, Fs 23. A large number of chromite grains and possibly partially weathered lawrencite grains were noted.

IN SITU SOURCE TREATMENT OF CR(VI) USING A FE(II)-BASED REDUCTANT BLEND: LONG-TERM MONITORING AND EVALUATION

EPA Science Inventory

The long-term effectiveness of a FeSO4 + Na2S2O4 reductant solution blend for in situ saturated zone treatment of dissolved and solid phase Cr(VI) in a high pH chromite ore processing solid waste (COPSW) fill material was investigated. Two field pilot injection studies were cond...

Nano-zinc oxide incorporated graphene oxide/nanocellulose composite for the adsorption and photo catalytic degradation of ciprofloxacin hydrochloride from aqueous solutions.

PubMed

Anirudhan, T S; Deepa, J R

2017-03-15

Purpose of this study is to report the synthetic procedure of a novel photo catalyst, nano zinc oxide incorporated graphene oxide/nanocellulose (ZnO-GO/NC) for the effective adsorption and subsequent photo degradation of ciprofloxacin (CF), an antibiotic widely used in the poultry. Self cleaning property in cellulose was achieved by introducing a nano zinc oxide incorporated graphene oxide into nanocellulose (NC) matrix. By incorporating nano zinc oxide (ZnO) in graphene oxide (GO), band gap could be tuned to 2.4eV and after the composite formation with NC, the band gap was enhanced to 2.8eV which is in the visible region. Thus the degradation of the CF was achieved under the visible light. Photo degradation was due to electron hole interaction. The step wise modification in the synthesis ZnO-GO/NC was characterized using FT-IR, XRD, SEM, EDS, AFM, DRS-UV and BET N 2 adsorption isotherm techniques. The values of surface area, pore volume and pore radius were found to be 12.68m 2 /g, 0.026mL/g and 12.5nm, respectively. Efficiency in the adsorption process of CF onto ZnO-GO/NC was verified by batch adsorption technique. The optimum pH was found to be 5.5 and dose of the ZnO-GO/NC was optimized as 2.0g/L. Equilibrium was attained at 120min and the adsorption of drug followed second-order kinetics. Sips isotherm was the best fitted model and could explain the nature of interaction of CF with ZnO-GO/NC. The studies revealed that the degradation followed first-order kinetics and the optimum pH for the degradation process was found to be 6.0 and achieved a maximum degradation efficiency of 98.0%. The reusability of ZnO-GO/NC after five consecutive cycles indicated it to be a potential candidate for the removal and degradation of CF from aquatic environment. Copyright © 2016 Elsevier Inc. All rights reserved.

Contingency plans for chromium utilization. Publication NMAB-335

NASA Technical Reports Server (NTRS)

1978-01-01

The United States depends entirely on foreign sources for the critical material, chromium, making it very vulnerable to supply disruptions. The effectiveness of programs such as stockpiling, conservation, and research and development for substitutes to reduce the impact of disruption of imports of chromite and ferrochromium are discussed. Alternatives for decreasing chromium consumption also are identified for chromium-containing materials in the areas of design, processing, and substitution.

Method of making highly sinterable lanthanum chromite powder

DOEpatents

Richards, V.L.; Singhal, S.C.

1992-09-01

A highly sinterable powder consisting essentially of LaCrO[sub 3], containing from 5 weight % to 20 weight % of a chromite of dopant Ca, Sr, Co, Ba, or Mg and a coating of a chromate of dopant Ca, Sr, Co, Ba, or Mg; is made by (1) forming a solution of La, Cr, and dopant; (2) heating their solutions; (3) forming a combined solution having a desired ratio of La, Cr, and dopant and heating to reduce solvent; (4) forming a foamed mass under vacuum; (5) burning off organic components and forming a charred material; (6) grinding the charred material; (7) heating the char at from 590 C to 950 C in inert gas containing up to 50,000 ppm O[sub 2] to provide high specific surface area particles; (8) adding that material to a mixture of a nitrate of Cr and dopant to form a slurry; (9) grinding the particles in the slurry; (10) freeze or spray drying the slurry to provide a coating of nitrates on the particles; and (11) heating the coated particles to convert the nitrate coating to a chromate coating and provide a highly sinterable material having a high specific surface area of over 7 m[sup 2]/g. 2 figs.

Superfund Record of Decision (EPA Region 9): Coalinga Asbestos Mine, Fresno County, CA. (Second remedial action), September 1990. Final report

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

Not Available

The 557-acre Coalinga Asbestos Mine site, a former asbestos processing area and chromite mine, comprises part of the Johns Manville Coalinga Asbestos Mill site in western Fresno County, California. This rural mountainous area is used primarily for recreational purposes. From 1962 to 1974, asbestos ore from several local mines was processed and sorted onsite, and the resulting asbestos mill tailings were periodically bulldozed into an intermittent stream channel. Subsequently, from 1975 to 1977, a chromite milling operation was conducted onsite. Tailings were often washed downstream during periods of stream flow, and the resuspension of asbestos fibers from the tailings intomore » the air produced a significant inhalation hazard. As a result of these activities, approximately 450,000 cubic yards of mill tailings and asbestos ore remain onsite within a large tailing pile. In 1980 and 1987, State investigations indicated that the site was contributing a significant amount of asbestos into the surface water. The site will be remediated as two Operable Units (OU). The Record of Decision (ROD) addresses the remedial action for OU2, the Johns Manville Coalinga Asbestos Mill Area. The primary contaminant of concern affecting the surface water is asbestos.« less

Characterization of the fine fraction of the argon oxygen decarburization with lance (AOD-L) sludge generated by the stainless steelmaking industry.

PubMed

Majuste, Daniel; Mansur, Marcelo Borges

2008-05-01

The argon oxygen decarburization with lance (AOD-L) sludge generated by the stainless steelmaking industry is a hazardous waste due to the presence of chromium. While its coarse fraction is usually recycled into the own industrial process, the fine fraction is normally disposed in landfills. Techniques such as briquetting or magnetic separation were found to be inadequate to treat it for reuse purposes. So, in this work, the fine fraction of the AOD-L sludge was characterized aiming to find alternative methods to treat it. This sludge consists of a fine powder (mean diameter of 1 microm) containing 34 +/- 2% (w/w) of iron, 10.2 +/- 0.9% (w/w) of chromium and 1.4 +/- 0.1% (w/w) of nickel. The main crystalline phases identified in this study were chromite (FeCr(2)O(4)), magnetite (Fe(3)O(4)), hematite (Fe(2)O(3)) and calcite (CaCO(3)). In the digestion tests, the addition of HClO(4) has favored the dissolution of chromite which is a very stable oxide in aqueous media. Nickel was found in very fine particles, probably in the metallic form or associated with iron and oxygen. The sludge was classified as hazardous waste, so its disposal in landfills should be avoided.

Production of Chromium Oxide from Turkish Chromite Concentrate Using Ethanol

NASA Astrophysics Data System (ADS)

Aktas, S.; Eyuboglu, C.; Morcali, M. H.; Özbey, S.; Sucuoglu, Y.

2015-05-01

In this study, the possibility of chromium extraction from Turkish chromite concentrate and the production of chromium oxide were investigated. For the conversion of chromium(III) into chromium(VI), NaOH was employed, as well as air with a rate of 20 L/min. The effects of the base amount, fusing temperature, and fusing time on the chromium conversion percentage were investigated in detail. The conversion kinetics of chromium(III) to chromium(VI) was also undertaken. Following the steps of dissolving the sodium chromate in water and filtering, aluminum hydroxide was precipitated by adjusting the pH level of the solution. The chromium(VI) solution was subsequently converted to Cr(III) by the combination of sulfuric acid and ethanol. Interestingly, it was observed that ethanol precipitated chromium as chromium(VI) at mildly acidic pH levels, although this effect is more pronounced for K2Cr2O7 than Na2Cr2O7. On the other hand, in the strongly acidic regime, ethanol acted as a reducing agent role in that chromium(VI) was converted into Cr(III) whereas ethanol itself was oxidized to carbon dioxide and water. Subsequently, chromium hydroxide was obtained by the help of sodium hydroxide and converted to chromium oxide by heating at 800 °C, as indicated in thermo gravimetric analysis (TGA).

The Uitkomst intrusion and Nkomati Ni-Cu-Cr-PGE deposit, South Africa: trace element geochemistry, Nd isotopes and high-precision geochronology

NASA Astrophysics Data System (ADS)

Maier, W. D.; Prevec, S. A.; Scoates, J. S.; Wall, C. J.; Barnes, S.-J.; Gomwe, T.

2018-01-01

The Uitkomst intrusion is a tubular mafic-ultramafic layered body that hosts one of South Africa's largest Ni-Cu-Cr-PGE deposits, Nkomati. The sulphide ore occurs in the form of massive lenses in the immediate quartzitic footwall and as disseminations within peridotite. The chromite ore forms an up to ˜10-m-thick layer in the lower portion of the intrusion. Uitkomst has generally been interpreted as a magma conduit, possibly related to the Bushveld event. Here, we present a new high-precision U-Pb zircon date of 2057.64 ± 0.69 Ma that overlaps with the age of the Merensky Reef of the Bushveld Complex and thus demonstrates a coeval relationship between the intrusions. Based on incompatible trace elements as well as O- and Nd isotope data (ɛNd -4.5 to -6.2), we show that the Uitkomst parent magmas were contaminated with up to 20% Archean upper crust prior to emplacement, and with up to 15% dolomitic country rock during emplacement. Ore formation at Nkomati was critically aided by substantial devolatisation and removal of dolomitic floor rocks leading to hydrodynamic concentration of sulphide and chromite during slumping of crystal mushes into the trough-like centre of the subsiding intrusion and its footwall.

Easy synthesis of hierarchical carbon spheres with superior capacitive performance in supercapacitors.

PubMed

Huang, Xinhua; Kim, Seok; Heo, Min Seon; Kim, Ji Eun; Suh, Hongsuk; Kim, Il

2013-10-01

An easy template-free approach to the fabrication of pure carbon microspheres has been achieved via direct pyrolysis of as-prepared polyaromatic hydrocarbons including polynaphthalene and polypyrene. The polyaromatics were synthesized from aromatic hydrocarbons (AHCs) using anhydrous zinc chloride as the Friedel-Crafts catalyst and chloromethyl methyl ether as a cross-linker. The experimental results show that the methylene bridges between phenyl rings generate a hierarchical porous polyaromatic precursor to form three-dimensionally (3D) interconnected micro-, meso-, and macroporous networks during carbonization. These hierarchical porous carbon aggregates of spherical carbon spheres exhibit faster ion transport/diffusion behavior and increased surface area usage in electric double-layer capacitors. Furthermore, micropores are present in the 3D interconnected network inside the cross-linked AHC-based carbon microspheres, thus imparting an exceptionally large, electrochemically accessible surface area for charge accumulation.

A practical synthesis of (+)-biotin from L-cysteine.

PubMed

Seki, Masahiko; Hatsuda, Masanori; Mori, Yoshikazu; Yoshida, Shin-ichi; Yamada, Shin-ichi; Shimizu, Toshiaki

2004-11-19

Alpha-amino aldehyde 4, which is readily derived from L-cysteine through cyclization and elaboration of the carboxy group, was subjected to the Strecker reaction, which, via sodium bisulfite adduct 16, afforded alpha-amino nitrile 5 with high diastereoselectivity (syn/anti=11:1) and in high yield. Amide 6, derived from 5, was converted to thiolactone 8, a key intermediate in the synthesis of (+)-biotin (1), by a novel S,N-carbonyl migration and cyclization reaction. The Fukuyama coupling reaction of 8 with the zinc reagent 21, which has an ester group, in the presence of a heterogeneous Pd/C catalyst allowed the efficient installation of the 4-carboxybutyl chain to provide 9. Compound 9 was hydrogenated and the protecting groups removed to furnish 1 in 10 steps and in 34 % overall yield from L-cysteine.

Fluidizable particulate materials and methods of making same

DOEpatents

Gupta, Raghubir P.

1999-01-01

The invention provides fluidizable, substantially spherical particulate material of improved attrition resistance having an average particle size from about 100 to about 400 microns useful as sorbents, catalysts, catalytic supports, specialty ceramics or the like. The particles are prepared by spray drying a slurry comprising inorganic starting materials and an organic binder. Exemplary inorganic starting materials include mixtures of zinc oxide with titanium dioxide, or with iron oxide, alumina or the like. Exemplary organic binders include polyvinyl alcohol, hydroxypropylemethyl cellulose, polyvinyl acetate and the like. The spray dried particles are heat treated at a first temperature wherein organic binder material is removed to thereby provide a porous structure to the particles, and thereafter the particles are calcined at a higher temperature to cause reaction of the inorganic starting materials and to thereby form the final inorganic particulate material.

Zinc oxide tetrapods as efficient photocatalysts for organic pollutant degradation

NASA Astrophysics Data System (ADS)

Liu, Fangzhou; Leung, Yu Hang; Djurisić, Aleksandra B.; Liao, Changzhong; Shih, Kaimin

2014-03-01

Bisphenol A (BPA) and other organic pollutants from industrial wastewater have drawn increasing concern in the past decades regarding their environmental and biological risks, and hence developing strategies of effective degradation of BPA and other organic pollutants is imperative. Metal oxide nanostructures, in particular titanium oxide (TiO2) and zinc oxide (ZnO), have been demonstrated to exhibit efficient photodegradation of various common organic dyes. ZnO tetrapods are of special interest due to their low density of native defects which consequently lead to lower recombination losses and higher photocatalytic efficiency. Tetrapods can be obtained by relatively simple and low-cost vapor phase deposition in large quantity; the micron-scale size would also be advantageous for catalyst recovery. In this study, the photodegradation of BPA with ZnO tetrapods and TiO2 nanostructures under UV illumination were compared. The concentration of BPA dissolved in DI water was analyzed by high-performance liquid chromatography (HPLC) at specified time intervals. It was observed that the photocatalytic efficiency of ZnO tetrapods eventually surpassed Degussa P25 in free-standing form, and more than 80% of BPA was degraded after 60 min. Photodegradation of other organic dye pollutants by tetrapods and P25 were also examined. The superior photocatalytic efficiency of ZnO tetrapods for degradation of BPA and other organic dye pollutants and its correlation with the material properties were discussed.

Mineral commodity profiles: Germanium

USGS Publications Warehouse

Butterman, W.C.; Jorgenson, John D.

2005-01-01

Overview -- Germanium is a hard, brittle semimetal that first came into use a half-century ago as a semiconductor material in radar units and as the material from which the first transistor was made. Today it is used principally as a component of the glass in telecommunications fiber optics; as a polymerization catalyst for polyethylene terephthalate (PET), a commercially important plastic; in infrared (IR) night vision devices; and as a semiconductor and substrate in electronics circuitry. Most germanium is recovered as a byproduct of zinc smelting, although it also has been recovered at some copper smelters and from the fly ash of coal-burning industrial powerplants. It is a highly dispersed element, associated primarily with base-metal sulfide ores. In the United States, germanium is recovered from zinc smelter residues and manufacturing scrap and is refined by two companies at four germanium refineries. One of the four refineries is dedicated to processing scrap. In 2000, producers sold zone-refined (high-purity) germanium at about $1,250 per kilogram and electronic-grade germanium dioxide (GeO2) at $800 per kilogram. Domestic refined production was valued at $22 million. Germanium is a critical component in highly technical devices and processes. It is likely to remain in demand in the future at levels at least as high as those of 2000. U.S. resources of germanium are probably adequate to meet domestic needs for several decades.

Visible light photocatalytic H2-production activity of wide band gap ZnS nanoparticles based on the photosensitization of graphene

NASA Astrophysics Data System (ADS)

Wang, Faze; Zheng, Maojun; Zhu, Changqing; Zhang, Bin; Chen, Wen; Ma, Li; Shen, Wenzhong

2015-08-01

Visible light photocatalytic H2 production from water splitting is considered an attractive way to solve the increasing global energy crisis in modern life. In this study, a series of zinc sulfide nanoparticles and graphene (GR) sheet composites were synthesized by a two-step hydrothermal method, which used zinc chloride, sodium sulfide, and graphite oxide (GO) as the starting materials. The as-prepared ZnS-GR showed highly efficient visible light photocatalytic activity in hydrogen generation. The morphology and structure of the composites obtained by transmission electron microscope and x-ray diffraction exhibited a small crystallite size and a good interfacial contact between the ZnS nanoparticles and the two-dimensional (2D) GR sheet, which were beneficial for the photocatalysis. When the content of the GR in the catalyst was 0.1%, the ZG0.1 sample exhibited the highest H2-production rate of 7.42 μmol h-1 g-1, eight times more than the pure ZnS sample. This high visible-light photocatalytic H2 production activity is attributed to the photosensitization of GR. Irradiated by visible light, the electrons photogenerated from GR transfer to the conduction band of ZnS to participate in the photocatalytic process. This study presents the visible-light photocatalytic activity of wide bandgap ZnS and its application in H2 evolution.

Cu-Doped ZnO Thin Films Deposited by a Sol-Gel Process Using Two Copper Precursors: Gas-Sensing Performance in a Propane Atmosphere

PubMed Central

Gómez-Pozos, Heberto; Arredondo, Emma Julia Luna; Maldonado Álvarez, Arturo; Biswal, Rajesh; Kudriavtsev, Yuriy; Pérez, Jaime Vega; Casallas-Moreno, Yenny Lucero; Olvera Amador, María de la Luz

2016-01-01

A study on the propane gas-sensing properties of Cu-doped ZnO thin films is presented in this work. The films were deposited on glass substrates by sol-gel and dip coating methods, using zinc acetate as a zinc precursor, copper acetate and copper chloride as precursors for doping. For higher sensitivity values, two film thickness values are controlled by the six and eight dippings, whereas for doping, three dippings were used, irrespective of the Cu precursor. The film structure was analyzed by X-ray diffractometry, and the analysis of the surface morphology and film composition was made through scanning electron microscopy (SEM) and secondary ion mass spectroscopy (SIMS), respectively. The sensing properties of Cu-doped ZnO thin films were then characterized in a propane atmosphere, C3H8, at different concentration levels and different operation temperatures of 100, 200 and 300 °C. Cu-doped ZnO films doped with copper chloride presented the highest sensitivity of approximately 6 × 104, confirming a strong dependence on the dopant precursor type. The results obtained in this work show that the use of Cu as a dopant in ZnO films processed by sol-gel produces excellent catalysts for sensing C3H8 gas. PMID:28787885

Visible light photocatalytic H2-production activity of wide band gap ZnS nanoparticles based on the photosensitization of grapheme.

PubMed

Wang, Faze; Zheng, Maojun; Zhu, Changqing; Zhang, Bin; Chen, Wen; Ma, Li; Shen, Wenzhong

2015-08-28

Visible light photocatalytic H(2) production from water splitting is considered an attractive way to solve the increasing global energy crisis in modern life. In this study, a series of zinc sulfide nanoparticles and graphene (GR) sheet composites were synthesized by a two-step hydrothermal method, which used zinc chloride, sodium sulfide, and graphite oxide (GO) as the starting materials. The as-prepared ZnS-GR showed highly efficient visible light photocatalytic activity in hydrogen generation. The morphology and structure of the composites obtained by transmission electron microscope and x-ray diffraction exhibited a small crystallite size and a good interfacial contact between the ZnS nanoparticles and the two-dimensional (2D) GR sheet,which were beneficial for the photocatalysis. When the content of the GR in the catalyst was 0.1%, the ZG0.1 sample exhibited the highest H(2)-production rate of 7.42 μmol h(−1) g(−1), eight times more than the pure ZnS sample. This high visible-light photocatalytic H(2) production activity is attributed to the photosensitization of GR. Irradiated by visible light, the electrons photogenerated from GR transfer to the conduction band of ZnS to participate in the photocatalytic process. This study presents the visible-light photocatalytic activity of wide bandgap ZnS and its application in H(2) evolution.

Effect of acetate and nitrate anions on the molecular structure of 3-(hydroxyimino)-2-butanone-2-(1H-benzimidazol-2-yl)hydrazone

NASA Astrophysics Data System (ADS)

Kamat, Vinayak; Naik, Krishna; Revankar, Vidyanand K.

2017-04-01

A novel Schiff base ligand 3-(hydroxyimino)-2-butanone-2-(1H-benzimidazol-2-yl)hydrazone has been synthesized by the condensation reaction of 2-Hydrazinobenzimidazole with diacetyl monoxime in presence of acetic acid catalyst. The ligand has crystallized as its acetate salt, due to the charge-assisted hydrogen bonding between protonated benzimidazole ring and acetate anion. Efforts to synthesize the zinc(II) complex of the title compound, has resulted in the formation of a nitrate salt of the ligand, instead of coordination complex of zinc(II). Acetate salt has crystallized in monoclinic P 21/n, while the nitrate salt has crystallized in a triclinic crystal system with P -1 space group. Hirshfeld surface analysis is presented for both of the crystal structures. Structures of synthesized molecules are even computationally optimized using DFT. A comparative structural approach between the synthesized molecules and DFT optimized structure of bare ligand without any counterions is analyzed in terms of bond parameters. Hydrogen bonding is explained keeping the anions as the central dogma. Mass fragmentation pattern of the organic molecule and comparative account of IR, 1H and 13C NMR chemical shifts are also presented. Compounds are screened for their antibacterial and antifungal potencies against few pathogenic microorganisms. The organic motif is found be an excellent antifungal agent.

The use of pyro-polymeric catalysts and a new cylindrical cell design in oxygen-aluminum generators

NASA Astrophysics Data System (ADS)

Kiseleva, E. A.; Zhuk, A. Z.; Kleymenov, B. V.; Oudaltsov, V. G.

2018-01-01

The increase in energy consumption, the economic crisis, the development of certain areas of engineering and energy, as well as the related deterioration of the environmental situation, require the development of new electrochemical current sources with high specific characteristics. In the field of creating air-hydrogen fuel cells, the problems of safety and mobile storage of hydrogen have not been completely solved, stagnation in the development of lithium-ion, lithium-air and lithium-sulfur batteries has been outlined. All this requires searching for new technological solutions, ways to increase the energy and resource characteristics of electrochemical current sources (ECS), reducing their cost [1-2]. The use of metals (aluminum, zinc, magnesium) as an energy carrier is due to their high energy intensity (in combination with the lack of transport, storage and on-board storage problems) of the relatively low cost of metals, their availability, storage safety and the absence of harmful emissions when used. As in the chemical and electrochemical use of metals, safe products (oxides, hydroxides) are formed, which are reduced to metals within the framework of traditional production technologies. Thus, a closed cycle of energy use is organized. The task of this paper is to evaluate the possibility of reducing the cost and increasing the specific power of ECS using oxygen depolarization. The goal is achieved by using non-platinum catalysts and optimizing the design of the current source.

Evaluating photo-degradation of COD and TOC in petroleum refinery wastewater by using TiO2/ZnO photo-catalyst.

PubMed

Aljuboury, Dheeaa Al Deen Atallah; Palaniandy, Puganeshwary; Abdul Aziz, Hamidi Bin; Feroz, Shaik; Abu Amr, Salem S

2016-09-01

The aim of this study is to investigate the performance of combined solar photo-catalyst of titanium oxide/zinc oxide (TiO 2 /ZnO) with aeration processes to treat petroleum wastewater. Central composite design with response surface methodology was used to evaluate the relationships between operating variables for TiO 2 dosage, ZnO dosage, air flow, pH, and reaction time to identify the optimum operating conditions. Quadratic models for chemical oxygen demand (COD) and total organic carbon (TOC) removals prove to be significant with low probabilities (<0.0001). The obtained optimum conditions included a reaction time of 170 min, TiO 2 dosage (0.5 g/L), ZnO dosage (0.54 g/L), air flow (4.3 L/min), and pH 6.8 COD and TOC removal rates of 99% and 74%, respectively. The TOC and COD removal rates correspond well with the predicted models. The maximum removal rate for TOC and COD was 99.3% and 76%, respectively at optimum operational conditions of TiO 2 dosage (0.5 g/L), ZnO dosage (0.54 g/L), air flow (4.3 L/min), reaction time (170 min) and pH (6.8). The new treatment process achieved higher degradation efficiencies for TOC and COD and reduced the treatment time comparing with other related processes.

Simultaneous sonosynthesis and sonofabrication of N-doped ZnO/TiO2 core-shell nanocomposite on wool fabric: Introducing various properties specially nano photo bleaching.

PubMed

Behzadnia, Amir; Montazer, Majid; Rad, Mahnaz Mahmoudi

2015-11-01

In this study, N-doped ZnO/TiO2 core-shell nanocomposite was successfully sonosynthesized and sonofabricated on wool fabric through a facile one-step method under ambient pressure and low temperature (75-80°C) as a novel photo-catalyst nanocomposite on textile material. The differences between crystalline phase transformation of conventional and ultrasound synthesized N-ZnO/TiO2 has been compared. The influence of different zinc acetate and titanium isopropoxide precursors in the formation of nanocomposite was studied and optimized through response surface methodology. The photocatalytic activity of the sonofabricated catalyst on the wool fabric surface was evaluated through decomposition of Methylene Blue as a model compound under sunlight irradiation. Also, N-doped ZnO/TiO2 nanocomposite sonosynthesized on wool fabric led to photo bleaching of wool fabric due to decomposition of the naturally occurred pigments under daylight irradiation. Further, yellowness index, antibacterial and antifungal activity against Escherichia coli, Staphylococcus aureus and Candida albicans, cell viability, char residual, alkali solubility, mechanical properties and water drop absorption time on the treated wool fabrics were evaluated. Also, the acid solubility of the synthesized nanopowder obtained from sonobath after treatment was characterized in acetic acid indicating higher acid resistance on N-doped ZnO/TiO2 nanocomposite. Copyright © 2015 Elsevier B.V. All rights reserved.

SPANISH PEAKS PRIMITIVE AREA, MONTANA.

USGS Publications Warehouse

Calkins, James A.; Pattee, Eldon C.

1984-01-01

A mineral survey of the Spanish Peaks Primitive Area, Montana, disclosed a small low-grade deposit of demonstrated chromite and asbestos resources. The chances for discovery of additional chrome resources are uncertain and the area has little promise for the occurrence of other mineral or energy resources. A reevaluation, sampling at depth, and testing for possible extensions of the Table Mountain asbestos and chromium deposit should be undertaken in the light of recent interpretations regarding its geologic setting.

Iron transformations during low temperature alteration of variably serpentinized rocks from the Samail ophiolite, Oman

NASA Astrophysics Data System (ADS)

Mayhew, Lisa E.; Ellison, Eric T.; Miller, Hannah M.; Kelemen, Peter B.; Templeton, Alexis S.

2018-02-01

Partially serpentinized peridotites in the Samail ophiolite in the Sultanate of Oman currently undergo low temperature alteration and hydration both at shallow levels, with water recently in contact with the atmosphere, and at depth, with anoxic, reducing fluids. However, it is unclear how changes in the distribution and oxidation state of Fe are driving the production of energy-rich gases such as hydrogen and methane detected in peridotite catchments. We track the Fe transformations in a suite of outcrop samples representing a subset of the spectrum of least to most altered end-members of the Oman peridotites. We use microscale mineralogical and geochemical analyses including QEMSCAN, Raman spectroscopy, synchrotron radiation X-ray fluorescence (XRF) mapping, and electron microprobe wavelength dispersive spectroscopy. The less-altered peridotites possess a diversity of Fe-bearing phases including relict primary minerals (e.g. olivine, pyroxene, chromite) and secondary phases (e.g. serpentine and brucite). Raman spectroscopy and electron microprobe data (Si/(Mg + Fe)) indicate that much of the serpentine is significantly intergrown with brucite on the sub-micron scale. These data also indicate that the Fe content of the brucite ranges from 10 to 20 wt% FeO. The mineral assemblage of the highly reacted rocks is less diverse, dominated by serpentine and carbonate while olivine and brucite are absent. Magnetite is relatively rare and mainly associated with chromite. Goethite and hematite, both Fe(III)-hydroxides, were also identified in the highly altered rocks. Whole rock chemical analyses reflect these mineralogical differences and show that Fe in the partially serpentinized samples is on average more reduced (∼0.40-0.55 Fe3+/FeTotal) than Fe in the highly reacted rocks (∼0.85-0.90 Fe3+/FeTotal). We propose that olivine, brucite, chromite and, perhaps, serpentine in the less-altered peridotites act as reactive phases during low temperature alteration of the Oman peridotite. The pervasive oxidation of Fe(II) in the less-altered peridotites to Fe(III) in the most-altered peridotites during water-rock reaction in the subsurface of the Samail ophiolite may produce H2 which will influence the development of microbial energy sources and habitats, and carbon cycling and sequestration within the (ultra)mafic ocean crust.

Petrology of metabasic and peridotitic rocks of the Songshugou ophiolite, Qinling orogen, China

NASA Astrophysics Data System (ADS)

Belic, Maximilian; Hauzenberger, Christoph; Dong, Yunpeng

2013-04-01

The Proterozoic Songshugou ophiolite outcrops as a rootless nappe which was emplaced into the southern margin of the Qinling Group. It consists mainly of amphibolite facies metamafic and -ultramafic rocks. Trace element geochemistry and isotope composition show that the mafic rocks are mainly E-MORB and T-MORB metabasalts (Dong et al., 2008b). Within the ophiolite sequence, ultramafic rocks consist mainly of peridotites and serpentinites. Particularly, extremely fresh dunites and harzburgites, are found which do not display a conspicuous metamorphic overprint. The low CaO (<0.39 wt.%) and Al2O3 (<0.51 wt.%) as well as high MgO (41-48 wt.%) contents classify them as depleted non-fertile mantle rocks. Chromite is found as disseminated phase but can sometimes form massive chromite bands. The platinumgroup mineral Laurite (RuS2) could be identified as inclusion in chromites. Usually part of Ru is substituted by Os and Ir. The metamafic rocks consist of garnet, amphibole, symplectitic pyroxenes, ilmenite, apatite, ±zoisite, ±sphene and show a strong metamorphic overprint. Garnet contains numerous inclusions in the core but are nearly inclusion free at the rim. The cores have sometimes snowball textures indicating initially syndeformative growth. Pure albite and prehnite were found in the central parts of the garnets. In the outer portions, pargasitic amphibole, rutile and rarely glaukophane were found. The symplectitic pyroxenes are of diopsidic composition which enclose prehnite and not albite, as common in retrograde eclogitic rocks. Different stages of garnet breakdown to plagioclase and amphibole, from thin plagioclase rims surrounding the garnets to plagioclase rich pseudomorphs, can be observed in different samples. Based on the glaukophane inclusions and symplectitic pyroxenes a high pressure metamorphic event can be concluded. The garnet breakdown to plagioclase and the symplectites clearly indicate a rapid exhumation phase. The age of the metamorphic event is unclear but probably related to the closure of the Shangdan ocean during the early Paleozoic. The financial support by Eurasia-Pacific Uninet is gratefully acknowledged. Dong, Y.P., Zhou, M.F., Zhang, G.W., Zhou, D.W., Liu, L., Zhang, Q., 2008. The Grenvillian Songshugou ophiolite in the Qinling Mountains, Central China: implications for the tectonic evolution of the Qinling orogenic belt. Journal of Asian Earth Science 32 (5-6), 325-335.

History of the Colorado-Wyoming state line diatremes.

USGS Publications Warehouse

Collins, D.S.; Heyl, A.V.

1984-01-01

Although >90 kimberlite diatremes have been found in the area, it was not until after 1963 that these bodies were correctly identified. The presence of large inclusions of sedimentary rocks had hindered their recognition. In 1975 a diamond crystal 3.5 carats). They are usually colourless, but light-brown, blue-white, pale orange, pale to bright yellow and nearly black crystals occur. Associated minerals, including chrome-diopside, chromite, magnesian ilmenite, pyrope and omphacite, are described.-R.S.M.

The Cedars ultramafic mass, Sonoma County, California

USGS Publications Warehouse

Blake, M. Clark; Bailey, Edgar H.; Wentworth, Carl M.

2012-01-01

The Cedars ultramafic mass is a mantle fragment that consists of partially serpentinized spinel harzburgite and dunite. Compositional layering and a chromite lineation define a penetrative metamorphic foliation that almost certainly formed in the upper mantle. Although detailed petrofabric and mineral chemistry are presently lacking, it seems reasonable that the Cedars peridotite represents a slice of mantle tectonite that once formed the base of the Coast Range ophiolite, and not an abyssal peridotite tectonically emplaced within the Franciscan accretionary prism.

Operation Chromite: A Case Study for the National Maneuver Force Exercise Concept of the Armed Forces of the Philippines

DTIC Science & Technology

2013-04-20

interest, and the country’s archipelagic landscape, there is no capability more functional and indispensable to the AFP than the full spectrum of...military operations other than war. 6 Considering the strategic environment, maritime interest, and its archipelagic landscape, there is no... doctrines . Massive firepower and superior leadership remained the centerpieces of US forces that checked the North Koreans. On the other hand, the

Mineral chemistry and geochemistry of ophiolitic metaultramafics from Um Halham and Fawakhir, Central Eastern Desert, Egypt

NASA Astrophysics Data System (ADS)

Abdel-Karim, Abdel-Aal M.; Ali, Shehata; El-Shafei, Shaimaa A.

2018-03-01

This study is focused on ophiolitic metaultramafics from Um Halham and Fawakhir, Central Eastern Desert of Egypt. The rocks include serpentinized peridotites, serpentinites together with talc- and quartz-carbonates. The primary spinel relict is Al-chromite [Cr# > 60], which is replaced by Cr-magnetite during metamorphism. The high Cr# of Al-chromites resembles supra-subduction zone (SSZ) peridotites and suggests derivation from the deeper portion of the mantle section with boninitic affinity. These mantle rocks equilibrated with boninitic melt have been generated by high melting degrees. The estimated melting degrees ( 19-24%) lie within the range of SSZ peridotites. The high Cr# of spinel and Fo content of olivine together with the narrow compositional range suggest a mantle residual origin. Serpentinized peridotite and serpentinites have low Al2O3/SiO2 ratios (mostly < 0.03) like fore-arc mantle wedge serpentinites and further indicate that their mantle protolith had experienced partial melting before serpentinization process. Moreover, they have very low Nb, Ta, Zr and Hf concentrations along with sub-chondritic Nb/Ta (0.3-16) and Zr/Hf (mostly 1-20) ratios further confirming that their mantle source was depleted by earlier melting extraction event. The high chondrite normalized (La/Sm)N ratios (average 10) reflect input of subduction-related slab melts/fluids into their mantle source.

Characterization of corrosion scale formed on stainless steel delivery pipe for reclaimed water treatment.

PubMed

Cui, Yong; Liu, Shuming; Smith, Kate; Yu, Kanghua; Hu, Hongying; Jiang, Wei; Li, Yuhong

2016-01-01

To reveal corrosion behavior of stainless steel delivery pipe used in reclaimed water treatment, this research focused on the morphological, mineralogical and chemical characteristics of stainless steel corrosion scale and corroded passive film. Corrosion scale and coupon samples were taken from a type 304 pipe delivering reclaimed water to a clear well in service for more than 12 years. Stainless steel corrosion scales and four representative pipe coupons were investigated using mineralogy and material science research methods. The results showed corrosion scale was predominantly composed of goethite, lepidocrocite, hematite, magnetite, ferrous oxide, siderite, chrome green and chromite, the same as that of corroded pipe coupons. Hence, corrosion scale can be identified as podiform chromite deposit. The loss of chromium in passive film is a critical phenomenon when stainless steel passive film is damaged by localized corrosion. This may provide key insights toward improving a better comprehension of the formation of stainless steel corrosion scale and the process of localized corrosion. The localized corrosion behavior of stainless steel is directly connected with reclaimed water quality parameters such as residual chlorine, DO, Cl(-) and SO4(2-). In particular, when a certain amount of residual chlorine in reclaimed water is present as an oxidant, ferric iron is the main chemical state of iron minerals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Microstructural analyses of Cr(VI) speciation in chromite ore processing Residue (COPR)

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

CHRYSOCHOOU, MARIA; FAKRA, SIRINE C .; Marcus, Matthew A.

2010-03-01

The speciation and distribution of Cr(VI) in the solid phase was investigated for two types of chromite ore processing residue (COPR) found at two deposition sites in the United States: gray-black (GB) granular and hard brown (HB) cemented COPR. COPR chemistry and mineralogy were investigated using micro-X-ray absorption spectroscopy and micro-X-ray diffraction, complemented by laboratory analyses. GB COPR contained 30percent of its total Cr(VI) (6000 mg/kg) as large crystals(>20 ?m diameter) of a previously unreported Na-rich analog of calcium aluminum chromate hydrates. These Cr(VI)-rich phases are thought to be vulnerable to reductive and pH treatments. More than 50percent of themore » Cr(VI) was located within nodules, not easily accessible to dissolved reductants, and bound to Fe-rich hydrogarnet, hydrotalcite, and possibly brucite. These phases are stable over a large pH range, thus harder to dissolve. Brownmilleritewasalso likely associated with physical entrapment of Cr(VI) in the interior of nodules. HB COPR contained no Cr(VI)-rich phases; all Cr(VI) was diffuse within the nodules and absent from the cementing matrix, with hydrogarnet and hydrotalcite being the main Cr(VI) binding phases. Treatment ofHBCOPRis challenging in terms of dissolving the acidity-resistant, inaccessible Cr(VI) compounds; the same applies to ~;;50percent of Cr(VI) in GB COPR.« less

Gas-to-particle conversion in the particle precipitation-aided chemical vapor deposition process II. Synthesis of the perovskite oxide yttrium chromite

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

Dieten, V.E.J. van; Dekker, J.P.; Hurkmans, E.J.

1993-11-01

In the particle precipitation-aided chemical vapor deposition process, an aerosol is formed in the gas phase at elevated temperatures. The particles are deposited on a cooled substrate. Coherent layers with a controlled porosity can be obtained by a simultaneous heterogeneous reaction, which interconnects the deposited particles. The synthesis of submicrometer powder of the perovskite oxide yttrium chromite (YCrO[sub 3]) by gas to particle conversion, which is the first step of the PP-CVD process, has been investigated, and preliminary results are shown. The powders have been synthesized using yttrium trichloride vapor (YCl[sub 3]), chromium trichloride vapor (CrCl[sub 3]), and steam andmore » oxygen as reactants. The influence of the input molar ratio of the elements on the composition and characteristics of the powders has been investigated. Phase composition has been determined by X-ray diffraction (XRD). The powders have been characterized by transmission electron microscopy (TEM) and sedimentation field flow fractionation (SF[sup 3]). At a reaction temperature of 1283 K the powders consist of the chromium sesquioxide (Cr[sub 2]O[sub 3]), or a mixture of Cr[sub 2]O[sub 3] and YCrO[sub 3]. At stoichiometeric input amounts of metal chlorides and steam the formation of YCrO[sub 3] seems to be favored. 19 refs., 6 figs., 3 tabs.« less

Growth of wurtzite CdTe nanowires on fluorine-doped tin oxide glass substrates and room-temperature bandgap parameter determination

NASA Astrophysics Data System (ADS)

Choi, Seon Bin; Song, Man Suk; Kim, Yong

2018-04-01

The growth of CdTe nanowires, catalyzed by Sn, was achieved on fluorine-doped tin oxide glass by physical vapor transport. CdTe nanowires grew along the 〈0001〉 direction, with a very rare and phase-pure wurtzite structure, at 290 °C. CdTe nanowires grew under Te-limited conditions by forming SnTe nanostructures in the catalysts and the wurtzite structure was energetically favored. By polarization-dependent and power-dependent micro-photoluminescence measurements of individual nanowires, heavy and light hole-related transitions could be differentiated, and the fundamental bandgap of wurtzite CdTe at room temperature was determined to be 1.562 eV, which was 52 meV higher than that of zinc-blende CdTe. From the analysis of doublet photoluminescence spectra, the valence band splitting energy between heavy hole and light hole bands was estimated to be 43 meV.

Systems including catalysts in porous zeolite materials within a reactor for use in synthesizing hydrocarbons

DOEpatents

Rolllins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2012-07-24

Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

A molecular approach to self-supported cobalt-substituted ZnO materials as remarkably stable electrocatalysts for water oxidation.

PubMed

Pfrommer, Johannes; Lublow, Michael; Azarpira, Anahita; Göbel, Caren; Lücke, Marcel; Steigert, Alexander; Pogrzeba, Martin; Menezes, Prashanth W; Fischer, Anna; Schedel-Niedrig, Thomas; Driess, Matthias

2014-05-12

In regard to earth-abundant cobalt water oxidation catalysts, very recent findings show the reorganization of the materials to amorphous active phases under catalytic conditions. To further understand this concept, a unique cobalt-substituted crystalline zinc oxide (Co:ZnO) precatalyst has been synthesized by low-temperature solvolysis of molecular heterobimetallic Co(4-x)Zn(x) O4 (x = 1-3) precursors in benzylamine. Its electrophoretic deposition onto fluorinated tin oxide electrodes leads after oxidative conditioning to an amorphous self-supported water-oxidation electrocatalyst, which was observed by HR-TEM on FIB lamellas of the EPD layers. The Co-rich hydroxide-oxidic electrocatalyst performs at very low overpotentials (512 mV at pH 7; 330 mV at pH 12), while chronoamperometry shows a stable catalytic current over several hours. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of Solvent Diols on the Synthesis of ZnFe2O4 Particles and Their Use as Heterogeneous Photo-Fenton Catalysts

PubMed Central

Anchieta, Chayene Gonçalves; Cancelier, Adriano; Mazutti, Marcio Antonio; Jahn, Sérgio Luiz; Kuhn, Raquel Cristine; Gündel, Andre; Chiavone-Filho, Osvaldo; Foletto, Edson Luiz

2014-01-01

A solvothermal method was used to prepare zinc ferrite spinel oxide (ZnFe2O4) using ethylene glycol and 1,4 butanediol as solvent diols, and the influence of diols on the physical properties of ZnFe2O4 particles was investigated. The produced particles were characterized by X-ray powder diffraction (XRD), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR) and nitrogen adsorption isotherms, and the catalytic activity for the organic pollutant decomposition by heterogeneous photo-Fenton reaction was investigated. Both solvents produced particles with cubic spinel structure. Microporous and mesoporous structures were obtained when ethylene glycol and 1,4 butanediol were used as diols, respectively. A higher pore volume and surface area, as well as a higher catalytic activity for the pollutant degradation were found when 1,4 butanediol was used as solvent. PMID:28788191

In situ spectroscopic characterization of Ni 1-xZn x/ZnO catalysts and their selectivity for acetylene semihydrogenation in excess ethylene

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

Spanjers, Charles S.; Sim, Richard S.; Sturgis, Nicholas P.

2015-10-30

The structures of ZnO-supported Ni catalysts were explored with in situ X-ray absorption spectroscopy, temperature-programmed reduction, X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy, and electron energy loss spectroscopy. Calcination of nickel nitrate on a nanoparticulate ZnO support at 450 °C results in the formation of Zn-doped NiO (ca. N₀̣̣₈₅ Zn₀̣̣₁₅O) nanoparticles with the rock salt crystal structure. Subsequent in situ reduction monitored by X-ray absorption near-edge structure (XANES) at the Ni K edge reveals a direct transformation of the Zn-doped NiO nanoparticles to a face-centered cubic alloy, Ni 1-xZn x, at ~400 °C with x increasingmore » with increasing temperature. Both in situ XANES and ex situ HRTEM provide evidence for intermetallic β₁-NiZn formation at ~550 °C. In comparison to a Ni/SiO₂ catalyst, Ni/ZnO necessitates a higher temperature for the reduction of Ni II to Ni⁰, which highlights the strong interaction between Ni and the ZnO support. The catalytic activity for acetylene removal from an ethylene feed stream is decreased by a factor of 20 on Ni/ZnO in comparison to Ni/SiO₂. The decrease in catalytic activity of Ni/ZnO is accompanied by a reduced absolute selectivity to ethylene. H–D exchange measurements demonstrate a reduced ability of Ni/ZnO to dissociate hydrogen in comparison to Ni/SiO₂.These results of the catalytic experiments suggest that the catalytic properties are controlled, in part, by the zinc oxide support and stress the importance of reporting absolute ethylene selectivity for the catalytic semihydrogenation of acetylene in excess ethylene.« less

The Miller Range 090340 and 090206 meteorites: Identification of new brachinite-like achondrites with implications for the diversity and petrogenesis of the brachinite clan

NASA Astrophysics Data System (ADS)

Goodrich, Cyrena Anne; Kita, Noriko T.; Sutton, Stephen R.; Wirick, Sue; Gross, Juliane

2017-05-01

Miller Range (MIL) 090340 and MIL 090206 are olivine-rich achondrites originally classified as ureilites. We investigate their petrography, mineral compositions, olivine Cr valences, equilibration temperatures, and (for MIL 090340) oxygen isotope compositions, and compare them with ureilites and other olivine-rich achondrites. We conclude that they are brachinite-like achondrites that provide new insights into the petrogenesis of brachinite clan meteorites. MIL 090340,6 has a granoblastic texture and consists of 97 modal % by area olivine (Fo = molar Mg/[Mg+Fe] = 71.3 ± 0.6). It also contains minor to trace augite, chromite, chlorapatite, orthopyroxene, metal, troilite, and terrestrial Fe-oxides. Approximately 80% by area of MIL 090206,5 has a granoblastic texture of olivine (Fo 72.3 ± 0.1) plus minor augite and chromite, similar to MIL 090340 but also containing minor plagioclase. The rest of the section consists of a single crystal of orthopyroxene ( 11 × 3 mm), poikilitically enclosing rounded grains of olivine (Fo = 76.1 ± 0.6), augite, chromite, metal, and sulfide. Equilibration temperatures for MIL 090340 and MIL 090206, calculated from olivine-spinel, olivine-augite, and two-pyroxene thermometry range from 800 to 930 °C. In both samples, symplectic intergrowths of Ca-poor orthopyroxene + opaque phases (Fe-oxides, sulfide, metal) occur as rims on and veins/patches within olivine. Before terrestrial weathering, the opaques were probably mostly sulfide, with minor metal. All petrologic properties of MIL 090340 and MIL 090206 are consistent with those of brachinite clan meteorites, and largely distinct from those of ureilites. Oxygen isotope compositions of olivine in MIL 090340 (δ18O = 5.08 ± 0.30‰, δ17O = 2.44 ± 0.21‰, and Δ17O = -0.20 ± 0.12‰) are also within the range of brachinite clan meteorites, and well distinguished from ureilites. Olivine Cr valences in MIL 090340 and the granoblastic area of MIL 090206 are 2.57 ± 0.06 and 2.59 ± 0.07, respectively, similar to those of three brachinites also analyzed here (Brachina, Hughes 026, Nova 003). They are higher than those of olivine in ureilites, even those containing chromite. The valence systematics of MIL 090340, MIL 090206, and the three analyzed brachinites (lower Fo = more oxidized Cr) are consistent with previous evidence that brachinite-like parent bodies were inherently more oxidized than the ureilite parent body. The symplectic orthopyroxene + sulfide/metal assemblages in MIL 090340, MIL 090206, and many brachinite clan meteorites have superficial similarities to characteristic "reduction rims" in ureilites. However, they differ significantly in detail. They likely formed by reaction of olivine with S-rich fluids, with only minor reduction. MIL 090340 and the granoblastic area of MIL 090206 are similar in modal mineralogy and texture to most brachinites, but have higher Fo values typical of brachinite-like achondrites. The poikilitic pyroxene area of MIL 090206 is more typical of brachinite-like achondrites. The majority of their properties suggest that MIL 090340 and MIL 090206 are residues of low-degree partial melting. The poikilitic area of MIL 090206 could be a result of limited melt migration, with trapping and recrystallization of a small volume of melt in the residual matrix. These two samples are so similar in mineral compositions, Cr valence, and cosmic ray exposure ages that they could be derived from the same lithologic unit on a common parent body.

The Miller Range 090340 and 090206 meteorites: Identification of new brachinite-like achondrites with implications for the diversity and petrogenesis of the brachinite clan

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

Goodrich, Cyrena Anne; Kita, Noriko T.; Sutton, Stephen R.

2017-05-01

Miller Range (MIL) 090340 and MIL 090206 are olivine-rich achondrites originally classified as ureilites. We investigate their petrography, mineral compositions, olivine Cr valences, equilibration temperatures, and (for MIL 090340) oxygen isotope compositions, and compare them with ureilites and other olivine-rich achondrites. We conclude that they are brachinite-like achondrites that provide new insights into the petrogenesis of brachinite clan meteorites. MIL 090340,6 has a granoblastic texture and consists of ~97 modal % by area olivine (Fo = molar Mg/[Mg+Fe] = 71.3 ± 0.6). It also contains minor to trace augite, chromite, chlorapatite, orthopyroxene, metal, troilite, and terrestrial Fe-oxides. Approximately 80% bymore » area of MIL 090206,5 has a granoblastic texture of olivine (Fo 72.3 ± 0.1) plus minor augite and chromite, similar to MIL 090340 but also containing minor plagioclase. The rest of the section consists of a single crystal of orthopyroxene (~11 × 3 mm), poikilitically enclosing rounded grains of olivine (Fo = 76.1 ± 0.6), augite, chromite, metal, and sulfide. Equilibration temperatures for MIL 090340 and MIL 090206, calculated from olivine-spinel, olivine-augite, and two-pyroxene thermometry range from ~800 to 930 °C. In both samples, symplectic intergrowths of Ca-poor orthopyroxene + opaque phases (Fe-oxides, sulfide, metal) occur as rims on and veins/patches within olivine. Before terrestrial weathering, the opaques were probably mostly sulfide, with minor metal. All petrologic properties of MIL 090340 and MIL 090206 are consistent with those of brachinite clan meteorites, and largely distinct from those of ureilites. Oxygen isotope compositions of olivine in MIL 090340 (δ18O = 5.08 ± 0.30‰, δ17O = 2.44 ± 0.21%, and Δ17O = -0.20 ± 0.12‰) are also within the range of brachinite clan meteorites, and well distinguished from ureilites. Olivine Cr valences in MIL 090340 and the granoblastic area of MIL 090206 are 2.57 ± 0.06 and 2.59 ± 0.07, respectively, similar to those of three brachinites also analyzed here (Brachina, Hughes 026, Nova 003). They are higher than those of olivine in ureilites, even those containing chromite. The valence systematics of MIL 090340, MIL 090206, and the three analyzed brachinites (lower Fo = more oxidized Cr) are consistent with previous evidence that brachinite-like parent bodies were inherently more oxidized than the ureilite parent body. The symplectic orthopyroxene + sulfide/metal assemblages in MIL 090340, MIL 090206, and many brachinite clan meteorites have superficial similarities to characteristic “reduction rims” in ureilites. However, they differ significantly in detail. They likely formed by reaction of olivine with S-rich fluids, with only minor reduction. MIL 090340 and the granoblastic area of MIL 090206 are similar in modal mineralogy and texture to most brachinites, but have higher Fo values typical of brachinite-like achondrites. The poikilitic pyroxene area of MIL 090206 is more typical of brachinite-like achondrites. The majority of their properties suggest that MIL 090340 and MIL 090206 are residues of low-degree partial melting. The poikilitic area of MIL 090206 could be a result of limited melt migration, with trapping and recrystallization of a small volume of melt in the residual matrix. These two samples are so similar in mineral compositions, Cr valence, and cosmic ray exposure ages that they could be derived from the same lithologic unit on a common parent body.« less

Ecosystem health in mineralized terrane: Data from podiform chromite (Chinese Camp mining district, California), quartz alunite (Castle Peak and Masonic mining districts, Nevada/California), and Mo/Cu porphyry (Battle Mountain mining district, Nevada) deposits

Treesearch

Steve W. Blecker; Lisa L. Stillings; Michael C. Amacher; James A. Ippolito; Nicole M. DeCrappeo

2010-01-01

The myriad definitions of soil/ecosystem quality or health are often driven by ecosystem and management concerns, and they typically focus on the ability of the soil to provide functions relating to biological productivity and/or environmental quality (Doran and Parkin, 1994; Karlen and others, 1997). A variety of attempts have been made to create indices that quantify...

Barium isotopes in Allende meteorite - Evidence against an extinct superheavy element

NASA Technical Reports Server (NTRS)

Lewis, R. S.; Anders, E.; Shimamura, T.; Lugmair, G. W.

1983-01-01

Carbon and chromite fractions from the Allende meteorite that contain isotopically anomalous xenon-131 to xenon-136 (carbonaceous chondrite fission or CCF xenon) at up to 5 x 10 to the 11th atoms per gram show no detectable isotopic anomalies in barium-130 to barium-138. This rules out the possibility that the CCF xenon was formed by in situ fission of an extinct superheavy element. Apparently the CCF xenon and its carbonaceous carrier are relics from stellar nucleosynthesis.

Ceramic component for electrodes

DOEpatents

Marchant, David D.; Bates, J. Lambert

1980-01-01

A ceramic component suitable for preparing MHD generator electrodes having the compositional formula: Y.sub.x (Mg.sub.y Cr.sub.z).sub.w Al.sub.(1-w) O.sub.3 where x=0.9 to 1.05, y=0.02 to 0.2, z=0.8 to 1.05 and w=1.0 to 0.5. The component is resistant to the formation of hydration products in an MHD environment, has good electrical conductivity and exhibits a lower electrochemical corrosion rate than do comparable compositions of lanthanum chromite.

Parent-Body Modification of Chondritic Meteorites

NASA Technical Reports Server (NTRS)

Rubin, Alan

2003-01-01

This proposal focused on the parent-body modification of chondritic materials and substantial progress was made in the last year. A summary of the work accomplished during this period is discussed. The topics include: 1) Chromite-Plagioclase Assemblages in Ordinary Chondrites; 2) The Gujba Bencubbin-like meteorite fall; 3) NWA428: A rock that Experienced Impact-induced Annealing; 4) Spade: An Annealed H-chondrite Impact-melt Breccia; and 5) Post-shock Annealing in Ordinary Chondrites. A list of the papers submitted or published during the period is also presented.

Great Dike of Zimbabwe, Zimbabwae, Africa

NASA Technical Reports Server (NTRS)

1993-01-01

The Great Dike of Zimbabwe (17.5S, 31.5E) bisects the entire length of Zimbabwae in southern Africa and is one of the prominent visual features easily recognized from low orbit. The volcanic rocks which make up the dike are about 1.2 billion years old and are rich in chromite and platinum which are mined from it. The straight line of the dike is offset in places by faults which are often occupied by streams flowing through the fractures.

Operation CHROMITE (INCHON), Offensive, Amphibious Assault, Joint, 15 September 1950

DTIC Science & Technology

1984-05-23

veterans and supported by over 210 [103 pI combat aircraft. (O’Ballance, p. 25) So this was the military system that procured the North Korean military...one; and, the commander then decides which course to adopt. INCHON was a product of MacArthur’s strategic vision. To K make that vision a reality he... systems radiate from Seoul to the east, north, and south. A force which controls Seoul controls the transportation arteries. (X Corps, p. 5) Seoul

Electrochemical growth of controlled tip shapes of ZnO nanorod arrays on silicon substrate and enhanced photoluminescence emission from nanopyramid arrays compared with flat-head nanorods

NASA Astrophysics Data System (ADS)

Alimanesh, Mahmoud; Hassan, Z.; Zainal, Norzaini

2017-10-01

Zinc oxide (ZnO) nanorod arrays (NRAs) with different morphologies such as; perfect hexagon flat-head, pyramidal, compact pencil, nail-shaped, and high-compact ZnO nanorod thin films, were successfully grown on silicon substrates. These NRAs were formed on substrates using a simple low-temperature electrochemical method without adding any catalyst or template via the precursors of zinc nitrate hexahydrate [Zn(NO3)2·6H2O] and hexamethylenetetramine [HMT; C6H12N4] with an equal molar concentration of 0.025 mol/l. The morphologies of the ZnO nanorods (NRs) could be controlled and transformed successfully in to other morphologies by changing the growth conditions, such as; growth temperature and applied current density. Detailed structural investigations reveal that the synthesized various NRs are single crystalline with wurtzite hexagonal phase and preferentially grow along the c-axis direction. The room temperature photoluminescence spectra show that each spectrum consists of an ultraviolet (UV) band and a relative broad visible light emission and infrared emission peak. The enhanced light emission intensity at UV peak (∼375 nm) is observed significantly from ZnO nanopyramid (NP) arrays because of the conical shape of NP. The photoluminescence intensity of the UV peak from the NPs is found to be 1.5-17 times larger than those from the other various NRs.

Carbon-based tribofilms from lubricating oils

NASA Astrophysics Data System (ADS)

Erdemir, Ali; Ramirez, Giovanni; Eryilmaz, Osman L.; Narayanan, Badri; Liao, Yifeng; Kamath, Ganesh; Sankaranarayanan, Subramanian K. R. S.

2016-08-01

Moving mechanical interfaces are commonly lubricated and separated by a combination of fluid films and solid ‘tribofilms’, which together ensure easy slippage and long wear life. The efficacy of the fluid film is governed by the viscosity of the base oil in the lubricant; the efficacy of the solid tribofilm, which is produced as a result of sliding contact between moving parts, relies upon the effectiveness of the lubricant’s anti-wear additive (typically zinc dialkyldithiophosphate). Minimizing friction and wear continues to be a challenge, and recent efforts have focused on enhancing the anti-friction and anti-wear properties of lubricants by incorporating inorganic nanoparticles and ionic liquids. Here, we describe the in operando formation of carbon-based tribofilms via dissociative extraction from base-oil molecules on catalytically active, sliding nanometre-scale crystalline surfaces, enabling base oils to provide not only the fluid but also the solid tribofilm. We study nanocrystalline catalytic coatings composed of nitrides of either molybdenum or vanadium, containing either copper or nickel catalysts, respectively. Structurally, the resulting tribofilms are similar to diamond-like carbon. Ball-on-disk tests at contact pressures of 1.3 gigapascals reveal that these tribofilms nearly eliminate wear, and provide lower friction than tribofilms formed with zinc dialkyldithiophosphate. Reactive and ab initio molecular-dynamics simulations show that the catalytic action of the coatings facilitates dehydrogenation of linear olefins in the lubricating oil and random scission of their carbon-carbon backbones; the products recombine to nucleate and grow a compact, amorphous lubricating tribofilm.

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

Erdemir, Ali; Ramirez, Giovanni; Eryilmaz, Osman L.

Moving mechanical interfaces are commonly lubricated and separated by a combination of fluid films and solid 'tribofilms', which together ensure easy slippage and long wear life(1). The efficacy of the fluid film is governed by the viscosity of the base oil in the lubricant; the efficacy of the solid tribofilm, which is produced as a result of sliding contact between moving parts, relies upon the effectiveness of the lubricant's anti-wear additive (typically zinc dialkyldithiophosphate)(2). Minimizing friction and wear continues to be a challenge, and recent efforts have focused on enhancing the anti-friction and anti-wear properties of lubricants by incorporating inorganicmore » nanoparticles and ionic liquids(3,4). Here, we describe the in operando formation of carbon-based tribofilms via dissociative extraction from base-oil molecules on catalytically active, sliding nanometre-scale crystalline surfaces, enabling base oils to provide not only the fluid but also the solid tribofilm. We study nanocrystalline catalytic coatings composed of nitrides of either molybdenum or vanadium, containing either copper or nickel catalysts, respectively. Structurally, the resulting tribofilms are similar to diamond-like carbon(5). Ball-on-disk tests at contact pressures of 1.3 gigapascals reveal that these tribofilms nearly eliminate wear, and provide lower friction than tribofilms formed with zinc dialkyldithiophosphate. Reactive and ab initio molecular-dynamics simulations show that the catalytic action of the coatings facilitates dehydrogenation of linear olefins in the lubricating oil and random scission of their carbon-carbon backbones; the products recombine to nucleate and grow a compact, amorphous lubricating tribofilm.« less

Cracking and aromatization of C{sub 6}-C{sub 10} n-alkanes and n-alkenes on a zeolite-containing catalyst

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

Gairbekov, T.M.; Takaeva, M.I.; Khadzhiev, S.N.

1992-05-10

Despite the extensive studies on catalysis on zeolites, the question of the mechanism of the reactions of cracking and aromatization of hydrocarbons is still debated. The classic Whitmore theory hypothesizes that cracking of alkanes and alkenes takes place through the formation of the same intermediate trivalent carbenium ions of the (C{sub n}H{sub 2n+1}){sup +} type. Ola`s protolytic mechanism hypothesizes nonclassic five- (four-)coordinated ions of the (C{sub n}H{sub 2n+3}){sup +} type for cracking of alkanes and classic carbenium ions for alkenes. When the classic mechanism occurs on zeolites, an analogous effect on the rate of the reactions of alkanes and alkenesmore » with the molecular weight of the starting hydrocarbons and similar compositions of the products obtained should be predicted. The authors investigated the transformation of individual n-alkanes and n-1-alkenes of C{sub 6}-C{sub 10} composition in the presence of a catalyst synthesized by addition of 30 wt.% decationized ultrahigh-silicon zeolite of the ZSM type (Si/Al - 16) modified with 1 wt.% zinc on {gamma}-Al{sub 2}O{sub 3}. The experiment was conducted on a flow-type laboratory setup at 425{degrees}C in conditions of the minimum effect of diffusion factors with the method described in detail previously. 13 refs., 4 figs., 1 tab.« less

Fe2 PO5 -Encapsulated Reverse Energetic ZnO/Fe2 O3 Heterojunction Nanowire for Enhanced Photoelectrochemical Oxidation of Water.

PubMed

Qin, Dong-Dong; He, Cai-Hua; Li, Yang; Trammel, Antonio C; Gu, Jing; Chen, Jing; Yan, Yong; Shan, Duo-Liang; Wang, Qiu-Hong; Quan, Jing-Jing; Tao, Chun-Lan; Lu, Xiao-Quan

2017-07-10

Zinc oxide is regarded as a promising candidate for application in photoelectrochemical water oxidation due to its higher electron mobility. However, its instability under alkaline conditions limits its application in a practical setting. Herein, we demonstrate an easily achieved wet-chemical route to chemically stabilize ZnO nanowires (NWs) by protecting them with a thin layer Fe 2 O 3 shell. This shell, in which the thickness can be tuned by varying reaction times, forms an intact interface with ZnO NWs, thus protecting ZnO from corrosion in a basic solution. The reverse energetic heterojunction nanowires are subsequently activated by introducing an amorphous iron phosphate, which substantially suppressed surface recombination as a passivation layer and improved photoelectrochemical performance as a potential catalyst. Compared with pure ZnO NWs (0.4 mA cm -2 ), a maximal photocurrent of 1.0 mA cm -2 is achieved with ZnO/Fe 2 O 3 core-shell NWs and 2.3 mA cm -2 was achieved for the PH 3 -treated NWs at 1.23 V versus RHE. The PH 3 low-temperature treatment creates a dual function, passivation and catalyst layer (Fe 2 PO 5 ), examined by X-ray photoelectron spectroscopy, TEM, photoelectrochemical characterization, and impedance measurements. Such a nano-composition design offers great promise to improve the overall performance of the photoanode material. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Review on Recent Advances in the Application of Nanocatalysts in A3 Coupling Reactions.

PubMed

Nasrollahzadeh, Mahmoud; Sajjadi, Mohaddeseh; Ghorbannezhad, Fatemeh; Sajadi, S Mohammad

2018-03-14

A 3 coupling is one of the few transition-metal catalyzed carbon-carbon bond forming reactions that have been established as a most direct, efficient and atom-economical synthetic approach to afford propargylamine derivatives using various catalysts. A large number of nanosized heterogeneous catalysts for three-component coupling reactions between an aldehyde, an amine, and a terminal alkyne have been popularly introduced as an A 3 coupling in the last decade. The coupling product has found a broad application as a key intermediate for a variety of heterocyclic useful compounds and numerous biologically active molecules such as β-lactams, conformationally restricted peptides, isosteres, herbicides, fungicides, indolizines, pyrroles, quinolines and therapeutic drug molecules. This review aims to give an overview of the current progress made towards the preparation and application of various nanocatalysts-catalyzed A 3 coupling transformations for the synthesis of propargylamines from 2007 to 2017. Several nanocatalysts based on metal and metal oxide nanoparticles (NPs) such as copper, gold, silver, iron, nickel, cobalt and zinc have successfully been employed in A 3 coupling reactions. Besides, core-shells NPs, polymers, complexes, graphenes, metal-organic frameworks and ionic liquids have also been used in these reactions. Abundant examples have been given in this area. Different aspects of the reactions, disparate methods of preparation of nanocatalysts, characterization and their reusability have been perused. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mineral and chemical composition of the Jezersko meteorite—A new chondrite from Slovenia

NASA Astrophysics Data System (ADS)

Miler, Miloš; Ambrožič, Bojan; Mirtič, Breda; Gosar, Mateja; Å turm, Sašo.; Dolenec, Matej; Jeršek, Miha

2014-10-01

The Jezersko meteorite is a newly confirmed stony meteorite found in 1992 in the Karavanke mountains, Slovenia. The meteorite is moderately weathered (W2), indicating short terrestrial residence time. Chondrules in partially recrystallized matrix are clearly discernible but often fragmented and have mean diameter of 0.73 mm. The meteorite consists of homogeneous olivine (Fa19.4) and low-Ca pyroxenes (Fs16.7Wo1.2), of which 34% are monoclinic, and minor plagioclase (Ab83An11Or6) and Ca-pyroxene (Fs6Wo45.8). Troilite, kamacite, zoned taenite, tetrataenite, chromite, and metallic copper comprise about 16.5 vol% of the meteorite. Phosphates are represented by merrillite and minor chlorapatite. Undulatory extinction in some olivine grains and other shock indicators suggests weak shock metamorphism between stages S2 and S3. The bulk chemical composition generally corresponds to the mean H chondrite composition. Low siderophile element contents indicate the oxidized character of the Jezersko parent body. The temperatures recorded by two-pyroxene, olivine-chromite, and olivine-orthopyroxene geothermometers are 854 °C, 737-787 °C, and 750 °C, respectively. Mg concentration profiles across orthopyroxenes and clinopyroxenes indicate relatively fast cooling at temperatures above 700 °C. A low cooling rate of 10 °C Myr-1 was obtained from metallographic data. Considering physical, chemical, and mineralogical properties, meteorite Jezersko was classified as an H4 S2(3) ordinary chondrite.

Weathering and transport of chromium and nickel from serpentinite in the Coast Range ophiolite to the Sacramento Valley, California, USA

USGS Publications Warehouse

Morrison, Jean M.; Goldhaber, Martin B.; Mills, Christopher T.; Breit, George N.; Hooper, Robert L.; Holloway, JoAnn M.; Diehl, Sharon F.; Ranville, James F.

2015-01-01

A soil geochemical study in northern California was done to investigate the role that weathering and transport play in the regional distribution and mobility of geogenic Cr and Ni, which are both potentially toxic and carcinogenic. These elements are enriched in ultramafic rocks (primarily serpentinite) and the soils derived from them (1700–10,000 mg Cr per kg soil and 1300–3900 mg Ni per kg soil) in the Coast Range ophiolite. Chromium and Ni have been transported eastward from the Coast Range into the western Sacramento Valley and as a result, valley soil is enriched in Cr (80–1420 mg kg−1) and Ni (65–224 mg kg−1) compared to median values of U.S. soils of 50 and 15 mg kg−1, respectively. Nickel in ultramafic source rocks and soils is present in serpentine minerals (lizardite, antigorite, and chrysotile) and is more easily weathered compared to Cr, which primarily resides in highly refractory chromite ([Mg,Fe2+][Cr3+,Al,Fe3+]2O4). Although the majority of Cr and Ni in soils are in refractory chromite and serpentine minerals, the etching and dissolution of these minerals, presence of Cr- and Ni-enriched clay minerals and development of nanocrystalline Fe (hydr)oxides is evidence that a significant fractions of these elements have been transferred to potentially more labile phases.

Detoxification and immobilization of chromite ore processing residue in spinel-based glass-ceramic.

PubMed

Liao, Chang-Zhong; Tang, Yuanyuan; Lee, Po-Heng; Liu, Chengshuai; Shih, Kaimin; Li, Fangbai

2017-01-05

A promising strategy for the detoxification and immobilization of chromite ore processing residue (COPR) in a spinel-based glass-ceramic matrix is reported in this study. In the search for a more chemically durable matrix for COPR, the most critical crystalline phase for Cr immobilization was found to be a spinel solid solution with a chemical composition of MgCr 1.32 Fe 0.19 Al 0.49 O 4 . Using Rietveld quantitative X-ray diffraction analysis, we identified this final product is with the phases of spinel (3.5wt.%), diopside (5.2wt.%), and some amorphous contents (91.2wt.%). The partitioning ratio of Cr reveals that about 77% of the Cr was incorporated into the more chemically durable spinel phase. The results of Cr K-edge X-ray absorption near-edge spectroscopy show that no Cr(VI) was observed after conversion of COPR into a glass-ceramic, which indicates successful detoxification of Cr(VI) into Cr(III) in the COPR-incorporated glass-ceramic. The leaching performances of Cr 2 O 3 and COPR-incorporated glass-ceramic were compared with a prolonged acid-leaching test, and the results demonstrate the superiority of the COPR-incorporated glass-ceramic matrix in the immobilization of Cr. The overall results suggest that the use of affordable additives has potential in more reliably immobilizing COPR with a spinel-based glass-ceramic for safer disposal of this hazardous waste. Copyright © 2016 Elsevier B.V. All rights reserved.

Mineral inclusions in diamonds from the Kelsey Lake Mine, Colorado, USA: Depleted Archean mantle beneath the Proterozoic Yavapai province

NASA Astrophysics Data System (ADS)

Schulze, Daniel J.; Coopersmith, Howard G.; Harte, Ben; Pizzolato, Lori-Ann

2008-03-01

Thirty-four silicate and oxide inclusions large enough for in situ WDS electron microprobe analysis were exposed by grinding/polishing of 19 diamonds from the Kelsey Lake Mine in the Colorado-Wyoming State Line Kimberlite district. Eighteen olivines, seven Cr-pyropes, four Mg-chromites, and one orthopyroxene in 15 stones belong to the peridotite (P) suite and three garnets and one omphacite in three stones belong to the eclogite (E) suite. The fact that this suite is dominated by the peridotite population is in stark contrast to the other diamond suites studied in the State Line district (Sloan, George Creek), which are overwhelmingly eclogitic. Kelsey Lake olivine inclusions are magnesian (17 of 18 grains in 9 stones are in the range Fo 92.7-93.1), typical of harzburgitic P-suite stones worldwide, but unlike the more Fe-rich (lherzolitic) Sloan olivine suite. Mg-chromites (wt% MgO = 12.8-13.8; wt% Cr 2O 3 = 61.4-66.6) are in the lower MgO range of diamond inclusion chromites worldwide. Seven harzburgitic Cr-pyropes in five stones have moderately low calcium contents (wt% CaO = 3.3-4.3) but are very Cr-rich (wt% Cr 2O 3 = 9.7-16.7). A few stones have been analyzed by SIMS for carbon isotope composition and nitrogen abundance. One peridotitic stone is apparently homogeneous in carbon isotope composition (δ 13C PDB = -6.2‰) but with variable nitrogen abundance (1296-2550 ppm). Carbon isotopes in eclogitic stones range from "normal" for the upper mantle (δ 13C PDB = -5.5‰) to somewhat low (δ 13C PDB = -10.2‰), with little internal variation in individual stones (maximum difference is 3.6‰). Nitrogen contents (2-779 ppm) are lower than in the peridotitic stone, and are lower in cores than in rims. As, worldwide, harzburgite-suite diamonds have been shown to have formed in Archean time, we suggest that the Kelsey Lake diamond population was derived from a block of Archean lithosphere that, at the time of kimberlite eruption, existed beneath the Proterozoic Yavapai province. The mixed diamond inclusion populations from the State Line kimberlites appear to support models in which volumes of Wyoming Craton Archean mantle survive buried beneath Proterozoic continental crust. Such material may be mixed with eclogitic/lherzolitic regimes emplaced beneath or intermingled with the Archean rocks by Proterozoic subduction.

Komatiites and nickel sulfide ores of the Black Swan area, Yilgarn Craton, Western Australia. 3: Komatiite geochemistry, and implications for ore forming processes

NASA Astrophysics Data System (ADS)

Barnes, Stephen J.; Hill, Robin E. T.; Evans, Noreen J.

2004-11-01

The Black Swan komatiite sequence is a package of dominantly olivine-rich cumulates with lesser volumes of spinifex textured rocks, interpreted as a section through an extensive komatiite lava flow field. The sequence hosts a number of nickel sulfide orebodies, including the Silver Swan massive shoot and the Cygnet and Black Swan disseminated orebodies. A large body of whole rock analyses on komatiitic rocks from the Black Swan area has been filtered for metasomatic effects. With the exception of mobile elements such as Ca and alkalis, most samples retain residual igneous geochemistry, and can be modelled predominantly by fractionation and accumulation of olivine. Whole rock MgO FeO relationships imply a relatively restricted range of olivine compositions, more primitive than the olivine which would have been in equilibrium with the transporting komatiite lavas, and together with textural data indicate that much of the cumulus olivine in the sequence was transported. Flow top compositions show evidence for chromite saturation, but the cumulates are deficient in accumulated chromite. Chromite compositions are typical of those found in compound flow-facies komatiites, and are distinct from those in komatiitic dunite bodies. Incompatible trace element abundances show three superimposed influences: control by the relative proportion of olivine to liquid; a signature of crustal contamination and an overprint of metasomatic introduction of LREE, Zr and Th. This overprint is most evident in cumulates, and relatively insignificant in the spinifex rocks. Platinum and palladium behaved as incompatible elements and are negatively correlated with MgO. They show no evidence for wholesale depletion due to sulfide extraction, which was evidently restricted to specific lava tubes or pathways. The lack of correspondence between PGE depletion and contamination by siliceous material implies that contamination alone is insufficient to generate S-saturation and ore formation in the absence of sulfide in the assimilant. Contamination signatures in spinifex-textured rocks may be a guide to Ni-sulfide mineralisation, but are not entirely reliable in the absence of other evidence. The widespread vesicularity of the sequence may be attributable to assimilated water rather than to primary mantle-derived volatiles, and cannot be taken as evidence for primary volatile-rich magmas. The characteristic signature of the Black Swan Succession is the presence of highly localised disseminated sulfide within a sequence showing more widespread evidence for crustal contamination and interaction with its immediate substrate. This has important implications for the applicability of trace element geochemistry in exploration for komatiite-hosted nickel deposits.

MOUNT EDDY AND CASTLE CRAGS ROADLESS AREAS, CALIFORNIA.

USGS Publications Warehouse

Peterson, Jocelyn A.; Denton, David K.

1984-01-01

A mineral survey of the Mount Eddy and Castle Crags Roadless Areas, California, shows probable mineral-resource potential for chromite and gold on the basis of local occurrences of these minerals and favorable geologic environment within the roadless areas. There is also geochemical evidence for mineralization, but surface evidence is scant. Although asbestos and copper minerals are present in the areas and the geologic environment is favorable for nickel and platinum-group metals, no resource potential for these was identified. No energy resources were identified in the study of the roadless areas.

Preparation of thin ceramic films via an aqueous solution route

DOEpatents

Pederson, Larry R.; Chick, Lawrence A.; Exarhos, Gregory J.

1989-01-01

A new chemical method of forming thin ceramic films has been developed. An aqueous solution of metal nitrates or other soluble metal salts and a low molecular weight amino acid is coated onto a substrate and pyrolyzed. The amino acid serves to prevent precipitation of individual solution components, forming a very viscous, glass-like material as excess water is evaporated. Using metal nitrates and glycine, the method has been demonstrated for zirconia with various levels of yttria stabilization, for lanthanum-strontium chromites, and for yttrium-barium-copper oxide superconductors on various substrates.

[Synthesis and Properties of 1,11,15,25-Tetrahydroxy-4,8,18,22-Di (Bridged Dipropionate Carboxyl) Phthalocyanine Copper].

PubMed

Xia, Dao-cheng; Li, Wan-cheng; Li, Jie-jun; Wang, Gai-ping; Duan, Hong-wei; Ren, Xu-wen; Feng, Kai; Li, Pei-tao; Wang, Hui-fang; Pu, Gai-qin

2015-08-01

In this dissertation, we study the synthesis and character of new substituted Phthalocyanine. Due to the widely application of Pcs in the fields, such as the communication, medical treatment, chemical industry and so on, therefore, they have been a hot topic over several decades by scientists. Nowadays, scientists have prepared thousands of Pcs and their derivatives. However, along with the human society development and the progress in science and technology, the new phthalocyanine with novle characteristics are still the goal of the scientists. In this dissertion, the synthetic methods of the phthlocyanine is improved. The synthesis and characterization of 1,11,15,25-tetrahydroxy-4,8,18,22-di(bridged dipropionate carboxyl) phthalocyanines are reported in this paper. The mixtures of malonic acid and 3,6-dihydroxy-phthalonitrile was added to water under stiriing. Then, a catalyst amount of sulfuric acid was added. The first synthetic precursor, i. e., malonic acid 3,3'-bis(6-hydroxy phthalonitrile) butter, its molecular formula is C19H8N4O6. phthalocyanines was prepared by malonic acid 3,3'-bis(6-hydroxy phthalonitrile) butter and dihydrate zinc acetate, copper acetate monohydrate in n-amyl alcohol, using DBU as a catalyst under the 135 °C, molecular formula of phthalocyanine complexes is C38H16N8O12M. The product was characterized by Ultraviolet-visible (UV/Vis) Spectrum absorption and fluorescence, The results are agreement with the proposed structures. And electrochemical properties were studied.

Zinc-Containing Magnetic Oxides Stabilized by a Polymer: One Phase or Two?

PubMed

Baird, Nicholas; Losovyj, Yaroslav; Yuzik-Klimova, Ekaterina Yu; Kuchkina, Nina V; Shifrina, Zinaida B; Pink, Maren; Stein, Barry D; Morgan, David Gene; Wang, Tianhao; Rubin, Mikhail A; Sidorov, Alexander I; Sulman, Esther M; Bronstein, Lyudmila M

2016-01-13

Here we developed a new family of Zn-containing magnetic oxides of different structures by thermal decomposition of Zn(acac)2 in the reaction solution of preformed magnetite nanoparticles (NPs) stabilized by polyphenylquinoxaline. Upon an increase of the Zn(acac)2 loading from 0.15 to 0.40 mmol (vs 1 mmol of Fe(acac)3), the Zn content increases, and the Zn-containing magnetic oxide NPs preserve a spinel structure of magnetite and an initial, predominantly multicore NP morphology. X-ray photoelectron spectroscopy (XPS) of these samples revealed that the surface of iron oxide NPs is enriched with Zn, although Zn species were also found deep under the iron oxide NP surface. For all the samples, XPS also demonstrates the atom ratio of Fe(3+)/Fe(2+) = 2:1, perfectly matching Fe3O4, but not ZnFe2O4, where Fe(2+) ions are replaced with Zn(2+). The combination of XPS with other physicochemical methods allowed us to propose that ZnO forms an ultrathin amorphous layer on the surface of iron oxide NPs and also diffuses inside the magnetite crystals. At higher Zn(acac)2 loading, cubic ZnO nanocrystals coexist with magnetite NPs, indicating a homogeneous nucleation of the former. The catalytic testing in syngas conversion to methanol demonstrated outstanding catalytic properties of Zn-containing magnetic oxides, whose activities are dependent on the Zn loading. Repeat experiments carried out with the best catalyst after magnetic separation showed remarkable catalyst stability even after five consecutive catalytic runs.

Synthesis of ZnO Photocatalysts Using Various Surfactants

NASA Astrophysics Data System (ADS)

Yao, Chengli; Zhu, Jinmiao; Li, Hongying; Zheng, Bin; Wei, Yanxin

2017-12-01

Zinc oxide (ZnO) nanostructured materials have received significant attention because of their unique physicochemical and electronic properties. In particular, the functional properties of ZnO are owed to its morphology and defect structure. ZnO particles were successfully synthesized by chemical precipitation. CTAB (cetyltrimethylammonium bromide), BS-12 (dodecyl dimethyl betaine) and graphene oxide (GO) were selected as templates to induce the formation of ZnO, respectively. By varying the amount of surfactant added during the synthesis process, the structural properties and the crystalline phase of the synthesized nanospheres were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), ultraviolet and visible spectrophotometry (UV‒Vis). Simultaneously, photo catalytic degradation of Rhodamine B (RhB) was carried out under natural sunlight irradiation while ZnO or ZnO/GO particles were used as catalyst. GO is prone to induce formation of wurtzite hexagonal phase of ZnO. Compared with CTAB and BS-12, ZnO/GO composites had a remarkably photocatalytic degradation.

Highly efficient one-pot/one-step synthesis of multiblock copolymers from three-component polymerization of carbon dioxide, epoxide and lactone.

PubMed

Li, Yang; Hong, Jiali; Wei, Renjian; Zhang, Yingying; Tong, Zaizai; Zhang, Xinghong; Du, Binyang; Xu, Junting; Fan, Zhiqiang

2015-02-01

It is a long-standing challenge to combine mixed monomers into multiblock copolymer (MBC) in a one-pot/one-step polymerization manner. We report the first example of MBC with biodegradable polycarbonate and polyester blocks that were synthesized from highly efficient one-pot/one-step polymerization of cyclohexene oxide (CHO), CO 2 and ε-caprolactone (ε-CL) in the presence of zinc-cobalt double metal cyanide complex and stannous octoate. In this protocol, two cross-chain exchange reactions (CCER) occurred at dual catalysts respectively and connected two independent chain propagation procedures ( i.e. , polycarbonate formation and polyester formation) simultaneously in a block-by-block manner, affording MBC without tapering structure. The multiblock structure of MBC was determined by the rate ratio of CCER to the two chain propagations and could be simply tuned by various kinetic factors. This protocol is also of significance due to partial utilization of renewable CO 2 and improved mechanical properties of the resultant MBC.

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

Shang Yazhuo; Hu Jun; Liu Honglai, E-mail: yazhuoshang@ecust.edu.c

Novel large-scale hollow ZnO spherical shells were synthesized by ionic liquids assisted hydrothermal oxidization of pure zinc powder without any catalyst at a relatively low temperature of 160 deg. C. X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and scanning electron microscopy (SEM) patterns show that the shells are composed of ZnO and the structure of the shells is very unique. Textured flower-like ZnO consisting of ZnO rods is grown on the outer surfaces of shells forming a triple assembly. Room-temperature photoluminescence spectra of the oxidized material show a sharp peak at 379 nm and a wider broad peak centeredmore » at 498 nm. The possible growth mechanism of the triple assembly of ZnO is discussed in detail. - Graphical abstract: A proposed growth mechanism of large scale hollow ZnO. Bubbles provide the aggregation center for ionic liquids that leads to the formation of hollow Zn particle-dotted shells, buoyancy promotes shells to go upward, the breach occurs when shells are subjected to overpressure.« less

Enhanced Photoelectrocatalytic Activity of BiOI Nanoplate-Zinc Oxide Nanorod p-n Heterojunction.

PubMed

Kuang, Pan-Yong; Ran, Jing-Run; Liu, Zhao-Qing; Wang, Hong-Juan; Li, Nan; Su, Yu-Zhi; Jin, Yong-Gang; Qiao, Shi-Zhang

2015-10-19

The development of highly efficient and robust photocatalysts has attracted great attention for solving the global energy crisis and environmental problems. Herein, we describe the synthesis of a p-n heterostructured photocatalyst, consisting of ZnO nanorod arrays (NRAs) decorated with BiOI nanoplates (NPs), by a facile solvothermal method. The product thus obtained shows high photoelectrochemical water splitting performance and enhanced photoelectrocatalytic activity for pollutant degradation under visible light irradiation. The p-type BiOI NPs, with a narrow band gap, not only act as a sensitizer to absorb visible light and promote electron transfer to the n-type ZnO NRAs, but also increase the contact area with organic pollutants. Meanwhile, ZnO NRAs provide a fast electron-transfer channel, thus resulting in efficient separation of photoinduced electron-hole pairs. Such a p-n heterojunction nanocomposite could serve as a novel and promising catalyst in energy and environmental applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The preparation and cathodoluminescence of ZnS nanowires grown by chemical vapor deposition

NASA Astrophysics Data System (ADS)

Huang, Meng-Wen; Cheng, Yin-Wei; Pan, Ko-Ying; Chang, Chen-Chuan; Shieu, F. S.; Shih, Han C.

2012-11-01

Single crystal ZnS nanowires were successfully synthesized in large quantities on Si (1 0 0) substrates by simple thermal chemical vapor deposition without using any catalyst. The morphology, composition, and crystal structure were characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and cathodoluminescence (CL) spectroscopy. SEM observations show that the nanowires have diameters about 20-50 nm and lengths up to several tens of micrometers. XRD and TEM results confirmed that the nanowires exhibited both wurtzite and zinc blende structures with growth directions aligned along [0 0 0 2] and [1 1 1], respectively. The CL spectrum revealed emission bands in the UV and blue regions. The blue emissions at 449 and ˜581 nm were attributed to surface states and impurity-related defects of the nanowires, respectively. The perfect crystal structure of the nanowires indicates their potential applications in nanotechnology and in the fabrication of nanodevices.

Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

DOEpatents

Nicholas, Christopher P; Boldingh, Edwin P

2014-04-29

A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

DOEpatents

Nicholas, Christopher P; Boldingh, Edwin P

2013-12-17

A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

Knoevenagel Reaction of Unprotected Sugars

NASA Astrophysics Data System (ADS)

Scherrmann, Marie-Christine

The Knoevenagel reaction of unprotected sugars was investigated in the 1950s using zinc chloride as promoter. The so-called Garcia Gonzalez reaction had been almost forgotten for 50 years, until the emergence of new water tolerant catalysts having Lewis acid behavior. The reaction was thus reinvestigated and optimal conditions have been found to prepare trihydroxylated furan derivatives from pentose or β-tetrahydrofuranylfuran from hexoses with non-cyclic β-keto ester or β-diketones. Other valuable compounds such as β-linked tetrahydrobenzofuranyl glycosides or hydroxyalkyl-3,3,6,6,-tetramethyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione can be obtained using cyclic β-dicarbonylic derivatives. Apart from one report in the 1950s, the Knoevenagel reaction of unprotected carbohydrate in basic condition has been studied only in the mid-1980s to prepare C-glycosyl barbiturates from barbituric acids and, later on, from non-cyclic β-diketones, β-C-glycosidic ketones. The efficient method exploited to prepare such compounds has found an industrial development in cosmetics.

Mapping Brain Metals to Evaluate Therapies for Neurodegenerative Disease

PubMed Central

Popescu, Bogdan Florin Gh; Nichol, Helen

2013-01-01

The brain is rich in metals and has a high metabolic rate, making it acutely vulnerable to the toxic effects of endogenously produced free radicals. The abundant metals, iron and copper, transfer single electrons as they cycle between their reduced (Fe2+, Cu1+) and oxidized (Fe3+, Cu2+) states making them powerful catalysts of reactive oxygen species (ROS) production. Even redox inert zinc, if present in excess, can trigger ROS production indirectly by altering mitochondrial function. While metal chelators seem to improve the clinical outcome of several neurodegenerative diseases, their mechanisms of action remain obscure and the effects of long-term use are largely unknown. Most chelators are not specific to a single metal and could alter the distribution of multiple metals in the brain, leading to unexpected consequences over the long-term. We show here how X-ray fluorescence will be a valuable tool to examine the effect of chelators on the distribution and amount of metals in the brain. PMID:20553312

From microporous regular frameworks to mesoporous materials with ultrahigh surface area: dynamic reorganization of porous polymer networks.

PubMed

Kuhn, Pierre; Forget, Aurélien; Su, Dangsheng; Thomas, Arne; Antonietti, Markus

2008-10-08

High surface area organic materials featuring both micro- and mesopores were synthesized under ionothermal conditions via the formation of polyaryltriazine networks. While the polytrimerization of nitriles in zinc chloride at 400 degrees C produces microporous polymers, higher reaction temperatures induce the formation of additional spherical mesopores with a narrow dispersity. The nitrogen-rich carbonaceous polymer materials thus obtained present surface areas and porosities up to 3300 m(2) g(-1) and 2.4 cm(3) g(-1), respectively. The key point of this synthesis relies on the occurrence of several high temperature polymerization reactions, where irreversible carbonization reactions coupled with the reversible trimerization of nitriles allow the reorganization of the dynamic triazine network. The ZnCl2 molten salt fulfills the requirement of a high temperature solvent, but is also required as catalyst. Thus, this dynamic polymerization system provides not only highly micro- and mesoporous materials, but also allows controlling the pore structure in amorphous organic materials.

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

Torlakoglu, A.; Gueclue, G.

Waste polyethylene terephthalate (PET) flakes were depolymerized by using propylene glycol (PG) in the presence of zinc acetate as catalyst. Glycolysis reaction products of waste PET obtained by using PET/glycol molar ratio 1/2. Two short oil alkyd resins of high acid values (30-40 mgKOH/g) were prepared from phthalic anhydride (PA), glycerin (G), coconut oil fatty acids (COFA) and glycolyzed products of waste PET (PET-based alkyd resins) or glycols (PG) (reference alkyd resins). These alkyd resins were blended with 30%, 40%, and 50% of a commercial urea-formaldehyde, melamine-formaldehyde and urea-formaldehyde/melamine-formaldehyde mixture (1/1 weight ratio) and heated at 140 deg. C. Themore » physical and chemical properties such as drying time, hardness, abrasion resistance, adhesion strength, water resistance, alkaline resistance, acid resistance, gelation time, and thermal oxidative degradation resistance (with thermogravimetric analysis, TGA) of these alkyd-amino resins were investigated. The properties of the waste PET-based resins were found to be compatible with the properties of the reference resins.« less

Cause-specific mortality in Finnish ferrochromium and stainless steel production workers.

PubMed

Huvinen, M; Pukkala, E

2016-04-01

Although stainless steel has been produced for more than a hundred years, exposure-related mortality data for production workers are limited. To describe cause-specific mortality in Finnish ferrochromium and stainless steel workers. We studied Finnish stainless steel production chain workers employed between 1967 and 2004, from chromite mining to cold rolling of stainless steel, divided into sub-cohorts by production units with specific exposure patterns. We obtained causes of death for the years 1971-2012 from Statistics Finland. We calculated standardized mortality ratios (SMRs) as ratios of observed and expected numbers of deaths based on population mortality rates of the same region. Among 8088 workers studied, overall mortality was significantly decreased (SMR 0.77; 95% confidence interval [CI] 0.70-0.84), largely due to low mortality from diseases of the circulatory system (SMR 0.71; 95% CI 0.61-0.81). In chromite mine, stainless steel melting shop and metallurgical laboratory workers, the SMR for circulatory disease was below 0.4 (SMR 0.33; 95% CI 0.07-0.95, SMR 0.22; 95% CI 0.05-0.65 and SMR 0.16; 95% CI 0.00-0.90, respectively). Mortality from accidents (SMR 0.84; 95% CI 0.67-1.04) and suicides (SMR 0.72; 95% CI 0.56-0.91) was also lower than in the reference population. Working in the Finnish ferrochromium and stainless steel industry appears not to be associated with increased mortality. © The Author 2015. Published by Oxford University Press on behalf of the Society of Occupational Medicine.

The soda-ash roasting of chromite ore processing residue for the reclamation of chromium

NASA Astrophysics Data System (ADS)

Antony, M. P.; Tathavadkar, V. D.; Calvert, C. C.; Jha, A.

2001-12-01

Sodium chromate is produced via the soda-ash roasting of chromite ore with sodium carbonate. After the reaction, nearly 15 pct of the chromium oxide remains unreacted and ends up in the waste stream, for landfills. In recent years, the concern over environmental pollution from hexavalent chromium (Cr6+) from the waste residue has become a major problem for the chromium chemical industry. The main purpose of this investigation is to recover chromium oxide present in the waste residue as sodium chromate. Cr2O3 in the residue is distributed between the two spinel solid solutions, Mg(Al,Cr)2O4 and γ-Fe2O3. The residue from the sodium chromate production process was analyzed both physically and chemically. The compositions of the mineral phases were determined by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron probe microanalysis (EPMA). The influence of alkali addition on the overall reaction rate is examined. The kinetics of the chromium extraction reaction resulting from the residue of the soda-ash roasting process under an oxidizing atmosphere is also investigated. It is shown that the experimental results for the roasting reaction can be best described by the Ginstling and Brounshtein (GB) equation for diffusion-controlled kinetics. The apparent activation energy for the roasting reaction was calculated to be between 85 and 90 kJ·mol-1 in the temperature range 1223 to 1473 K. The kinetics of leaching of Cr3+ ions using the aqueous phase from the process residue is also studied by treating the waste into acid solutions with different concentrations.

Phase-dependent space weathering effects and spectroscopic identification of retained helium in a lunar soil grain

NASA Astrophysics Data System (ADS)

Burgess, K. D.; Stroud, R. M.

2018-03-01

The solar wind is an important driver of space weathering on airless bodies. Over time, solar wind exposure alters the physical, chemical, and optical properties of exposed materials and can also impart a significant amount of helium into the surfaces of these bodies. However, common materials on the surface of the Moon, such as glass, crystalline silicates, and oxides, have highly variable responses to solar wind irradiation. We used scanning transmission electron microscopy (STEM) with electron energy loss spectroscopy (EELS) to examine the morphology and chemistry of a single grain of lunar soil that includes silicate glass, chromite and ilmenite, all present and exposed along the same surface. The exposure of the silicate glass and oxides to the same space weathering conditions allows for direct comparisons of the responses of natural materials to the complex lunar surface environment. The silicate glass shows minimal effects of solar wind irradiation, whereas both the chromite and ilmenite exhibit defect-rich rims that currently contain trapped helium. Only the weathered rim in ilmenite is rich in nanophase metallic iron (npFe0) and larger vesicles that retain helium at a range of internal pressures. The multiple exposed surfaces of the single grain of ilmenite demonstrate strong crystallographic controls of planar defects and non-spherical npFe0. The direct spectroscopic identification of helium in the vesicles and planar defects in the oxides provides additional evidence of the central role of solar wind irradiation in the formation of some common space weathering features.

Long-term stability of FeSO4 and H2SO4 treated chromite ore processing residue (COPR): Importance of H+ and SO42.

PubMed

Wang, Xin; Zhang, Jingdong; Wang, Linling; Chen, Jing; Hou, Huijie; Yang, Jiakuan; Lu, Xiaohua

2017-01-05

In this study, the long-term stability of Cr(VI) in the FeSO 4 and H 2 SO 4 (FeSO 4 -H 2 SO 4 ) treated chromite ore processing residue (COPR) after 400 curing days and the stabilization mechanisms were investigated. FeSO 4 -H 2 SO 4 treatment significantly reduced toxicity characteristic leaching procedure (TCLP) and synthetic precipitation leaching procedure (SPLP) Cr(VI) concentrations to lower than the regulatory limit of 1.5mgL -1 (HJ/T 301-2007, China EPA) even for the samples curing 400days, achieving an outstanding long-term stability. Our independent leaching tests revealed that H + and SO 4 2- have synergistic effect on promoting the release of Cr(VI), which would make Cr(VI) easier accessed by Fe(II) during stabilization. The contributions of H + and SO 4 2- to Cr(VI) release ratio were 25%-44% and 19%-38%, respectively, as 5mol H 2 SO 4 per kg COPR was used. X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and alkaline digestion analyses were also employed to interpret the possible stabilization mechanism. Cr(VI) released from COPR solid was reduced to Cr(III) by Fe(II), and then formed stable Fe x Cr (1-x) (OH) 3 precipitate. This study provides a facile and reliable scheme for COPR stabilization, and verifies the excellent long-term stability of the FeSO 4 -H 2 SO 4 treated COPR. Copyright © 2016 Elsevier B.V. All rights reserved.

Assessment of ferrous chloride and Portland cement for the remediation of chromite ore processing residue.

PubMed

Jagupilla, Santhi C; Wazne, Mahmoud; Moon, Deok Hyun

2015-10-01

Chromite Ore Processing Residue (COPR) is an industrial waste containing up to 7% chromium (Cr) including up to 5% hexavalent chromium [Cr(VI)]. The remediation of COPR has been challenging due to the slow release of Cr(VI) from a clinker like material and thereby the incomplete detoxification of Cr(VI) by chemical reagents. The use of sulfur based reagents such as ferrous sulfate and calcium polysulfide to detoxify Cr(VI) has exasperated the swell potential of COPR upon treatment. This study investigated the use of ferrous chloride alone and in combination with Portland cement to address the detoxification of Cr(VI) in COPR and the potential swell of COPR. Chromium regulatory tests, X-ray powder diffraction (XRPD) analyses and X-ray absorption near edge structure (XANES) analyses were used to assess the treatment results. The treatment results indicated that Cr(VI) concentrations for the acid pretreated micronized COPR as measured by XANES analyses were below the New Jersey Department of Environmental Protection (NJDEP) standard of 20 mg kg(-1). The Toxicity characteristic leaching procedure (TCLP) Cr concentrations for all acid pretreated samples also were reduced below the TCLP regulatory limit of 5 mg L(-1). Moreover, the TCLP Cr concentration for the acid pretreated COPR with particle size ⩽0.010 mm were less than the universal treatment standard (UTS) of 0.6 mg L(-1). The treatment appears to have destabilized all COPR potential swell causing minerals. The unconfined compressive strength (UCS) for the treated samples increased significantly upon treatment with Portland cement. Copyright © 2015 Elsevier Ltd. All rights reserved.

High-resolution analyses reveal structural diversity patterns of microbial communities in Chromite Ore Processing Residue (COPR) contaminated soils.

PubMed

Min, Xiaobo; Wang, Yangyang; Chai, Liyuan; Yang, Zhihui; Liao, Qi

2017-09-01

To explore how heavy metal contamination in Chromite Ore Processing Residue (COPR) disposal sites determine the dissimilarities of indigenous microbial communities, 16S rRNA gene MiSeq sequencing and advanced statistical methods were applied. 13 soil samples were collected from three COPR disposal sites in Mouding of southwestern, Shangnan of northwestern and Yima of central China. The results of analyses of variance (ANOVA), similarities (ANOSIM), and non-metric multidimensional scaling (NMDS) showed that the structural diversity of the microbial communities in the samples with high total chromium (Cr) content (more than 300 mg kg -1 ; High group) were significantly lesser than in the Low group (less than 90 mg kg -1 ) regardless of their geographical distribution. But their diversity had virtually rehabilitated under the pressures of long-term metal contamination. Furthermore, the similarity percentage (SIMPER) analysis indicated that the major dissimilarity contributors Micrococcaceae, Delftia, and Streptophyta, possibly having Cr(VI)-resistant and/or Cr(VI)-reducing capability, were dominant in the High group, while Ramlibacter and Gemmatimonas with potential resistances to other heavy metals were prevalent in the Low group. In addition, the multivariate regression tree (MRT), aggregated boosted tree (ABT), and Mantel test revealed that total Cr content affiliated with Cr(VI) was the principal factor shaping the dissimilarities between the soil microbial communities in the COPR sites. Our findings provide a deep insight of the influence of these heavy metals on the microbial communities in the COPR disposal sites and will facilitate bioremediation on such site. Copyright © 2017 Elsevier Ltd. All rights reserved.

Acute changes in cellular zinc alters zinc uptake rates prior to zinc transporter gene expression in Jurkat cells.

PubMed

Holland, Tai C; Killilea, David W; Shenvi, Swapna V; King, Janet C

2015-12-01

A coordinated network of zinc transporters and binding proteins tightly regulate cellular zinc levels. Canonical responses to zinc availability are thought to be mediated by changes in gene expression of key zinc transporters. We investigated the temporal relationships of actual zinc uptake with patterns of gene expression in membrane-bound zinc transporters in the human immortalized T lymphocyte Jurkat cell line. Cellular zinc levels were elevated or reduced with exogenous zinc sulfate or N,N,N',N-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN), respectively. Excess zinc resulted in a rapid 44 % decrease in the rate of zinc uptake within 10 min. After 120 min, the expression of metallothionein (positive control) increased, as well as the zinc exporter, ZnT1; however, the expression of zinc importers did not change during this time period. Zinc chelation with TPEN resulted in a rapid twofold increase in the rate of zinc uptake within 10 min. After 120 min, the expression of ZnT1 decreased, while again the expression of zinc importers did not change. Overall, zinc transporter gene expression kinetics did not match actual changes in cellular zinc uptake with exogenous zinc or TPEN treatments. This suggests zinc transporter regulation may be the initial response to changes in zinc within Jurkat cells.

Maternal Zinc Intakes and Homeostatic Adjustments during Pregnancy and Lactation

PubMed Central

Donangelo, Carmen Marino; King, Janet C.

2012-01-01

Zinc plays critical roles during embryogenesis, fetal growth, and milk secretion, which increase the zinc need for pregnancy and lactation. Increased needs can be met by increasing the dietary zinc intake, along with making homeostatic adjustments in zinc utilization. Potential homeostatic adjustments include changes in circulating zinc, increased zinc absorption, decreased zinc losses, and changes in whole body zinc kinetics. Although severe zinc deficiency during pregnancy has devastating effects, systematic reviews and meta-analysis of the effect of maternal zinc supplementation on pregnancy outcomes have consistently shown a limited benefit. We hypothesize, therefore, that zinc homeostatic adjustments during pregnancy and lactation improve zinc utilization sufficiently to provide the increased zinc needs in these stages and, therefore, mitigate immediate detrimental effects due to a low zinc intake. The specific questions addressed are the following: How is zinc utilization altered during pregnancy and lactation? Are those homeostatic adjustments influenced by maternal zinc status, dietary zinc, or zinc supplementation? These questions are addressed by critically reviewing results from published human studies on zinc homeostasis during pregnancy and lactation carried out in different populations worldwide. PMID:22852063

Platinum mineralization in the Kapalagulu Intrusion, western Tanzania

NASA Astrophysics Data System (ADS)

Wilhelmij, Harry R.; Cabri, Louis J.

2016-03-01

Low-grade copper and nickel mineralization was found near the eastern shore of Lake Tanganyika at Kungwe Bay in the early part of the twentieth century. The mineralization occurs in harzburgite at the base of a layered gabbro complex known as the Kapalagulu Intrusion, emplaced between the Paleoproterozoic Ubendian basement and overlying Neoproterozoic Itiaso Group metasediments. Several mining and exploration companies continued the geophysical and drilling exploration for base metals throughout the last century culminating in the discovery of high-grade platinum-group element (PGE) mineralization associated with chromitite and sulfide-bearing harzburgite within the southeastern extension of the Kapalagulu Intrusion (known as the Lubalisi Zone) that is covered by a layer of nickel-rich laterite regolith. The poorly layered southeastern harzburgite forms part of the >1500 m-thick Lower Ultramafic Sequence and resembles a dike-like body that flares upwards into a succession of well-layered gabbroic rocks of the Upper Mafic Sequence. No PGE mineralization has been found in the layered gabbro; all the mineralization is associated with the chromite- and sulfide-rich harzburgite of the Lower Ultramafic Sequence and the laterite regolith overlying the mineralized harzburgite. The Lubalisi Zone harzburgite is underlain by basal dunite and overlain by an interval of layered harzburgite and troctolite and this ultramafic sequence is folded into a syncline that plunges towards the northwest that has been modified by major dolerite-filled faults orientated subparallel to the fold axial surface. Extensive deep drilling in the Lubalisi Zone of the Kapalagulu Intrusion shows that the folded harzburgite can be subdivided into a lower feldspathic harzburgite, a harzburgite containing chromitite seams and intervals of sulfide and chromite mineralization known as the Main Chromite Sulfide Succession (MCSS), an overlying sulfide-rich harzburgite, and an upper feldspathic harzburgite. Impersistent, stratiform PGE mineralized horizons occur within the MCSS harzburgite from which drill core samples were taken for platinum-group mineral (PGM) characterization from two drill holes. Where the PGE reefs reach the surface there is residual PGE mineralization within the laterite regolith from which drill core samples were taken from various laterite lithological units for PGM characterization. As the harzburgite PGE reefs contain significant concentrations of both sulfide and chromite (including chromitite seams) they resemble the PGE-rich chromitite seams of the Bushveld Complex rather than the PGE-bearing Main Sulfide Zone of the Great Dyke and Main Sulfide Layer of the Munni Munni Complex. The dominant Pd PGM in three PGE reef samples varies, ranging ( n = 164, relative wt%) from bismuthides (63 %), bismuthtellurides (19 %), and tellurides (6 %), to tellurides (39 %), bismuthtellurides (24 %), stannides (14 %), and alloys (13 %), and to antimon-arsenides (33 %), stannides (21 %), bismuthides (17 %), tellurides (13 %), and alloys (10 %). From 13.5 % to 21.0 % of the total Pd occurs as a solid solution in pentlandite. The three samples have similar Pt PGM modal distributions ( n = 172, relative wt%); the dominant Pt mineral is sperrylite (79, 58, and 47 %) followed by tellurides (15, 17, 21 %), alloys (2, 1, 1 %), and sulfides (2, 1, 0 %). Comparison of Pd/Pt ratios from assays to those calculated from minerals show that the data for the Pt and Pd PGM are very robust, confirming the concentration methodology and characterization. Study of samples from a shallow drill hole penetrating the laterite regolith shows that the primary Pd mineralization has not survived oxidation, is mainly dispersed, but some was reconstituted to form secondary minerals: cabriite, unnamed tellurides, a selenide, a Pd-Te-Hg mineral, alloys and Pd-bearing secondary sulfides (millerite and heazlewoodite). The primary Pt minerals are more resistant to oxidation and dissolution, especially sperrylite and isoferroplatinum, but it is likely that other Pt alloys (tetraferroplatinum and tulameenite) are of secondary origin after dissolution of Pt tellurides.

Biomarkers of Nutrition for Development (BOND)—Zinc Review12345

PubMed Central

King, Janet C; Brown, Kenneth H; Gibson, Rosalind S; Krebs, Nancy F; Lowe, Nicola M; Siekmann, Jonathan H; Raiten, Daniel J

2016-01-01

Zinc is required for multiple metabolic processes as a structural, regulatory, or catalytic ion. Cellular, tissue, and whole-body zinc homeostasis is tightly controlled to sustain metabolic functions over a wide range of zinc intakes, making it difficult to assess zinc insufficiency or excess. The BOND (Biomarkers of Nutrition for Development) Zinc Expert Panel recommends 3 measurements for estimating zinc status: dietary zinc intake, plasma zinc concentration (PZC), and height-for-age of growing infants and children. The amount of dietary zinc potentially available for absorption, which requires an estimate of dietary zinc and phytate, can be used to identify individuals and populations at risk of zinc deficiency. PZCs respond to severe dietary zinc restriction and to zinc supplementation; they also change with shifts in whole-body zinc balance and clinical signs of zinc deficiency. PZC cutoffs are available to identify individuals and populations at risk of zinc deficiency. However, there are limitations in using the PZC to assess zinc status. PZCs respond less to additional zinc provided in food than to a supplement administered between meals, there is considerable interindividual variability in PZCs with changes in dietary zinc, and PZCs are influenced by recent meal consumption, the time of day, inflammation, and certain drugs and hormones. Insufficient data are available on hair, urinary, nail, and blood cell zinc responses to changes in dietary zinc to recommend these biomarkers for assessing zinc status. Of the potential functional indicators of zinc, growth is the only one that is recommended. Because pharmacologic zinc doses are unlikely to enhance growth, a growth response to supplemental zinc is interpreted as indicating pre-existing zinc deficiency. Other functional indicators reviewed but not recommended for assessing zinc nutrition in clinical or field settings because of insufficient information are the activity or amounts of zinc-dependent enzymes and proteins and biomarkers of oxidative stress, inflammation, or DNA damage. PMID:26962190

Zinc starvation induces autophagy in yeast

PubMed Central

Kawamata, Tomoko; Horie, Tetsuro; Matsunami, Miou; Sasaki, Michiko; Ohsumi, Yoshinori

2017-01-01

Zinc is an essential nutrient for all forms of life. Within cells, most zinc is bound to protein. Because zinc serves as a catalytic or structural cofactor for many proteins, cells must maintain zinc homeostasis under severely zinc-deficient conditions. In yeast, the transcription factor Zap1 controls the expression of genes required for uptake and mobilization of zinc, but to date the fate of existing zinc-binding proteins under zinc starvation remains poorly understood. Autophagy is an evolutionarily conserved cellular degradation/recycling process in which cytoplasmic proteins and organelles are sequestered for degradation in the vacuole/lysosome. In this study, we investigated how autophagy functions under zinc starvation. Zinc depletion induced non-selective autophagy, which is important for zinc-limited growth. Induction of autophagy by zinc starvation was not directly related to transcriptional activation of Zap1. Instead, TORC1 inactivation directed zinc starvation-induced autophagy. Abundant zinc proteins, such as Adh1, Fba1, and ribosomal protein Rpl37, were degraded in an autophagy-dependent manner. But the targets of autophagy were not restricted to zinc-binding proteins. When cellular zinc is severely depleted, this non-selective autophagy plays a role in releasing zinc from the degraded proteins and recycling zinc for other essential purposes. PMID:28264932

A dynamic model for predicting growth in zinc-deficient stunted infants given supplemental zinc.

PubMed

Wastney, Meryl E; McDonald, Christine M; King, Janet C

2018-05-01

Zinc deficiency limits infant growth and increases susceptibility to infections, which further compromises growth. Zinc supplementation improves the growth of zinc-deficient stunted infants, but the amount, frequency, and duration of zinc supplementation required to restore growth in an individual child is unknown. A dynamic model of zinc metabolism that predicts changes in weight and length of zinc-deficient, stunted infants with dietary zinc would be useful to define effective zinc supplementation regimens. The aims of this study were to develop a dynamic model for zinc metabolism in stunted, zinc-deficient infants and to use that model to predict the growth response when those infants are given zinc supplements. A model of zinc metabolism was developed using data on zinc kinetics, tissue zinc, and growth requirements for healthy 9-mo-old infants. The kinetic model was converted to a dynamic model by replacing the rate constants for zinc absorption and excretion with functions for these processes that change with zinc intake. Predictions of the dynamic model, parameterized for zinc-deficient, stunted infants, were compared with the results of 5 published zinc intervention trials. The model was then used to predict the results for zinc supplementation regimes that varied in the amount, frequency, and duration of zinc dosing. Model predictions agreed with published changes in plasma zinc after zinc supplementation. Predictions of weight and length agreed with 2 studies, but overpredicted values from a third study in which other nutrient deficiencies may have been growth limiting; the model predicted that zinc absorption was impaired in that study. The model suggests that frequent, smaller doses (5-10 mg Zn/d) are more effective for increasing growth in stunted, zinc-deficient 9-mo-old infants than are larger, less-frequent doses. The dose amount affects the duration of dosing necessary to restore and maintain plasma zinc concentration and growth.

Plunder behind the bamboo curtain. [Environmental effects of mining and deforestation in Tibet

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

Denniston, D.

Significant environmental degradation has occurred in Tibet as China has stripped forests and minerals from the ground. Uranium, borax, lithium, copper, iron, chromite are all being exploited. High pasture is being overgrazed because fertile valleys are being inhabited by workers. Shortages of timber and paper pulp in China have meant cutting of dense stands of spruce, fir, larch, oak maple, and pine. Ground and surface waters are contaminated from mining, severe erosion is increasing from deforestation, overgrazing and mining on the high plateau. Importation of large numbers of Chinese workers has further threatened the Tibetian culture.

CHATTAHOOCHEE ROADLESS AREA, GEORGIA.

USGS Publications Warehouse

Nelson, Arthur E.; Welsh, Robert A.

1984-01-01

A mineral survey indicates that the Chattahoochee Roadless Area, Georgia, offers little promise for the occurrence of mineral resources even though gold, mica, sillimanite, soapstone, dunite, chromite, and nickel have been mined nearby, and source rocks for these commodities are present in the roadless area. Granite gneiss, gneiss, schist, and metasandstone in the roadless area are suitable for stone, crushed rock, or aggregate; however, other sources for these materials are available outside the roadless area, closer to present markets. The potential for the occurrence of hydrocarbons (probably gas) beneath the thick regional thrust sheets in this area cannot be adequately evaluated from available data.

Petrologic and Oxygen-Isotopic Investigations of Eucritic and Anomalous Mafic Achondrites

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Greenwood, R. C.; Peng, Z. X.; Ross, D. K.; Berger, E. L.; Barrett, T. J.

2016-01-01

The most common asteroidal igneous meteorites are eucrite-type basalts and gabbros rocks composed of ferroan pigeonite and augite, calcic plagioclase, silica, ilmenite, troilite, Ca-phosphate, chromite and Fe-metal. These rocks are thought to have formed on a single asteroid along with howardites and diogenites (HEDs). However, Northwest Africa (NWA) 011 is mineralogically identical to eucrites, but has an O-isotopic composition distinct from them and was derived from a different asteroid. Modern analyses with higher precision have shown that some eucrites have smaller O-isotopic differences that are nevertheless well-resolved from the group mean.

Oceanic crust within the paleozoic Granjeno Schist, northeastern Mexico. Remnants of the Rheic and paleo-Pacific Ocean.

NASA Astrophysics Data System (ADS)

Torres Sanchez, Sonia Alejandra; Augustsson, Carita; Rafael Barboza Gudiño, Jose; Jenchen, Uwe; Torres Sanchez, Dario; Aleman Gallardo, Eduardo; Abratis, Michael

2015-04-01

Late Paleozoic metamorphic rocks in Mexico are related to the Laurentia-Gondwana collision in Carboniferous time, during Pangaea amalgamation. Vestiges of the Mexican Paleozoic continental configuration are present in the Granjeno Schist, the metamorphic basement of the Sierra Madre Oriental. Field work and petrographic analysis reveal that the Granjeno Schist comprises metamorphic rocks with both sedimentary (psammite, pelite, turbidite, conglomerate, black shale) and igneous (tuff, lava flows, pillow lava and ultramafic bodies) protoliths. The chlorite geothermometer and the presence of phengite in the metasedimentary units as well as 40Ar/39Ar ages on metavolcanic and metaultramafic rocks indicate that the Granjeno Schist was metamorphosed under sub-greenschist to greenschist facies with temperatures ranging from 250-345°C with 2.5 kbar during Carboniferous time (330±30 Ma). The presence of metabasalt, metacumulate, serpentinite and talc bodies suggests an oceanic tectonic setting for the evolution of the Granjeno Schist. Serpetinite rocks have mesh, granular and ribbon textures which indicate recrystallization and metasomatic events. The serpentinite rocks are enriched in the very large incompatible elements Cs, U, and Zr and depleted in Ba, Sr, Pb, Zr and Ce. Normalized REE patterns (LaN/YbN = 0.51 - 19.95 and LaN/SmN = 0.72 - 9.08) of the serpentinite and talc/soapstone are characteristic of peridotite from both suprasubduction and mid-ocean ridge zones. Serpentinite from the Granjeno Schist have spinel content which can reveal different stages of evolution in host serpentinite. The composition of chromite indicates that they belong to podiform chromite that may have crystallized from mid-ocean ridge magma. Al-chromite in the serpentinite is characterized by #Cr 0.48 to 0.55, which indicates a depleted mantle source affected by 17 to 18% of partial melting. The ferritchromite has #Cr values of 0.93 to 1.00 which indicates a metamorphic origin. Our study suggests at least two serpentinization stages. The first serpentinization stage is related to an ocean-floor environment. At this stage, mesh-textured serpentinite formed under static conditions under subgreenschist to greenschist conditions. The second serpentinization stage occurred under greenschist to low amphibole conditions. During this stage Cr-spinel progressively was replaced by ferritchromite with magnetite rims due to regional metamorphism. Tectonic contact of the serpentinite with metavolcanic and metasedimentary rocks indicates lithospheric mantle slivers juxtaposed during the metamorphism of the Granjeno Schist during Pennsylvanian time. This metamorphic event occurred in an active continental margin. It represents the last events of the southern closure of the Rheic Ocean and Permo-Carboniferous convergence of Pacific plates on the western margin of Pangea.

Eclogite-facies guyanaite, carmichaelite and eskolaite in xenoliths of Cr-omphacitite from Navajo diatremes, Utah: Hydration and dehydration in the subducted Farallon plate

NASA Astrophysics Data System (ADS)

Schulze, D. J.; Helmstaedt, H.

2013-12-01

The mantle-derived xenolith suite in the Navajo serpentinized ultramafic diatremes includes low-temperature metamorphic rocks such as lawsonite- and phengite-bearing eclogites, Cr-pyrope xenocrysts with inclusions of hydrous minerals and hydrated peridotites and pyroxenites containing minerals such as chlorite, pargasite, tremolite and antigorite. We have now also identified a suite of bright green Cr-rich clinopyroxenites from the Moses Rock and Mule's Ear diatremes that contain unusual assemblages of dark to opaque accessory minerals such as guyanaite [CrOOH], carmichaelite [(Ti,Cr)2-x(OH)x], eskolaite [Cr2O3], chromite and rutile. The xenoliths are dominated by omphacitic pyroxenes (most in the range 10-55 mole% jadeite) that are locally enriched in Cr adjacent to clots of accessory minerals (to 35 mole% kosmochlor). Most samples have small clusters of scattered accessory minerals (individual grains on the scale of tens of microns) but one sample has clusters to 2 mm dominated by guyanaite blades intergrown with Cr-rich omphacite. Thin grains of eskolaite traverse the guyanaite and occur at the guyanaite-omphacite interfaces. Patches of zincian chromite (to 5.7 wt% ZnO) are associated with some of the guyanaite-dominated clusters and consist of lamellar intergrowths of two texturally and compositionally different types of chromite, interpreted as an exsolution feature and precursor to hydration and metasomatic development of guyanaite-omphacite intergrowths. Minor carmichaelite occurs in these clusters. In another sample carmichaelite with finely intergrown patches of rutile dominates the clusters. Equilibration conditions of these assemblages are poorly constrained, but the reaction guyanaite = eskolaite + H2O (Jahn et al., Eur. J. Min., 2012) is consistent with an estimate for equilibration conditions of a phengite eclogite (700oC, 3.4GPa - Smith et al., GGG, 2013). We interpret these rocks to be Na-metasomatized and hydrated basalts (small clusters) and peridotites (clusters to 2mm), formed in serpentinites during subduction of the Farallon Plate under the Colorado Plateau in Laramide time, based on similarities with subduction-origin Cr-jade bodies associated with serpentinites (e.g., Myanmar). At the time of entrainment in the host diatremes, these rocks were undergoing dehydration reactions (guyanaite to eskolaite, carmichaelite to rutile) providing water to the overlying subcrustal mantle section and contributing to Plateau uplift. The occurrence of carmichaelite as inclusions armoured within pyrope garnet xenocrysts from the nearby Garnet Ridge diatreme is now linked to the presence of carmichaelite in the open system of the upper mantle in these Cr-omphacitites (the only two known occurrences of carmichaelite), complicating interpretation of the pyropes as being derived from subcontinental upper mantle formed by Proterozoic subduction.

High-pressure behaviour of Cr-Fe-Mg-Al spinels: applications to diamond geobarometry

NASA Astrophysics Data System (ADS)

Periotto, Benedetta; Bruschini, Enrico; Nestola, Fabrizio; Lenaz, Davide; Princivalle, Francesco; Andreozzi, Giovanni B.; Bosi, Ferdinando

2014-05-01

Spinels belonging to the chromite - magnesiochromite - hercynite (FeCr2O4-MgCr2O4-FeAl2O4) system are among the most common inclusions found in diamonds (Stachel and Harris 2008). In particular, although FeCr2O4 and MgCr2O4 components sum to between 85 and 88% of spinels found in diamonds, hercynite FeAl2O4 plays a not negligible role in determining their thermo-elastic properties with concentrations reaching 7-9 % (other minor end-members like MgAl2O4, MgFe2O4 and Fe2O3 rarely reach 2-3% in total, see Lenaz et al. 2009). Recent studies were focused on the determination of the diamond formation pressure by the so-called "elastic method" (see for example Nestola et al. 2011 and references therein). It was demonstrated that accurate and precise thermo-elastic parameters are fundamental to minimize the uncertainty of formation pressure. In this work we have determined the equations of state at room temperature of three synthetic spinel end-members chromite - magnesiochromite - hercynite and one natural spinel crystal extracted from a diamond (from Udachnaya mine, Siberia, Russia) by single-crystal X-ray diffraction in situ at high-pressure. A diamond-anvil cell was mounted on a STADI IV diffractometer equipped with a point detector and motorized by SINGLE software (Angel and Finger 2011). The natural crystal was investigated to test (and possibly validate) the "empirical prediction model", capable to provide bulk modulus and its first pressure derivative only knowing the composition of the spinels found in diamonds. Such prediction model could be used to obtain pressure of formation for the diamond-spinel pair through the elastic method. Details and results will be discussed. The research was funded by the ERC Starting Grant to FN (grant agreement n° 307322). References Angel R.J., Finger L.W. (2011) SINGLE A program to control single-crystal diffractometers. Journal of Applied Crystallography, 44, 247-251. Lenaz D., Logvinova A.M., Princivalle F., Sobolev N. (2009) Structural parameters of chromite included in diamond and kimberlites from Siberia: a new tool for discriminating source. American Mineralogist, 94, 1067-1070. Nestola F., Nimis P., Ziberna L., Longo M., Marzoli A., Harris J.W., Manghnani M.H., Fedortchouk Y. (2011) First crystal-structure determination of olivine in diamond: composition and implications for provenance in the Earth's mantle. Earth and Planetary Science Letters, 305, 249-255. Stachel, T., and Harris, J.W. (2008) The origin of cratonic diamonds - constraints from mineral inclusions. Ore Geology Reviews, 34, 5-32.

Effect of heterovalent substitutions in yttrium chromite on the hyperfine interactions of {sup 119}Sn{sup 4+} studied by Mössbauer spectroscopy

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

Fabritchnyi, Pavel B., E-mail: pf_1404@yahoo.fr; Afanasov, Mikhail I.; Mezhuev, Evgeny M.

2016-03-15

In order to develop the {sup 119}Sn Mössbauer spectroscopic probe technique to study magnetically ordered materials, three Ca-substituted yttrium chromites, i.e. Y{sub 0.9}Ca{sub 0.1}CrO{sub 3}, Y{sub 0.9}Ca{sub 0.1}Cr{sub 0.9}Ti{sub 0.1}O{sub 3} and Y{sub 0.8}Ca{sub 0.2}Cr{sub 0.8}Ti{sub 0.2}O{sub 3}, doped with 0.3 atom-% Sn{sup 4+}, were for the first time investigated. {sup 119}Sn Mössbauer spectra, recorded at 4.2 K, have allowed, through analysis of the magnetic hyperfine field values, probed by {sup 119}Sn nuclei, to gain insight into the local magnetically active surrounding of different Sn{sup 4+} ions. In all of these compounds, partial segregation of Sn{sup 4+} ions is revealed.more » In the case of Y{sub 0.9}Ca{sub 0.1}CrO{sub 3}, neither highly oxidized Cr{sup 4+} nor Cr{sup 6+} species, expected to compensate for the Ca{sup 2+} positive charge deficit, is found in the vicinity of the {sup 119}Sn{sup 4+} probe. In the case of both studied Ti-containing chromites, {sup 119}Sn Mössbauer spectra have provided the original indirect evidence for the statistical distribution of Cr{sup 3+} and Ti{sup 4+} ions over the octahedral sites and permitted characterization of the occurring associates of Sn{sup 4+}. - Graphical abstract: Two kinds of Sn{sup 4+} associates allowing {sup 119}Sn Mössbauer spectra of tin-doped Y{sub 0.9}Ca{sub 0.1}Cr{sub 0.9}Ti{sub 0.1}O{sub 3} and Y{sub 0.8}Ca{sub 0.2}Cr{sub 0.8}Ti{sub 0.2}O{sub 3} to be accounted for. - Highlights: • {sup 119}Sn probe is tested as a source of information on the B-sublattice of AF perovskites. • Neither Cr{sup 3+} nor Cr{sup 6+} is detected nearby {sup 119}Sn{sup 4+} ions in Y{sub 0.9}Ca{sub 0.1}CrO{sub 3}. • Cr{sup 3+} and Ti{sup 4+} are found to be randomly distributed in Y{sub 1−x}Ca{sub x}Cr{sub 1−x}Ti{sub x}O{sub 3} (x=0.1 or 0.2). • Sn{sup 4+} dopant segregations are revealed in all of the studied materials.« less

A moderate increase in dietary zinc reduces DNA strand breaks in leukocytes and alters plasma proteins without changing plasma zinc concentrations123

PubMed Central

Zyba, Sarah J; Killilea, David W; Holland, Tai C; Kim, Elijah; Moy, Adrian; Sutherland, Barbara; Shigenaga, Mark K

2017-01-01

Background: Food fortification has been recommended to improve a population’s micronutrient status. Biofortification techniques modestly elevate the zinc content of cereals, but few studies have reported a positive impact on functional indicators of zinc status. Objective: We determined the impact of a modest increase in dietary zinc that was similar to that provided by biofortification programs on whole-body and cellular indicators of zinc status. Design: Eighteen men participated in a 6-wk controlled consumption study of a low-zinc, rice-based diet. The diet contained 6 mg Zn/d for 2 wk and was followed by 10 mg Zn/d for 4 wk. To reduce zinc absorption, phytate was added to the diet during the initial period. Indicators of zinc homeostasis, including total absorbed zinc (TAZ), the exchangeable zinc pool (EZP), plasma and cellular zinc concentrations, zinc transporter gene expression, and other metabolic indicators (i.e., DNA damage, inflammation, and oxidative stress), were measured before and after each dietary-zinc period. Results: TAZ increased with increased dietary zinc, but plasma zinc concentrations and EZP size were unchanged. Erythrocyte and leukocyte zinc concentrations and zinc transporter expressions were not altered. However, leukocyte DNA strand breaks decreased with increased dietary zinc, and the level of proteins involved in DNA repair and antioxidant and immune functions were restored after the dietary-zinc increase. Conclusions: A moderate 4-mg/d increase in dietary zinc, similar to that which would be expected from zinc-biofortified crops, improves zinc absorption but does not alter plasma zinc. The repair of DNA strand breaks improves, as do serum protein concentrations that are associated with the DNA repair process. This trial was registered at clinicaltrials.gov as NCT02861352. PMID:28003206

Zinc as a Gatekeeper of Immune Function

PubMed Central

Wessels, Inga; Maywald, Martina; Rink, Lothar

2017-01-01

After the discovery of zinc deficiency in the 1960s, it soon became clear that zinc is essential for the function of the immune system. Zinc ions are involved in regulating intracellular signaling pathways in innate and adaptive immune cells. Zinc homeostasis is largely controlled via the expression and action of zinc “importers” (ZIP 1–14), zinc “exporters” (ZnT 1–10), and zinc-binding proteins. Anti-inflammatory and anti-oxidant properties of zinc have long been documented, however, underlying mechanisms are still not entirely clear. Here, we report molecular mechanisms underlying the development of a pro-inflammatory phenotype during zinc deficiency. Furthermore, we describe links between altered zinc homeostasis and disease development. Consequently, the benefits of zinc supplementation for a malfunctioning immune system become clear. This article will focus on underlying mechanisms responsible for the regulation of cellular signaling by alterations in zinc homeostasis. Effects of fast zinc flux, intermediate “zinc waves”, and late homeostatic zinc signals will be discriminated. Description of zinc homeostasis-related effects on the activation of key signaling molecules, as well as on epigenetic modifications, are included to emphasize the role of zinc as a gatekeeper of immune function. PMID:29186856

Zinc starvation induces autophagy in yeast.

PubMed

Kawamata, Tomoko; Horie, Tetsuro; Matsunami, Miou; Sasaki, Michiko; Ohsumi, Yoshinori

2017-05-19

Zinc is an essential nutrient for all forms of life. Within cells, most zinc is bound to protein. Because zinc serves as a catalytic or structural cofactor for many proteins, cells must maintain zinc homeostasis under severely zinc-deficient conditions. In yeast, the transcription factor Zap1 controls the expression of genes required for uptake and mobilization of zinc, but to date the fate of existing zinc-binding proteins under zinc starvation remains poorly understood. Autophagy is an evolutionarily conserved cellular degradation/recycling process in which cytoplasmic proteins and organelles are sequestered for degradation in the vacuole/lysosome. In this study, we investigated how autophagy functions under zinc starvation. Zinc depletion induced non-selective autophagy, which is important for zinc-limited growth. Induction of autophagy by zinc starvation was not directly related to transcriptional activation of Zap1. Instead, TORC1 inactivation directed zinc starvation-induced autophagy. Abundant zinc proteins, such as Adh1, Fba1, and ribosomal protein Rpl37, were degraded in an autophagy-dependent manner. But the targets of autophagy were not restricted to zinc-binding proteins. When cellular zinc is severely depleted, this non-selective autophagy plays a role in releasing zinc from the degraded proteins and recycling zinc for other essential purposes. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Intracellular zinc distribution in mitochondria, ER and the Golgi apparatus

PubMed Central

Lu, Qiping; Haragopal, Hariprakash; Slepchenko, Kira G; Stork, Christian; Li, Yang V

2016-01-01

Zinc (Zn2+) is required for numerous cellular functions. As such, the homeostasis and distribution of intracellular zinc can influence cellular metabolism and signaling. However, the exact distribution of free zinc within live cells remains elusive. Previously we showed the release of zinc from thapsigargin/IP3-sensitive endoplasmic reticulum (ER) storage in cortical neurons. In the present study, we investigated if other cellular organelles also contain free chelatable zinc and function as organelle storage for zinc. To identify free zinc within the organelles, live cells were co-stained with Zinpyr-1, a zinc fluorescent dye, and organelle-specific fluorescent dyes (MitoFluor Red 589: mitochondria; ER Tracker Red: endoplasmic reticulum; BODIPY TR ceramide: Golgi apparatus; Syto Red 64: nucleus). We examined organelles that represent potential storing sites for intracellular zinc. We showed that zinc fluorescence staining was co-localized with MitoFluor Red 589, ER Tracker Red, and BODIPY TR ceramide respectively, suggesting the presence of free zinc in mitochondria, endoplasmic reticulum, and the Golgi apparatus. On the other hand, cytosol and nucleus had nearly no detectable zinc fluorescence. It is known that nucleus contains high amount of zinc binding proteins that have high zinc binding affinity. The absence of zinc fluorescence suggests that there is little free zinc in these two regions. It also indicates that the zinc fluorescence detected in mitochondria, ER and Golgi apparatus represents free chelatable zinc. Taken together, our results support that these organelles are potential zinc storing organelles during cellular zinc homeostasis. PMID:27186321

Zinc Absorption by Young Adults from Supplemental Zinc Citrate Is Comparable with That from Zinc Gluconate and Higher than from Zinc Oxide123

PubMed Central

Wegmüller, Rita; Tay, Fabian; Zeder, Christophe; Brnić, Marica; Hurrell, Richard F.

2014-01-01

The water-soluble zinc salts gluconate, sulfate, and acetate are commonly used as supplements in tablet or syrup form to prevent zinc deficiency and to treat diarrhea in children in combination with oral rehydration. Zinc citrate is an alternative compound with high zinc content, slightly soluble in water, which has better sensory properties in syrups but no absorption data in humans. We used the double-isotope tracer method with 67Zn and 70Zn to measure zinc absorption from zinc citrate given as supplements containing 10 mg of zinc to 15 healthy adults without food and compared absorption with that from zinc gluconate and zinc oxide (insoluble in water) using a randomized, double-masked, 3-way crossover design. Median (IQR) fractional absorption of zinc from zinc citrate was 61.3% (56.6–71.0) and was not different from that from zinc gluconate with 60.9% (50.6–71.7). Absorption from zinc oxide at 49.9% (40.9–57.7) was significantly lower than from both other supplements (P < 0.01). Three participants had little or no absorption from zinc oxide. We conclude that zinc citrate, given as a supplement without food, is as well absorbed by healthy adults as zinc gluconate and may thus be a useful alternative for preventing zinc deficiency and treating diarrhea. The more insoluble zinc oxide is less well absorbed when given as a supplement without food and may be minimally absorbed by some individuals. This trial was registered at clinicaltrials.gov as NCT01576627. PMID:24259556

Rising intracellular zinc by membrane depolarization and glucose in insulin-secreting clonal HIT-T15 beta cells.

PubMed

Slepchenko, Kira G; Li, Yang V

2012-01-01

Zinc (Zn(2+)) appears to be intimately involved in insulin metabolism since insulin secretion is correlated with zinc secretion in response to glucose stimulation, but little is known about the regulation of zinc homeostasis in pancreatic beta-cells. This study set out to identify the intracellular zinc transient by imaging free cytosolic zinc in HIT-T15 beta-cells with fluorescent zinc indicators. We observed that membrane depolarization by KCl (30-60 mM) was able to induce a rapid increase in cytosolic concentration of zinc. Multiple zinc transients of similar magnitude were elicited during repeated stimulations. The amplitude of zinc responses was not affected by the removal of extracellular calcium or zinc. However, the half-time of the rising slope was significantly slower after removing extracellular zinc with zinc chelator CaEDTA, suggesting that extracellular zinc affect the initial rising phase of zinc response. Glucose (10 mM) induced substantial and progressive increases in intracellular zinc concentration in a similar way as KCl, with variation in the onset and the duration of zinc mobilization. It is known that the depolarization of beta-cell membrane is coupled with the secretion of insulin. Rising intracellular zinc concentration may act as a critical signaling factor in insulin metabolism of pancreatic beta-cells.

Plasma zinc's alter ego is a low-molecular-weight humoral factor.

PubMed

Ou, Ou; Allen-Redpath, Keith; Urgast, Dagmar; Gordon, Margaret-Jane; Campbell, Gill; Feldmann, Jörg; Nixon, Graeme F; Mayer, Claus-Dieter; Kwun, In-Sook; Beattie, John H

2013-09-01

Mild dietary zinc deprivation in humans and rodents has little effect on blood plasma zinc levels, and yet cellular consequences of zinc depletion can be detected in vascular and other tissues. We proposed that a zinc-regulated humoral factor might mediate the effects of zinc deprivation. Using a novel approach, primary rat vascular smooth muscle cells (VSMCs) were treated with plasma from zinc-deficient (<1 mg Zn/kg) or zinc-adequate (35 mg Zn/kg, pair-fed) adult male rats, and zinc levels were manipulated to distinguish direct and indirect effects of plasma zinc. Gene expression changes were analyzed by microarray and qPCR, and incubation of VSMCs with blood plasma from zinc-deficient rats strongly changed the expression of >2500 genes, compared to incubation of cells with zinc-adequate rat plasma. We demonstrated that this effect was caused by a low-molecular-weight (∼2-kDa) zinc-regulated humoral factor but that changes in gene expression were mostly reversed by adding zinc back to zinc-deficient plasma. Strongly regulated genes were overrepresented in pathways associated with immune function and development. We conclude that zinc deficiency induces the production of a low-molecular-weight humoral factor whose influence on VSMC gene expression is blocked by plasma zinc. This factor is therefore under dual control by zinc.

Uptake and partitioning of zinc in Lemnaceae.

PubMed

Lahive, Elma; O'Callaghan, Michael J A; Jansen, Marcel A K; O'Halloran, John

2011-11-01

Macrophytes provide food and shelter for aquatic invertebrates and fish, while also acting as reservoirs for nutrients and trace elements. Zinc accumulation has been reported for various Lemnaceae species. However, comparative accumulation across species and the link between zinc accumulation and toxicity are poorly understood. Morphological distribution and cellular storage, in either bound or soluble form, are important for zinc tolerance. This study shows differences in the uptake and accumulation of zinc by three duckweed species. Landoltia punctata and Lemna minor generally accumulated more zinc than Lemna gibba. L. minor, but not L. gibba or L. punctata, accumulated greater concentrations of zinc in roots compared to fronds when exposed to high levels of zinc. The proportion of zinc stored in the bound form relative to the soluble-form was higher in L. minor. L. punctata accumulated greater concentrations of zinc in fronds compared to roots and increased the proportion of zinc it stored in the soluble form, when exposed to high zinc levels. L. gibba is the only species that significantly accumulated zinc at low concentrations, and was zinc-sensitive. Overall, internal zinc concentrations showed no consistent correlation with toxic effect. We conclude that relationships between zinc toxicity and uptake and accumulation are species specific reflecting, among others, zinc distribution and storage. Differences in zinc distribution and storage are also likely to have implications for zinc bioavailability and trophic mobility.

Modulation of extrasynaptic NMDA receptors by synaptic and tonic zinc.

PubMed

Anderson, Charles T; Radford, Robert J; Zastrow, Melissa L; Zhang, Daniel Y; Apfel, Ulf-Peter; Lippard, Stephen J; Tzounopoulos, Thanos

2015-05-19

Many excitatory synapses contain high levels of mobile zinc within glutamatergic vesicles. Although synaptic zinc and glutamate are coreleased, it is controversial whether zinc diffuses away from the release site or whether it remains bound to presynaptic membranes or proteins after its release. To study zinc transmission and quantify zinc levels, we required a high-affinity rapid zinc chelator as well as an extracellular ratiometric fluorescent zinc sensor. We demonstrate that tricine, considered a preferred chelator for studying the role of synaptic zinc, is unable to efficiently prevent zinc from binding low-nanomolar zinc-binding sites, such as the high-affinity zinc-binding site found in NMDA receptors (NMDARs). Here, we used ZX1, which has a 1 nM zinc dissociation constant and second-order rate constant for binding zinc that is 200-fold higher than those for tricine and CaEDTA. We find that synaptic zinc is phasically released during action potentials. In response to short trains of presynaptic stimulation, synaptic zinc diffuses beyond the synaptic cleft where it inhibits extrasynaptic NMDARs. During higher rates of presynaptic stimulation, released glutamate activates additional extrasynaptic NMDARs that are not reached by synaptically released zinc, but which are inhibited by ambient, tonic levels of nonsynaptic zinc. By performing a ratiometric evaluation of extracellular zinc levels in the dorsal cochlear nucleus, we determined the tonic zinc levels to be low nanomolar. These results demonstrate a physiological role for endogenous synaptic as well as tonic zinc in inhibiting extrasynaptic NMDARs and thereby fine tuning neuronal excitability and signaling.

Modulation of extrasynaptic NMDA receptors by synaptic and tonic zinc

PubMed Central

Anderson, Charles T.; Radford, Robert J.; Zastrow, Melissa L.; Zhang, Daniel Y.; Apfel, Ulf-Peter; Lippard, Stephen J.; Tzounopoulos, Thanos

2015-01-01

Many excitatory synapses contain high levels of mobile zinc within glutamatergic vesicles. Although synaptic zinc and glutamate are coreleased, it is controversial whether zinc diffuses away from the release site or whether it remains bound to presynaptic membranes or proteins after its release. To study zinc transmission and quantify zinc levels, we required a high-affinity rapid zinc chelator as well as an extracellular ratiometric fluorescent zinc sensor. We demonstrate that tricine, considered a preferred chelator for studying the role of synaptic zinc, is unable to efficiently prevent zinc from binding low-nanomolar zinc-binding sites, such as the high-affinity zinc-binding site found in NMDA receptors (NMDARs). Here, we used ZX1, which has a 1 nM zinc dissociation constant and second-order rate constant for binding zinc that is 200-fold higher than those for tricine and CaEDTA. We find that synaptic zinc is phasically released during action potentials. In response to short trains of presynaptic stimulation, synaptic zinc diffuses beyond the synaptic cleft where it inhibits extrasynaptic NMDARs. During higher rates of presynaptic stimulation, released glutamate activates additional extrasynaptic NMDARs that are not reached by synaptically released zinc, but which are inhibited by ambient, tonic levels of nonsynaptic zinc. By performing a ratiometric evaluation of extracellular zinc levels in the dorsal cochlear nucleus, we determined the tonic zinc levels to be low nanomolar. These results demonstrate a physiological role for endogenous synaptic as well as tonic zinc in inhibiting extrasynaptic NMDARs and thereby fine tuning neuronal excitability and signaling. PMID:25947151

Zinc: an essential but elusive nutrient123

PubMed Central

King, Janet C

2011-01-01

Zinc is essential for multiple aspects of metabolism. Physiologic signs of zinc depletion are linked with diverse biochemical functions rather than with a specific function, which makes it difficult to identify biomarkers of zinc nutrition. Nutrients, such as zinc, that are required for general metabolism are called type 2 nutrients. Protein and magnesium are examples of other type 2 nutrients. Type 1 nutrients are required for one or more specific functions: examples include iron, vitamin A, iodine, folate, and copper. When dietary zinc is insufficient, a marked reduction in endogenous zinc loss occurs immediately to conserve the nutrient. If zinc balance is not reestablished, other metabolic adjustments occur to mobilize zinc from small body pools. The location of those pools is not known, but all cells probably have a small zinc reserve that includes zinc bound to metallothionein or zinc stored in the Golgi or in other organelles. Plasma zinc is also part of this small zinc pool that is vulnerable to insufficient intakes. Plasma zinc concentrations decline rapidly with severe deficiencies and more moderately with marginal depletion. Unfortunately, plasma zinc concentrations also decrease with a number of conditions (eg, infection, trauma, stress, steroid use, after a meal) due to a metabolic redistribution of zinc from the plasma to the tissues. This redistribution confounds the interpretation of low plasma zinc concentrations. Biomarkers of metabolic zinc redistribution are needed to determine whether this redistribution is the cause of a low plasma zinc rather than poor nutrition. Measures of metallothionein or cellular zinc transporters may fulfill that role. PMID:21715515

A Direct Redox Regulation of Protein Kinase C Isoenzymes Mediates Oxidant-induced Neuritogenesis in PC12 Cells*

PubMed Central

Gopalakrishna, Rayudu; Gundimeda, Usha; Schiffman, Jason Eric; McNeill, Thomas H.

2008-01-01

In this study, we have used the PC12 cell model to elucidate the mechanisms by which sublethal doses of oxidants induce neuritogenesis. The xanthine/xanthine oxidase (X/XO) system was used for the steady state generation of superoxide, and CoCl2 was used as a representative transition metal redox catalyst. Upon treatment of purified protein kinase C (PKC) with these oxidants, there was an increase in its cofactor-independent activation. Redox-active cobalt competed with the redoxinert zinc present in the zinc-thiolates of the PKC regulatory domain and induced the oxidation of these cysteine-rich regions. Both CoCl2 and X/XO induced neurite outgrowth in PC12 cells, as determined by an overexpression of neuronal marker genes. Furthermore, these oxidants induced a translocation of PKC from cytosol to membrane and subsequent conversion of PKC to a cofactor-independent form. Isoenzyme-specific PKC inhibitors demonstrated that PKCε plays a crucial role in neuritogenesis. Moreover, oxidant-induced neurite outgrowth was increased with a conditional overexpression of PKCε and decreased with its knock-out by small interfering RNA. Parallel with PKC activation, an increase in phosphorylation of the growth-associated neuronal protein GAP-43 at Ser41 was observed. Additionally, there was a sustained activation of extracellular signal-regulated kinases 1 and 2, which was correlated with activating phosphorylation (Ser133) of cAMP-responsive element-binding protein. All of these signaling events that are causally linked to neuritogenesis were blocked by antioxidant N-acetylcysteine (both l and d-forms) and by a variety of PKC-specific inhibitors. Taken together, these results strongly suggest that sublethal doses of oxidants induce neuritogenesis via a direct redox activation of PKCε. PMID:18375950

Samuel P. Massie Chair of Excellence In Environmental Disciplines: Hampton University 1994-2010 Year Report

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

Adeyiga, Adeyinka A.

2014-12-17

The establishment of the DOE-EM Dr. Samuel P. Massie Chair of Excellence provides an excellent opportunity for Hampton University to be involved in key environmental issues in the 21 st Century. The main areas of focus are on: 1. Coal gasification with respect to pollution prevention and reduction. 2. Solid waste treatment through bioremediation technology and 3. Industrial wastewater treatment Synthesizing ion catalysts suitable for use in slurry bubble column reaction was carried out. Construction of an autoclave continuous stirred tank reactor has been completed. At the initial stage of the development of this program, work was conducted in themore » area of formic acid recovery from waste streams, which yielded useful results. We also succeeded in the removal of priority metal ions such as cadmium, chromium, copper, lead, mercury, nickel, silver, thallium, zinc, etc., from industrial and municipal wastewater by using natural wastes. The process uses tree leaves to adsorb the metal ions in the wastewater. The ultimate goal is to develop inexpensive, highly available, effective metal ion adsorbents from natural wastes as an alternative to existing commercial adsorbents, and also to explain the possible adsorption mechanism that is taking place. This technology uses natural wastes to eliminate other wastes. Obviously, there are several advantages: (1) the negative impact on environment is eliminated, (2) the complicated regeneration step is not needed, and (3) the procedure saves money and energy. Twelve different types of leaves have been tested with lead, zinc, and nickel. The study mechanism showed that the leaf tannin is an active ingredient in the adsorption of metal ions. The ion-exchange mechanism controlled the adsorption process.« less

Prediction of Serum Zinc Levels in Mexican Children at 2 Years of Age Using a Food Frequency Questionnaire and Different Zinc Bioavailability Criteria

PubMed Central

Cantoral, Alejandra; Téllez-Rojo, Martha; Shamah-Levy, Teresa; Schnaas, Lourdes; Hernández-Ávila, Mauricio; Peterson, Karen; Ettinger, Adrienne

2017-01-01

Background The 2006 Mexican National Health and Nutrition Survey documented a prevalence of zinc deficiency of almost 30% in children aged one to two years old. Objective We sought to validate a Food Frequency Questionnaire (FFQ) for quantifying dietary bioavailable zinc intake in two-year old Mexican children accounting for phytic acid intake and using serum zinc as a reference. Methods This cross-sectional study was nested within a longitudinal birth cohort of 333 young children in Mexico City. Non-fasting serum zinc concentration was measured and dietary zinc intake was calculated on the basis of a semi-quantitative FFQ administered to their mothers. The relationship between dietary zinc intake and serum zinc was assessed using linear regression, adjusting for phytic acid intake, and analyzed according to two distinct international criteria to estimate bioavailable zinc. Models were stratified by zinc deficiency status. Results Dietary zinc, adjusted for phytic acid intake, explained the greatest proportion of the variance of serum zinc. For each mg of dietary zinc intake, serum zinc increased on average by 0.95 μg/dL (0.15 μmol/L) (p=0.06). When stratified by zinc status, this increase was 0.74 μg/dL (p=0.12) for each milligram of zinc consumed among children with adequate serum zinc (N=276) whereas among those children with zinc deficiency (N=57), serum zinc increased by only 0.11 μg/dL (p=0.82). Conclusion A semi-quantitative FFQ can be used for predicting serum zinc in relation to dietary intake in young children, particularly among those who are zinc-replete, and when phytic acid/phytate intake is considered. Future studies should be conducted accounting for both zinc status and dietary zinc inhibitors to further elucidate and validate these findings. PMID:26121697

Design and analysis of novel photocatalytic materials

NASA Astrophysics Data System (ADS)

Boppana, Venkata Bharat Ram

The development of sustainable sources of energy to decrease our dependence on non-renewable fossil fuels and the reduction of emissions causing global warming are important technological challenges of the 21st century. Production of solar fuels by photocatalysis is one potential route to reduce the impact of those problems. The most widely applied photocatalyst is TiO2 because it is stable, non-toxic and inexpensive. Still, it cannot utilize the solar spectrum efficiently as its band gap is 3.2 eV thus able to absorb only 3% of sun light. This thesis therefore explores multiple avenues towards improving the light absorption capability of semiconductor materials without loss in activity. To achieve this objective, the valence band hybridization method of band gap reduction was utilized. This technique is based on introducing new orbitals at the top of valence band of the semiconductor that can then hybridize with existing orbitals. The hybridization then raises the maximum of the valence band thereby reducing the band gap. This technique has the added advantage of increasing the mobility of oxidizing holes in the now dispersed valence band. In practice, this can be achieved by introducing N 2p or Sn 5s orbitals in the valence band of an oxide. We initially designed novel zinc gallium oxy-nitrides, with the spinel structure and band gaps in the visible region of the solar spectrum, by nitridation of a zinc gallate precursor produced by sol-gel synthesis. These spinel oxy-nitrides have band gaps of 2.5 to 2.7 eV, surface areas of 16 to 36 m 2/g, and nitrogen content less than 1.5%. They are active towards degradation of organic molecules in visible light. Density functional theory calculations show that this band gap reduction in part is associated with hybridization between the dopant N 2p states with Zn 3d orbitals at the top of the valence band. While spinel oxy-nitrides are produced under nitridation at 550°C, at higher temperatures they are consumed to form wurzitic oxy-nitrides. The wurzite materials also have band gaps less than 3 eV but their surface areas are 2 to 5 m2/g. The thesis explores in detail the changes associated with the gallium coordination as the spinel zinc gallate precursor transforms into the spinel oxy-nitride at 550°C, and further changes into the wurzite oxy-nitride at 850°C are studied through X-ray diffraction, ultraviolet-visible diffuse reflectance spectroscopy, neutron powder diffraction, X-ray absorption spectroscopy and other techniques. We believe that the protocol developed in this thesis opens an avenue for the synthesis of semiconductors having the spinel crystal structure and band gaps engineered to the visible region with potential applications for opto-electronic devices and photocatalytic processes. Though these spinel oxynitrides are interesting, they suffer from vacancies and low surface areas from the high temperature nitridation step. This could be overcome by synthesizing photocatalysts hydrothermally. We proceeded to explore the interactions of Sn2+ 5s orbitals with O 2p orbitals towards hybridizing the valence band. This led to the development of novel visible-light-active Sn2+ - TiO2 and SnOx -- ZnGa2O4 materials. The former catalysts are prepared from the reaction of titanium butoxide and several tin precursors at 80°C in aqueous solutions. Samples synthesized with SnCl2 have lower band gaps (red-shifted to the visible region) with respect to anatase TiO2. The catalysts are isostructural with anatase TiO2 even at the highest loadings of Sn2+. When the precursor is changed to SnCl4, rutile is the predominant phase obtained but no reduction in the band gap is observed. The experiments also indicate the presence of chlorine in the samples, also influencing the optical and catalytic properties as confirmed by comparison to materials prepared using bromide precursors. These catalysts are photocatalytically active for the degradation of organic molecules with rates higher than the standard (P25 TiO2) and also evidenced from the generation of hydroxyl radicals using visible light. This protocol could be extended to incorporate Sn2+ 5s orbitals into other oxide semiconductors to prepare photocatalysts with interesting electronic properties.

ADVANCED SULFUR CONTROL CONCEPTS

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

Apostolos A. Nikolopoulos; Santosh K. Gangwal; William J. McMichael

Conventional sulfur removal in integrated gasification combined cycle (IGCC) power plants involves numerous steps: COS (carbonyl sulfide) hydrolysis, amine scrubbing/regeneration, Claus process, and tail-gas treatment. Advanced sulfur removal in IGCC systems involves typically the use of zinc oxide-based sorbents. The sulfides sorbent is regenerated using dilute air to produce a dilute SO{sub 2} (sulfur dioxide) tail gas. Under previous contracts the highly effective first generation Direct Sulfur Recovery Process (DSRP) for catalytic reduction of this SO{sub 2} tail gas to elemental sulfur was developed. This process is currently undergoing field-testing. In this project, advanced concepts were evaluated to reduce themore » number of unit operations in sulfur removal and recovery. Substantial effort was directed towards developing sorbents that could be directly regenerated to elemental sulfur in an Advanced Hot Gas Process (AHGP). Development of this process has been described in detail in Appendices A-F. RTI began the development of the Single-step Sulfur Recovery Process (SSRP) to eliminate the use of sorbents and multiple reactors in sulfur removal and recovery. This process showed promising preliminary results and thus further process development of AHGP was abandoned in favor of SSRP. The SSRP is a direct Claus process that consists of injecting SO{sub 2} directly into the quenched coal gas from a coal gasifier, and reacting the H{sub 2}S-SO{sub 2} mixture over a selective catalyst to both remove and recover sulfur in a single step. The process is conducted at gasifier pressure and 125 to 160 C. The proposed commercial embodiment of the SSRP involves a liquid phase of molten sulfur with dispersed catalyst in a slurry bubble-column reactor (SBCR).« less

The preparation and use of metal salen complexes derived from cyclobutane diamine

NASA Astrophysics Data System (ADS)

Patil, Smita

The helix is an important chiral motif in nature, there is increasing development in field of helical transition metal complexes and related supramolecular structures. Hence, the goals of this work are to apply the principles of helicity in order to produce metal complexes with predictable molecular shapes and to study their properties as asymmetric catalysts. Computational studies suggest that the (1R,2 R)-cyclobutyldiamine unit can produce highly twisted salen complexes with a large energy barrier between the M and P helical forms. To test this prediction, the tartrate salt of (1R,2R)-cyclobutyldiamine was synthesized and condensed with a series of saliclaldehydes to produce novel salen ligands. The salicylaldehydes chosen have extended phenanthryl or benz[a]anthryl sidearms to encourage formation of helical coordination complexes. These ligands were metallated with zinc, iron and manganese salts to produce salen metal complexes which were characterized by NMR analysis, high-resolution mass spectrometry, and IR spectroscopy. A second ligand type, neutral bis(pyridine-imine) has also been synthesized from (1R,2R)-cyclobutyldiamine and quinolylaldehydes. The synthesis of bis(pyridine-imine) ligands was conducted using greener method, solvent assisted grinding. These ligands, in-situ with nickel metal salts, showed good catalytic activity for asymmetric Diels-Alder reactions. The third ligand type studied was chiral acid-functionalized Schiff-base ligands. These were synthesized by the condensation of 3-formyl-5-methyl salicylic acid and (1R,2R)-cyclobutyldiamine. With this type of ligand, there is possibility of producing both mono and dinuclear metal complexes. In our studies, we were only able to synthesize mononuclear complexs. These were tested as catalysts for asymmetric direct Mannich-type reaction, but were found to be ineffective.

Interdiffusion Reaction-Assisted Hybridization of Two-Dimensional Metal-Organic Frameworks and Ti3C2Tx Nanosheets for Electrocatalytic Oxygen Evolution.

PubMed

Zhao, Li; Dong, Biliang; Li, Shaozhou; Zhou, Lijun; Lai, Linfei; Wang, Zhiwei; Zhao, Shulin; Han, Min; Gao, Kai; Lu, Min; Xie, Xiaoji; Chen, Bo; Liu, Zhengdong; Wang, Xiangjing; Zhang, Hao; Li, Hai; Liu, Juqing; Zhang, Hua; Huang, Xiao; Huang, Wei

2017-06-27

Two-dimensional (2D) metal-organic framework (MOF) nanosheets have been recently regarded as the model electrocatalysts due to their porous structure, fast mass and ion transfer through the thickness, and large portion of exposed active metal centers. Combining them with electrically conductive 2D nanosheets is anticipated to achieve further improved performance in electrocatalysis. In this work, we in situ hybridized 2D cobalt 1,4-benzenedicarboxylate (CoBDC) with Ti 3 C 2 T x (the MXene phase) nanosheets via an interdiffusion reaction-assisted process. The resulting hybrid material was applied in the oxygen evolution reaction and achieved a current density of 10 mA cm -2 at a potential of 1.64 V vs reversible hydrogen electrode and a Tafel slope of 48.2 mV dec -1 in 0.1 M KOH. These results outperform those obtained by the standard IrO 2 -based catalyst and are comparable with or even better than those achieved by the previously reported state-of-the-art transition-metal-based catalysts. While the CoBDC layer provided the highly porous structure and large active surface area, the electrically conductive and hydrophilic Ti 3 C 2 T x nanosheets enabled the rapid charge and ion transfer across the well-defined Ti 3 C 2 T x -CoBDC interface and facilitated the access of aqueous electrolyte to the catalytically active CoBDC surfaces. The hybrid nanosheets were further fabricated into an air cathode for a rechargeable zinc-air battery, which was successfully used to power a light-emitting diode. We believe that the in situ hybridization of MXenes and 2D MOFs with interface control will provide more opportunities for their use in energy-based applications.

Catalytic co-aromatization of ethanol and methane

DOE PAGES

Wang, Aiguo; He, Peng; Yung, Matthew; ...

2016-06-06

This study demonstrates the technical feasibility of simultaneously converting ethanol and methane into liquid hydrocarbons at mild reaction conditions (400 °C and 1 atm) over silver and/or zinc modified zeolite catalysts. After GC-MS analysis, it is worth noting that aromatics are the major compounds contained in the liquid product collected from the run when 1%Ag/ZSM-5, particularly after H 2 pretreatment, is charged. Compared to the performance exhibited from the run with pure HZSM-5 support engaged, Ag addition into the HZSM-5 framework favors aromatics formation, which might be closely associated with better Ag dispersion and more abundance of strong surface acidicmore » sites where aromatization might take place while Zn loading exerts a detrimental effect on the production of aromatics but promotes the ether generation possibly through dehydration reaction. Referred to that from its N 2 counterpart, the increased aromatics formation of the collected liquid product when methane is present indicates that methane existence might facilitate ethanol aromatization. Moreover, combined with the increased carbon number in the formed aromatics from CH 4 run when H 2 run is referred and zero liquid formation from CH 4-alone test as well as more prominent endothermic feature of methane run and more importantly the notably increased 13C signals in 13C NMR spectra of the liquid product collected during ethanol conversion under 13CH 4 environment, all the observations suggest that methane might be activated nonoxidatively and converted into higher hydrocarbons, preferentially into aromatics if suitable catalyst is charged under the assistance of co-existing oxygenated hydrocarbon. Lastly, the reported synergetic effect could potentially lead to the more economic utilization of abundant natural gas and cellulosic ethanol.« less

ttm-1 Encodes CDF Transporters That Excrete Zinc from Intestinal Cells of C. elegans and Act in a Parallel Negative Feedback Circuit That Promotes Homeostasis

PubMed Central

Roh, Hyun Cheol; Collier, Sara; Deshmukh, Krupa; Guthrie, James; Robertson, J. David; Kornfeld, Kerry

2013-01-01

Zinc is an essential metal involved in a wide range of biological processes, and aberrant zinc metabolism is implicated in human diseases. The gastrointestinal tract of animals is a critical site of zinc metabolism that is responsible for dietary zinc uptake and distribution to the body. However, the role of the gastrointestinal tract in zinc excretion remains unclear. Zinc transporters are key regulators of zinc metabolism that mediate the movement of zinc ions across membranes. Here, we identified a comprehensive list of 14 predicted Cation Diffusion Facilitator (CDF) family zinc transporters in Caenorhabditis elegans and demonstrated that zinc is excreted from intestinal cells by one of these CDF proteins, TTM-1B. The ttm-1 locus encodes two transcripts, ttm-1a and ttm-1b, that use different transcription start sites. ttm-1b expression was induced by high levels of zinc specifically in intestinal cells, whereas ttm-1a was not induced by zinc. TTM-1B was localized to the apical plasma membrane of intestinal cells, and analyses of loss-of-function mutant animals indicated that TTM-1B promotes zinc excretion into the intestinal lumen. Zinc excretion mediated by TTM-1B contributes to zinc detoxification. These observations indicate that ttm-1 is a component of a negative feedback circuit, since high levels of cytoplasmic zinc increase ttm-1b transcript levels and TTM-1B protein functions to reduce the level of cytoplasmic zinc. We showed that TTM-1 isoforms function in tandem with CDF-2, which is also induced by high levels of cytoplasmic zinc and reduces cytoplasmic zinc levels by sequestering zinc in lysosome-related organelles. These findings define a parallel negative feedback circuit that promotes zinc homeostasis and advance the understanding of the physiological roles of the gastrointestinal tract in zinc metabolism in animals. PMID:23717214

Photo-oxidation catalysts

DOEpatents

Pitts, J Roland [Lakewood, CO; Liu, Ping [Irvine, CA; Smith, R Davis [Golden, CO

2009-07-14

Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

Galvanizing action: conclusions and next steps for mainstreaming zinc interventions in public health programs.

PubMed

Brown, Kenneth H; Baker, Shawn K

2009-03-01

This paper summarizes the results of the foregoing reviews of the impact of different intervention strategies designed to enhance zinc nutrition, including supplementation, fortification, and dietary diversification or modification. Current evidence indicates a beneficial impact of such interventions on zinc status and zinc-related functional outcomes. Preventive zinc supplementation reduces the incidence of diarrhea and acute lower respiratory tract infection among young children, decreases mortality of children over 12 months of age, and increases growth velocity. Therapeutic zinc supplementation during episodes of diarrhea reduces the duration and severity of illness. Zinc fortification increases zinc intake and total absorbed zinc, and recent studies are beginning to confirm a positive impact of zinc fortification on indicators of population zinc status. To assist with the development of zinc intervention programs, more information is needed on the prevalence of zinc deficiency in different countries, and rigorous evaluations of the effectiveness of large-scale zinc intervention programs should be planned. Recommended steps for scaling up zinc intervention programs, with or without other micronutrients, are described. In summary, there is now clear evidence of the benefit of selected interventions to reduce the risk of zinc deficiency, and a global commitment is urgently needed to conduct systematic assessments of population zinc status and to develop interventions to control zinc deficiency in the context of existing public health and nutrition programs.

Rising Intracellular Zinc by Membrane Depolarization and Glucose in Insulin-Secreting Clonal HIT-T15 Beta Cells

PubMed Central

Slepchenko, Kira G.; Li, Yang V.

2012-01-01

Zinc (Zn2+) appears to be intimately involved in insulin metabolism since insulin secretion is correlated with zinc secretion in response to glucose stimulation, but little is known about the regulation of zinc homeostasis in pancreatic beta-cells. This study set out to identify the intracellular zinc transient by imaging free cytosolic zinc in HIT-T15 beta-cells with fluorescent zinc indicators. We observed that membrane depolarization by KCl (30–60 mM) was able to induce a rapid increase in cytosolic concentration of zinc. Multiple zinc transients of similar magnitude were elicited during repeated stimulations. The amplitude of zinc responses was not affected by the removal of extracellular calcium or zinc. However, the half-time of the rising slope was significantly slower after removing extracellular zinc with zinc chelator CaEDTA, suggesting that extracellular zinc affect the initial rising phase of zinc response. Glucose (10 mM) induced substantial and progressive increases in intracellular zinc concentration in a similar way as KCl, with variation in the onset and the duration of zinc mobilization. It is known that the depolarization of beta-cell membrane is coupled with the secretion of insulin. Rising intracellular zinc concentration may act as a critical signaling factor in insulin metabolism of pancreatic beta-cells. PMID:22536213

Development and evaluation of unmanned aerial vehicle (UAV) magnetometry systems

NASA Astrophysics Data System (ADS)

Parvar, Kiyavash

In this thesis, the procedure of conducting magnetic surveys from a UAV platform is investigated. In the process of evaluating UAVs for such surveys, magnetic sensors capable of operating on a UAV platform were tested using a terrestrial survey, as well as on a UAV-platform. Results were then compared to a model of the area generated using a proton precession magnetometer. Magnetic signature of the UAVs are discussed and impact values are calculated. For a better understanding of the magnetic fields around UAVs some micro-surveys were conducted with the help of a fluxgate magnetometer around two UAVs. Results of such surveys were used to determine a location to mount the magnetometer during the survey. A test survey over a known anomaly (a visible chromite outcrop in Oman) is conducted in order to determine the feasibility of using UAV-based magnetometry for chromite exploration. Observations were taken at two different elevations in order to generate a 3-D model of the magnetic field. Later, after applying upward continuation filters and comparing the calculated results to the real values, the reliability and uncertainty levels of such filters were investigated. Results show that magnetometery on UAV platforms is feasible. Unwanted signals can be noticeable and produce fake anomalies by the end of each line because of the swinging effect of the suspended magnetometer below the UAV. This should be reduced by hardware and software modifications i.e. applying non-linear filters and mounting the sensor on a rigid rod. Also, it was derived that the error level associated with upward continuation filters exceeds 45% and thus, using such filters instead of actual observations is not suggested in gradiometry. Moreover, 3-D magnetic gradient surveys can be beneficial for future inversion problems.