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Sample records for copper oxide catalyst

  1. Cobalt promoted copper manganese oxide catalysts for ambient temperature carbon monoxide oxidation.

    Science.gov (United States)

    Jones, Christopher; Taylor, Stuart H; Burrows, Andrew; Crudace, Mandy J; Kiely, Christopher J; Hutchings, Graham J

    2008-04-14

    Low levels of cobalt doping (1 wt%) of copper manganese oxide enhances its activity for carbon monoxide oxidation under ambient conditions and the doped catalyst can display higher activity than current commercial catalysts.

  2. The copper recovery from cupric oxide catalysts by plasma reduction process

    Energy Technology Data Exchange (ETDEWEB)

    Imris, I.; Klenovcanova, A. [Technical Univ. of Kosice, Kosice (Slovakia). Dept. of Power Engineering

    2007-07-01

    A plasma reduction process was used to recover copper from cupric oxide catalysts. Two types of plasma reduction smelting tests were conducted to verify the thermodynamic calculations. The plasma reactor consisted of a cylindrical steel shell lined with a castable alumina and a graphite crucible. Cupric oxide catalyst ESM 461 was mixed with stoichiometric amounts of carbon reductant and a 10 per cent addition of calcium oxide flux. Results of the experimental tests and the thermodynamic analysis showed that the copper can be extracted from cupric oxide using the plasma reduction process. Copper recovery was limited by physico-chemical copper losses. Copper oxide solubility was relatively high, so that copper recovery was low in their first series of plasma tests. The addition of calcium oxide flux improved copper recovery rates when dicalcium silicate was formed in the slag. The offgas samples indicated that concentrations of carbon monoxide (CO) in the gas phase was very high. It was concluded that the process is both commercially feasible and does not produce liquid or solid wastes. 7 refs., 2 tabs., 4 figs.

  3. Effect of copper loading on copper-ceria catalysts performance in CO selective oxidation for fuel cell applications

    Energy Technology Data Exchange (ETDEWEB)

    Ayastuy, J.L.; Gurbani, A.; Gonzalez-Marcos, M.P.; Gutierrez-Ortiz, M.A. [Departamento de Ingenieria Quimica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/EHU, E-48080 Bilbao (Spain); Unidad Asociada ' ' Tecnologias Quimicas para la Sostenibilidad Ambiental' ' , CSIC-UPV/EHU (Spain)

    2010-02-15

    Copper-ceria catalysts with three different Cu loadings (1, 7 and 15 wt%) were prepared by incipient wet impregnation, dried at 120 C and calcined in air at 500 C. The as-prepared catalysts were characterized by XRD, BET, Diffuse Reflectance Spectroscopy (DRS-UV-visible), Raman spectroscopy, CO and H{sub 2}-TPR, CO-TPR, CO-TPD and Oxygen Storage Capacity (OSC) measurements (with CO and O{sub 2} concentration step-changes). The results indicated a good dispersion of copper for catalysts with 1 and 7 wt% Cu; however, bulk CuO was present for catalyst with 15 wt% Cu loading. Catalyst with 7 wt% Cu was observed to have very high capacity to release lattice oxygen to oxidize CO at low temperature. Activity results for CO oxidation in the absence and in the presence of 60% H{sub 2}, demonstrated a very similar performance for catalysts with 7 and 15 wt% Cu (both with T{sub 100} = 112 C), and much better than that of catalyst loaded with 1 wt% Cu. Catalyst with 7 wt% of copper shows very high activity (100% in a wide temperature window) and selectivity (higher than 85%), which makes an attractive for its use in purification of hydrogen for fuel cell applications. The presence of a mixture of CO{sub 2} and H{sub 2}O inhibited catalyst activity, with CuO/CeO{sub 2} catalyst with 7 wt% Cu exhibiting the best performance in the overall reaction temperature range. This could be attributed to the presence of highly disperse copper, only part of it in deep interaction with ceria. The effect of O{sub 2}/CO ratio ({lambda}) and the potential reversibility of the inhibitory effect of CO{sub 2} and H{sub 2}O were also investigated. (author)

  4. A biomimetic copper water oxidation catalyst with low overpotential.

    Science.gov (United States)

    Zhang, Teng; Wang, Cheng; Liu, Shubin; Wang, Jin-Liang; Lin, Wenbin

    2014-01-08

    Simply mixing a Cu(II) salt and 6,6'-dihydroxy-2,2'-bipyridine (H2L) in a basic aqueous solution afforded a highly active water oxidation catalyst (WOC). Cyclic voltammetry of the solution at pH = 12-14 shows irreversible catalytic current with an onset potential of ~0.8 V versus NHE. Catalytic oxygen evolution takes place in controlled potential electrolysis at a relatively low overpotential of 640 mV. Experimental and computational studies suggest that the L ligand participates in electron transfer processes to facilitate the oxidation of the Cu center to lead to an active WOC with low overpotential, akin to the use of the tyrosine radical by Photosystem II to oxidize the CaMn4 center for water oxidation.

  5. Selective catalytic oxidation of ammonia over copper-cerium composite catalyst.

    Science.gov (United States)

    Lou, Jie-Chung; Hung, Chang-Mao; Yang, Sheng-Fu

    2004-01-01

    This work considers the oxidation of ammonia (NH3) by selective catalytic oxidation (SCO) over a copper (Cu)-cerium (Ce) composite catalyst at temperatures between 150 and 400 degrees C. A Cu-Ce composite catalyst was prepared by coprecipitation of copper nitrate and cerium nitrate at various molar concentrations. This study also considers how the concentration of influent NH3 (500-1000 ppm), the space velocity (72,000-110,000 hr(-1)), the relative humidity (12-18%) and the concentration of oxygen (4-20%) affect the operational stability and the capacity for removing NH3. The effects of the O2 and NH3 content of the carrier gas on the catalyst's reaction rate also are considered. The experimental results show that the extent of conversion of NH3 by SCO in the presence of the Cu-Ce composite catalyst was a function of the molar ratio. The NH3 was removed by oxidation in the absence of Cu-Ce composite catalyst, and approximately 99.2% NH3 reduction was achieved during catalytic oxidation over the Cu-Ce (6:4, molar/molar) catalyst at 400 degrees C with an O2 content of 4%. Moreover, the effect of the initial concentration and reaction temperature on the removal of NH3 in the gaseous phase was also monitored at a gas hourly space velocity of less than 92,000 hr(-1).

  6. Valence State of Active Copper in CuOx/CeO2 Catalysts for CO Oxidation

    Institute of Scientific and Technical Information of China (English)

    Zeng Shanghong; Bai Xue; Wang Xiaoyan; Yu Wenguo; Liu Yuan

    2006-01-01

    CuOx/CeO2 catalysts were prepared by adsorption-impregnation method.CO conversion was tested over the catalysts pretreated under different conditions for preferential CO oxidation in H2, and the catalysts were characterized with X-ray photoelectron spectroscopy and temperature programmed reduction.Experimental results show that there are two kinds of copper, which are Cu+ and Cu2+ in calcined CuOx/CeO2.Among them, the Cu+ is the key active component for CO oxidation.The main reason is as follows: CO is activated by copper for CO oxidation over CuOx/CeO2, while CO can not be activated by Cu2+.Only when Cu2+ is reduced to Cu+ or Cu0, the copper may be active for CO oxidation, moreover, the experimental results show that the reduction of Cu2+ does not lead to an increase of catalytic activity.So the active species is Cu+ in CuOx/CeO2 catalysts.

  7. Comparison of Preparation Methods of Copper Based PGMFree Diesel-Soot Oxidation Catalysts

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    R. Prasad

    2011-05-01

    Full Text Available CuO-CeO2 systems have been proposed as a promising catalyst for low temperature diesel-soot oxidation. CuO-CeO2 catalysts prepared by various methods were examined for air oxidation of the soot in a semi batch tubular flow reactor. The air oxidation of soot was carried out under tight contact with soot/catalyst ratio of 1/10. Air flow rate was 150 ml/min, soot-catalyst mixture was 110 mg, heating rate was 5 0C/min. Prepared catalysts were calcined at 500 0C and their stability was examined by further heating to 800 0C for 4 hours. It was found that the selectivity of all the catalysts was nearly 100% to CO2 production. It was observed that the activity and stability of the catalysts greatly influenced by the preparation methods. The strong interaction between CuO and CeO2 is closely related to the preparation route that plays a crucial role in the soot oxidation over the CuO-CeO2 catalysts. The ranking order of the preparation methods of the catalysts in the soot oxidation performance is as follows: sol-gel > urea nitrate combustion > Urea gelation method > thermal decomposition > co-precipitation. Copyright © 2011 BCREC UNDIP. All rights reserved.(Received: 27th June 2010, Revised: 7th August 2010; Accepted: 13rd October 2010[How to Cite: R. Prasad, V.R. Bella. (2011. Comparison of Preparation Methods of Copper Based PGMFree Diesel-Soot Oxidation Catalysts. Bulletin of Chemical Reaction Engineering and Catalysis, 6(1: 15-21. doi:10.9767/bcrec.6.1.822.15-21][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.1.822.15-21 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/822 | View in 

  8. Catalytic wet oxidation of thiocyanate with homogeneous copper(II) sulphate catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Collado, Sergio; Laca, Adriana [Department of Chemical Engineering and Environmental Technology, University of Oviedo, c/ Julian Claveria s/n, E-33071, Oviedo (Spain); Diaz, Mario, E-mail: mariodiaz@uniovi.es [Department of Chemical Engineering and Environmental Technology, University of Oviedo, c/ Julian Claveria s/n, E-33071, Oviedo (Spain)

    2010-05-15

    The wet oxidation of thiocyanate has been investigated in a semi-batch reactor at temperatures between 423 and 473 K and pressures between 6.1 x 10{sup 3} and 1.0 x 10{sup 4} kPa in the presence of copper(II) sulphate as catalyst. The effects of copper concentration, initial thiocyanate concentration, pressure and temperature on the reaction rate were analyzed and the main products of reaction were identified. A kinetic model for the Cu-catalyzed reaction is here proposed, including temperature, oxygen concentration, and the reduction of Cu{sup 2+} to Cu{sup +} that gives an accurate prediction of the oxidation process under the assayed conditions. A mechanistic model based on the formation of a transition complex between a copper cation and two thiocyanate anions has been proposed for the catalytic wet oxidation.

  9. Catalytic wet oxidation of thiocyanate with homogeneous copper(II) sulphate catalyst.

    Science.gov (United States)

    Collado, Sergio; Laca, Adriana; Díaz, Mario

    2010-05-15

    The wet oxidation of thiocyanate has been investigated in a semi-batch reactor at temperatures between 423 and 473 K and pressures between 6.1 x 10(3) and 1.0 x 10(4)kPa in the presence of copper(II) sulphate as catalyst. The effects of copper concentration, initial thiocyanate concentration, pressure and temperature on the reaction rate were analyzed and the main products of reaction were identified. A kinetic model for the Cu-catalyzed reaction is here proposed, including temperature, oxygen concentration, and the reduction of Cu(2+) to Cu(+) that gives an accurate prediction of the oxidation process under the assayed conditions. A mechanistic model based on the formation of a transition complex between a copper cation and two thiocyanate anions has been proposed for the catalytic wet oxidation.

  10. Oxidation catalyst

    Science.gov (United States)

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

    The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

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

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    Tetsuo Umegaki

    2015-11-01

    Full Text Available 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.

  12. Efficient Copper-bisisoquinoline-based Catalysts for Selective Aerobic Oxidation of Alcohols to Aldehydes and Ketones

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    Zaher M. A. Judeh

    2007-06-01

    Full Text Available The selective oxidation of alcohols with molecular oxygen was efficientlycompleted in high conversion and selectivity using copper-bisisoquinoline-based catalystsunder mild reaction condition. The effects of various parameters such as reactiontemperature, reaction time, oxidant, ligands, etc, were studied. Solvent effect has been aswell studied in ionic liquids [bmim]PF6, [omim]BF4 and [hmim]BF4, comparing totraditional volatile organic solvent. The use of ionic liquids was found to enhance thecatalytic properties of the catalysts used.

  13. Bottom-Up Design of a Copper-Ruthenium Nanoparticulate Catalyst for Low-Temperature Ammonia Oxidation

    DEFF Research Database (Denmark)

    Chakraborty, Debasish; Damsgaard, Christian Danvad; Silva, Hugo José Lopes

    2017-01-01

    A novel nanoparticulate catalyst of copper (Cu) and ruthenium (Ru) was designed for low-temperature ammonia oxidation at near-stoichiometric mixtures using a bottom-up approach. A synergistic effect of the two metals was found. An optimum CuRu catalyst presents a reaction rate threefold higher than...

  14. Effect of loading content of copper oxides on performance of Mn-Cu mixed oxide catalysts for catalytic combustion of benzene

    Institute of Scientific and Technical Information of China (English)

    CAO Hongyan; LI Xiaoshuang; CHEN Yaoqiang; GONG Maochu; WANG Jianli

    2012-01-01

    A series of Mn-Cu mixed oxide catalysts were prepared by precipitation method.The catalysts were characterized by N2 adsorption-desorption,H2-TPR and XPS.When the loading ratio of manganese oxides to copper oxides was 8:2 or 7:3,the catalysts possessed better catalytic activity,and benzene was converted completely at 558 K.Results of H2-TPR showed that the loading of a small amount of copper oxides decreased the reduction temperature of catalysts.Results of XPS showed that the loading of a small amount of copper oxides increased the proportion of manganese and defective oxygen on the surface of catalysts,and stabilized manganese at higher oxidation state.And the catalyst with the loading ratio 7:3 was a little worse than 8:2,since the interaction between manganese oxides and copper oxides is too strong,copper oxides migrate to the surface of catalysts and manganese oxides in excess are immerged.

  15. Catalytic wet peroxide oxidation of aniline in wastewater using copper modified SBA-15 as catalyst.

    Science.gov (United States)

    Kong, Liming; Zhou, Xiang; Yao, Yuan; Jian, Panming; Diao, Guowang

    2016-01-01

    SBA-15 mesoporous molecular sieves modified with copper (Cu-SBA-15) were prepared by pH-adjusting hydrothermal method and characterized by X-ray diffraction, BET, transmission electron microscopy, UV-Vis and (29)Si MAS NMR. The pH of the synthesis gel has a significant effect on the amount and the dispersion of copper on SBA-15. The Cu-SBA-15(4.5) (where 4.5 denotes the pH value of the synthesis gel) modified with highly dispersed copper was used as catalyst for the oxidation of aniline by H2O2. The Cu-SBA-15(4.5) shows a higher catalytic activity compared to CuO on the surface of SBA-15. The influences of reaction conditions, such as initial pH of the aqueous solutions, temperature, as well as the dosages of H2O2 and catalyst were investigated. Under weakly alkaline aqueous solution conditions, the aniline conversion, the H2O2 decomposition and the total organic carbon (TOC) removal could be increased significantly compared to the acid conditions. The percentage of leaching Cu(2+) could be decreased from 45.0% to 3.66% when the initial pH of solution was increased from 5 to 10. The TOC removal could be enhanced with the increases of temperature, H2O2 and catalyst dosage, but the aniline conversion and H2O2 decomposition change slightly with further increasing dosage of catalyst and H2O2. At 343 K and pH 8.0, 100% aniline conversion and 66.9% TOC removal can be achieved under the conditions of 1.0 g/L catalyst and 0.05 mol/L H2O2 after 180 min. Although copper might be slightly leached from catalyst, the homogeneous Cu(2+) contribution to the whole catalytic activity is unimportant, and the highly dispersed copper on SBA-15 plays a dominant role.

  16. A simple granulation technique for preparing high-porosity nano copper oxide(Ⅱ) catalyst beads

    Institute of Scientific and Technical Information of China (English)

    Seyed Javad Ahmadia; Mohammad Outokesh; Morteza Hosseinpour; Tahereh Mousavand

    2011-01-01

    A simple and efficient method was developed for fabricating spherical granules of CuO catalyst via a three-step procedure.In the first step,copper oxide nanoparticles were synthesized by hydrothermal decomposition of copper nitrate solution under supercritical condition.Then,they were immobilized in the polymeric matrix of calcium alginate,and followed by high-temperature calcination in an air stream as the third step,in which carbonaceous materials were oxidized,to result in a pebble-type catalyst of high porosity.The produced CuO nanoparticles were characterized by transmission electron microscopy (TEM) that revealed an average size of 5 nm,X-ray diffractometry (XRD),and thermo gravimetric (TG)analysis.The catalysts were further investigated by BET test for measurement of their surface area,and by temperature-programmed reduction analysis (H2-TPR) for determination of catalytic activity.The results demonstrated that immobilization of the CuO nanoparticle in the polymeric matrix of calcium alginate,followed by calcination at elevated temperatures,could result in notable mechanical strength and enhanced catalytic activity due to preservation of the high surface area,both valuable for practical applications.

  17. Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts

    Science.gov (United States)

    Senanayake, Sanjaya D.; Pappoe, Naa Adokaley; Nguyen-Phan, Thuy-Duong; Luo, Si; Li, Yuanyuan; Xu, Wenqian; Liu, Zongyuan; Mudiyanselage, Kumudu; Johnston-Peck, Aaron C.; Frenkel, Anatoly I.; Heckler, Ilana; Stacchiola, Dario; Rodriguez, José A.

    2016-10-01

    We have studied the catalytic carbon monoxide (CO) oxidation (CO + 0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5 wt.% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface states or intermediates of this reaction. With the aid of several ex situ characterization techniques including transmission electron microscopy (TEM), the local catalyst morphology and structure were also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggest that surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Both in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.

  18. Copper oxide as efficient catalyst for oxidative dehydrogenation of alcohols with air

    DEFF Research Database (Denmark)

    Poreddy, Raju; Engelbrekt, Christian; Riisager, Anders

    2015-01-01

    The oxidative dehydrogenation of alcohols to carbonyl compounds was studied using CuO nanoparticle catalysts prepared by solution synthesis in buffered media. CuO nanoparticles synthesized in N-cyclohexyl- 3-aminopropanesulfonic acid buffer showed high catalytic activity for the oxidation...

  19. Selective oxidation of benzylic alcohols using copper-manganese mixed oxide nanoparticles as catalyst

    Directory of Open Access Journals (Sweden)

    Roushown Ali

    2015-07-01

    Full Text Available The catalytic activity of copper-manganese (CuMn2 mixed oxide nanoparticles (Cu/Mn = 1:2 has been studied for the selective oxidation of benzylic alcohols to the corresponding aldehydes using molecular oxygen as an oxidizing agent. The CuMn2 mixed oxide showed excellent catalytic activity for the oxidation of benzylic alcohols to the corresponding aldehydes with high selectivity (>99%. The complete conversion (100% of all the benzylic alcohols to the corresponding aldehydes is achieved within a short reaction period at 102 °C. The catalytic performance is obtained to be dependent on the electronic and steric effects of the substituents present on the phenyl ring. Electron withdrawing and bulky groups attached to the phenyl ring required longer reaction time for a complete conversion of the benzylic alcohols.

  20. Impact of carbon on the surface and activity of silica-carbon supported copper catalysts for reduction of nitrogen oxides

    Science.gov (United States)

    Spassova, I.; Stoeva, N.; Nickolov, R.; Atanasova, G.; Khristova, M.

    2016-04-01

    Composite catalysts, prepared by one or more active components supported on a support are of interest because of the possible interaction between the catalytic components and the support materials. The supports of combined hydrophilic-hydrophobic type may influence how these materials maintain an active phase and as a result a possible cooperation between active components and the support material could occur and affects the catalytic behavior. Silica-carbon nanocomposites were prepared by sol-gel, using different in specific surface areas and porous texture carbon materials. Catalysts were obtained after copper deposition on these composites. The nanocomposites and the catalysts were characterized by nitrogen adsorption, TG, XRD, TEM- HRTEM, H2-TPR, and XPS. The nature of the carbon predetermines the composite's texture. The IEPs of carbon materials and silica is a force of composites formation and determines the respective distribution of the silica and carbon components on the surface of the composites. Copper deposition over the investigated silica-carbon composites leads to formation of active phases in which copper is in different oxidation states. The reduction of NO with CO proceeds by different paths on different catalysts due to the textural differences of the composites, maintaining different surface composition and oxidation states of copper.

  1. Catalytic wet peroxide oxidation of azo dye (Direct Blue 15) using solvothermally synthesized copper hydroxide nitrate as catalyst.

    Science.gov (United States)

    Zhan, Yuzhong; Zhou, Xiang; Fu, Bei; Chen, Yiliang

    2011-03-15

    Copper hydroxide nitrate (Cu(2)(OH)(3)NO(3)) was synthesized solvothermally in anhydrous ethanol and characterized by XRD, FTIR, TG-DTA and SEM. The peroxide degradation of an azo dye (Direct Blue 15) on this material was evaluated by examining catalyst loading, initial pH, hydrogen peroxide dosage, initial dye concentration and temperature. The leaching of Cu from the copper hydroxide nitrate during the reaction was also measured. The copper hydroxide nitrate synthesized solvothermally, which was of a novel spherical morphology with complex secondary structures and contained high-dispersed Cu(2)O impurity, showed good performance for oxidation degradation of the azo dye, especially high catalytic activity, high utilization of hydrogen peroxide and a wide pH range, whereas the copper hydroxide nitrate synthesized by the direct reaction of copper nitrate and sodium hydroxide showed low catalytic activity. Copyright © 2011 Elsevier B.V. All rights reserved.

  2. Effect of doping rare earth oxide on performance of copper-manganese catalysts for water-gas shift reaction

    Institute of Scientific and Technical Information of China (English)

    何润霞; 姜浩强; 武芳; 智科端; 王娜; 周晨亮; 刘全生

    2014-01-01

    Rare earth-doped copper-manganese mixed oxide catalysts were prepared by coprecipitation and mechanical mixing using copper sulfate, manganese sulfate, and rare-earth oxides REO (REO indicates La2O3, CeO2, Y2O3, or Pr6O11) as raw materials. The samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), temperature-programmed reduc-tion of oxidized surfaces (s-TPR), and temperature-programmed desorption (TPD). Catalytic activities were tested for a water-gas shift reaction. Doping rare earth oxides did not alter the crystal structure of the original copper-manganese mixed oxides but changed the interplanar spacing, adsorption performance and reaction performance. Doping with La2O3 enhanced the activity and stability of Cu-Mn mixed oxides because of high copper distribution and fine reduction. Doping with CeO2 and Y2O3 also decreased the reduc-tion temperatures of the samples to different degrees while improving the dispersion of Cu on the surface, thus, catalytic activity was better than that of undoped Cu-Mn sample. The Pr6O11-doped sample was difficult to reduce, the dispersion of surface coppers was lowered, resulting in poor activity.

  3. Enhanced catalytic toluene oxidation by interaction between copper oxide and manganese oxide in Cu-O-Mn/γ-Al2O3 catalysts

    Science.gov (United States)

    Wang, Hongpei; Lu, Yiyuan; Han, YuXiang; Lu, Chunliang; Wan, Haiqin; Xu, Zhaoyi; Zheng, Shourong

    2017-10-01

    Toward catalytic oxidation of toluene, Cu-O-Mn/γ-Al2O3 catalysts with series molar ratios of Cu/Mn were prepared using an impregnation method. The surface structure and chemical state of the as-prepared catalysts were characterized by the combination of X-ray diffraction (XRD), N2 adsorption/desorption, UV-vis spectroscopy (UV-vis), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and H2 temperature programmed reduction (H2-TPR). The results demonstrated that copper oxide and manganese oxide were highly dispersed on the γ-Al2O3 support. Meanwhile, there is an interaction between copper oxide and manganese oxide, depending on the atomic ratio of Cu/Mn. At the ratio of Cu/Mn = 1:1.5, the interaction between Cu and Mn oxides reached the strongest, thus leading to the highest catalytic activity and turn over frequency among all of the ratios. The temperature for complete combustion of toluene over the strongest interaction sample could be 350 °C, which could further decrease to 300 °C when tuning the loading amount of Cu and Mn. Findings in this work are important for the design of efficient catalyst by tuning the interaction between each components.

  4. Copper Tetrahydrosalen Complex Encapsulated in Zeolite Y:an Effective Heterogeneous Catalyst for the Oxidation of Cycloalkanes

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A new heterogeneous catalyst, copper tetrahydrosalen complex encapsulated in zeolite Y (denoted as Cu[H4]salen/Y) has been developed with flexible ligand method, and characterized by FTIR, DR UV-Vis spectroscopy, N2 adsorption/desorption at -196℃. This catalyst behaved like a bio-mimic enzyme, and exhibited much higher activity for the oxidation of cycloalkanes than Cusalen/Y prepared with the same method. The effects of the reaction conditions on the catalytic performance were investigated.

  5. Photo-oxidation catalysts

    Science.gov (United States)

    Pitts, J. Roland; Liu, Ping; Smith, R. Davis

    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.

  6. Performance of supported catalysts based on a new copper vanadate-type precursor for catalytic oxidation of toluene

    Energy Technology Data Exchange (ETDEWEB)

    Palacio, L.A. [Grupo Catalizadores y Adsorbentes, Universidad de Antioquia, A.A. 1226 - Medellin (Colombia); Silva, E.R.; Catalao, R. [IBB-Institute for Biotechnology and Bioengineering, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Silva, J.M. [IBB-Institute for Biotechnology and Bioengineering, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Instituto Superior Engenharia de Lisboa, Departamento de Engenharia Quimica. Av. Cons. Emidio Navarro, 1959-007 Lisboa (Portugal); Hoyos, D.A. [Grupo Catalizadores y Adsorbentes, Universidad de Antioquia, A.A. 1226 - Medellin (Colombia); Ribeiro, F.R. [IBB-Institute for Biotechnology and Bioengineering, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Ribeiro, M.F. [IBB-Institute for Biotechnology and Bioengineering, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001 Lisboa (Portugal)], E-mail: filipa.ribeiro@ist.utl.pt

    2008-05-01

    A new copper vanadate precursor with the formula NH{sub 4}[Cu{sub 2.5}V{sub 2}O{sub 7}(OH){sub 2}].H{sub 2}O was synthesized and deposited on two different supports, ZSM-5 and amorphous SiO{sub 2}, by a hydrothermal method or by mechanical mixture. The catalytic behaviour was evaluated in the total oxidation of toluene and the characterization was performed by H{sub 2}-temperature-programmed reduction (H{sub 2}-TPR), thermogravimetric analysis, elemental analysis, UV-vis diffuse reflectance spectroscopy and X-ray diffraction. It was found that the copper vanadate phase comprises two mixed oxides, one of them crystalline, the Ziesite phase, and the other one amorphous. The supported catalysts presented a content of copper vanadate phase of about 9-11 wt.%. The copper vanadate deposited on ZSM-5 by the hydrothermal method evidences the best performance in the oxidation of toluene. This behaviour can be associated with the smaller size and higher dispersion of the particles on the support, which was confirmed by their better reducibility and higher band gap energy value compared with the other series of studied catalysts.

  7. Highly practical copper(I)/TEMPO catalyst system for chemoselective aerobic oxidation of primary alcohols.

    Science.gov (United States)

    Hoover, Jessica M; Stahl, Shannon S

    2011-10-26

    Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O(2) as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)Cu(I)/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic, and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups.

  8. CO Selective Oxidation in Hydrogen-Rich Gas over Copper-Series Catalysts

    Institute of Scientific and Technical Information of China (English)

    Hanbo Zou; Xinfa Dong; Weiming Lin

    2005-01-01

    The performances of CO selective oxidation in hydrogen-rich gas over four catalytic systems of CuO/ZrO2, CuO/MnO2, CuO/CoO and CuO/CeO2 were compared. The reducibility of these catalysts and the effect of CuO and CeO2 molar ratio of CuO/CeO2 catalysts on the activity of selective CO oxidation are investigated by XRD and TPR methods. The results show that the catalysts with the exception of CuO/ZrO2 have the interactions between CuO and CoO, CeO2 or MnO2, which result in a decrease in the reduction temperature. Among the catalysts studied, CuO/ZrO2 catalyst shows the lowest catalytic activity while CuO/CeO2 catalyst exhibits the best catalytic performance. The CuO(10%)/CeO2 catalyst attains the highest CO conversion and selectivity at 140 and 160 ℃. The addition of 9% H2O in the reactant feed decreases the activity of CuO/CeO2 catalyst but increases its CO selectivity.

  9. PdCl2-loading mesoporous copper oxide as a novel and environmentally friendly catalyst for diethyl carbonate synthesis

    Science.gov (United States)

    Zhang, Pingbo; Zhou, Yan; Fan, Mingming; Jiang, Pingping

    2015-03-01

    PdCl2-loading mesoporous copper oxide (PdCl2/mCuO) catalysts were successfully synthesized via a hard template with copper carbonate basic (Cu2(OH)2CO3), cupric nitrate (Cu(NO3)2·3H2O) and copper citrate (Cu2C6H4O7·2.5H2O) as the copper(II) precursors, respectively. Their catalytic performances were investigated in the synthesis of diethyl carbonate (DEC) by oxidative carbonylation of ethanol with CO and O2. The catalysts were characterized by TGA, XRD, nitrogen adsorption-desorption analysis and SEM with the aim of establishing their composition, morphology and structure. It was observed that the catalysts all showed a good selectivity to diethyl carbonate. However, due to a better mesoporous structure such as a bigger surface area, more uniform particle size and less agglomeration, the PdCl2/mCuO-1 catalyst prepared with Cu2(OH)2CO3 precursor showed a better catalytic activity that the conversion of EtOH was about 4.8% and the STY of DEC was 97.1 mg g-1 h-1. This was because the highly developed mesoporous structure could generate a bigger surface area, which benefited the contact between reactants and active sites, improved the conversion of ethanol, and thus enhanced the catalytic performance. Furthermore, a synthetic procedure diagram about "wet impregnation" method of mesoporous CuO prepared with Cu2(OH)2CO3 precursor was given to illustrate these results intuitively.

  10. Nanoscaled copper metal-organic framework (MOF) based on carboxylate ligands as an efficient heterogeneous catalyst for aerobic epoxidation of olefins and oxidation of benzylic and allylic alcohols.

    Science.gov (United States)

    Qi, Yue; Luan, Yi; Yu, Jie; Peng, Xiong; Wang, Ge

    2015-01-19

    Aerobic epoxidation of olefins at a mild reaction temperature has been carried out by using nanomorphology of [Cu3(BTC)2] (BTC = 1,3,5-benzenetricarboxylate) as a high-performance catalyst through a simple synthetic strategy. An aromatic carboxylate ligand was employed to furnish a heterogeneous copper catalyst and also serves as the ligand for enhanced catalytic activities in the catalytic reaction. The utilization of a copper metal-organic framework catalyst was further extended to the aerobic oxidation of aromatic alcohols. The shape and size selectivity of the catalyst in olefin epoxidation and alcohol oxidation was investigated. Furthermore, the as-synthesized copper catalyst can be easily recovered and reused several times without leaching of active species or significant loss of activity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Intrinsic kinetics of the oxidation of methane over an industrial copper II oxide catalyst on a gamma-alumina support

    NARCIS (Netherlands)

    Veldsink, J.W.; Veldsink, J.W.; Versteeg, Geert; van Swaaij, Willibrordus Petrus Maria

    1995-01-01

    The kinetic rate of the heterogeneously catalysed methane oxidation reaction was studied at temperatures ranging from 723 to 923 K and atmospheric pressure. A commercially available CuO catalyst supported by thermally stable γ-Al2O3 was used as the catalyst. This kinetic study was carried out in ord

  12. OXIDATION OF PHENOL IN AQUEOUS SOLUTION WITH COPPER OXIDE CATALYSTS SUPPORTED ON γ-Al2O3, PILLARED CLAY AND TiO2: COMPARISON OF THE PERFORMANCE AND COSTS ASSOCIATED WITH EACH CATALYST

    Directory of Open Access Journals (Sweden)

    C. A. Pires

    2015-12-01

    Full Text Available Abstract The Catalytic Wet Air Oxidation (CWAO of phenol using copper oxide catalysts supported by γ-Al2O3, TiO2, and pillared clay was evaluated to identify which of these catalysts was the most appropriate for this reaction. The CuO/PILC, CuO/γ-Al2O3 and CuO/TiO2 catalysts were the most successful at removing phenol and resulted in more than 96% conversion. Among these catalysts, CuO/γ-Al2O3 produced the largest amount of CO2, the lowest amount of intermediate products and the lowest amount of copper leaching. These results showed that the CuO/γ-Al2O3catalyst was the best for the end of the reaction. However, the methods used in this study did not allow us to identify the most appropriate reaction time (or catalyst. An alternative approach for this problem was to quantify the costs for each reaction time. Using this approach, the CuO/γ-Al2O3 catalyst was the most economically favorable catalyst when it was used during the first hour of the reaction.

  13. Sustainable hydrogen production by ethanol steam reforming using a partially reduced copper-nickel oxide catalyst.

    Science.gov (United States)

    Chen, Li-Chung; Cheng, Hongkui; Chiang, Chih-Wei; Lin, Shawn D

    2015-05-22

    Hydrogen production through the use of renewable raw materials and renewable energy is crucial for advancing its applications as an energy carrier. In this study, we fabricated a solid oxide solution of Cu and Ni within a confined pore space, followed by a partial reduction, to produce a highly efficient catalyst for ethanol steam reforming (ESR). At 300 °C, EtOH is completely converted, a H2 yield of approximately 5 mol per mol is achieved, and CO2 is the main carbon-containing product. This demonstrates that H2 production from bioethanol is an efficient and sustainable approach. Such a highly efficient ESR catalyst is attributed to the ability of the metal-oxide interface to facilitate the transformation of CHx adspecies from acetaldehyde decomposition into methoxy-like adspecies, which are reformed readily to produce H2 and consequently reduce CH4 formation.

  14. Practical aerobic oxidations of alcohols and amines with homogeneous copper/TEMPO and related catalyst systems.

    Science.gov (United States)

    Ryland, Bradford L; Stahl, Shannon S

    2014-08-18

    Oxidations of alcohols and amines are common reactions in the synthesis of organic molecules in the laboratory and industry. Aerobic oxidation methods have long been sought for these transformations, but few practical methods exist that offer advantages over traditional oxidation methods. Recently developed homogeneous Cu/TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidinyl-N-oxyl) and related catalyst systems appear to fill this void. The reactions exhibit high levels of chemoselectivity and broad functional-group tolerance, and they often operate efficiently at room temperature with ambient air as the oxidant. These advances, together with their historical context and recent applications, are highlighted in this Minireview. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Oxide catalysts for oxidation of xylene

    Directory of Open Access Journals (Sweden)

    Kusman Dossumov

    2013-09-01

    Full Text Available Polioxide granulated catalysts based on transition and rare earth metals for oxidative conversion of xylene by oxygen have been investigated. It was defined the effect of the composition and concentration of the active phase of oxide catalysts: Cu-Mn-Ln; Cu-Mn-Ce and Cu-Mn-Nd on the o-xylene oxidation. It was found that the Cu-Mn-Ce catalyst has the highest activity at the concentrations of metals: copper – 3.0%; manganese – 3.0%; cerium – 1.0%.

  16. Nanostructured copper, chromium, and tin oxide multicomponent materials as catalysts for methanol decomposition: 11C-radiolabeling study.

    Science.gov (United States)

    Tsoncheva, Tanya; Sarkadi-Priboczki, Eva; Dimitrov, Momtchil; Genova, Izabela

    2013-01-01

    Copper and chromium modified tin oxide nanocomposites were obtained via incipient wetness impregnation of high surface area nanosized SnO(2) with the corresponding metal acetylacetonates and their further decomposition in air. Powder X-ray diffraction (XRD), Nitrogen physisorption, UV-Vis, and Temperature-programmed reduction (TPR) with hydrogen were applied for the samples characterization. The catalytic activity of the obtained materials was tested in methanol conversion. A new approach based on the selective coverage of the surface with (11)C-methanol was used for the characterization of the catalytic sites. It was demonstrated that the products distribution could be controlled by the surface coverage with methanol and the role of different active sites was discussed. The modification of SnO(2) with copper oxide increased the activity in methanol decomposition to CO(2)via dioxymethylene intermediates, but the catalyst suffered considerable loss of activity due to the reduction transformations by the reaction medium and formation of an inactive intermetallic alloy. The modification with chromium changed the acid-basic properties of SnO(2) by the formation of Cr(2)O(3) nanoparticles as well as anchored to the support chromate species. The former particles facilitated the formation of dimethyl ether (DME), while the latter species converted methanol predominantly to hydrocarbons. The fraction of chromate species increased in Cu-Cr-Sn oxide multicomponent nanocomposites and promoted the formation of hydrocarbons over DME at low temperatures, while at higher temperatures, the activity of the copper species leading to CO(2) formation was more pronounced.

  17. Polymer-modified copper catalysts on carbon-containing support for reactions of H2O2 decomposition and cyclohexane oxidation

    Directory of Open Access Journals (Sweden)

    S. Auezkhanova

    2012-12-01

    Full Text Available Polymer-copper catalysts supported on a carbon-containing sorbent(CS, obtained by rice husk pyrolysis have been studied in the reactions of hydrogen peroxide decomposition and cyclohexane oxidation by hydrogen peroxide at 40°C and atmospheric pressure. The effect of the polymer nature on the activity of the developed catalysts have been shown. Polyhexamethyleneguanidine (PHMG was an optimal modifier for the developed catalysts. The calculated number of catalytic cycles (TON for 7% Cu-PGMG/CS was 450.

  18. Poly(N-4-vinylbenzyl-1,4,7-triazacyclononane Copper Complex Grafted Solid Catalyst for Oxidative Polymerization of 2,6-Dimethylphenol

    Directory of Open Access Journals (Sweden)

    Kei Saito

    2016-01-01

    Full Text Available A new solid phase catalyst, poly(N-4-vinylbenzyl-1,4,7-triazacyclononane copper(I complex, grafted onto polystyrene particles, has been employed for the oxidative polymerization of 2,6-dimethylphenol using an aqueous biphasic (water/toluene solvent system. The solid catalyst was synthesized by first grafting N-(4-vinylbenzyl-1,4,7-triaza-cyclononane onto polystyrene particles using a radical mediated polymerization method and next by creating the polymer-metal complex of copper-triazacyclononane with these modified particles. Poly(2,6-dimethyl-1,4-phenylene oxide was successfully obtained from the polymerization of 2,6-dimethylphenol using this new metal-organic solid phase catalyst.

  19. Poly(N-4-vinylbenzyl-1,4,7-triazacyclononane) Copper Complex Grafted Solid Catalyst for Oxidative Polymerization of 2,6-Dimethylphenol.

    Science.gov (United States)

    Saito, Kei; Miyamoto, Koji; Nanayakkara, Sepa; Ihara, Hirotaka; Hearn, Milton T W

    2016-01-26

    A new solid phase catalyst, poly(N-4-vinylbenzyl-1,4,7-triazacyclononane) copper(I) complex, grafted onto polystyrene particles, has been employed for the oxidative polymerization of 2,6-dimethylphenol using an aqueous biphasic (water/toluene) solvent system. The solid catalyst was synthesized by first grafting N-(4-vinylbenzyl)-1,4,7-triaza-cyclononane onto polystyrene particles using a radical mediated polymerization method and next by creating the polymer-metal complex of copper-triazacyclononane with these modified particles. Poly(2,6-dimethyl-1,4-phenylene oxide) was successfully obtained from the polymerization of 2,6-dimethylphenol using this new metal-organic solid phase catalyst.

  20. Highly efficient aerobic oxidation of alcohols by using less-hindered nitroxyl-radical/copper catalysis: optimum catalyst combinations and their substrate scope.

    Science.gov (United States)

    Sasano, Yusuke; Kogure, Naoki; Nishiyama, Tomohiro; Nagasawa, Shota; Iwabuchi, Yoshiharu

    2015-04-01

    The oxidation of alcohols into their corresponding carbonyl compounds is one of the most fundamental transformations in organic chemistry. In our recent report, 2-azaadamantane N-oxyl (AZADO)/copper catalysis promoted the highly chemoselective aerobic oxidation of unprotected amino alcohols into amino carbonyl compounds. Herein, we investigated the extension of the promising AZADO/copper-catalyzed aerobic oxidation of alcohols to other types of alcohol. During close optimization of the reaction conditions by using various alcohols, we found that the optimum combination of nitroxyl radical, copper salt, and solution concentration was dependent on the type of substrate. Various alcohols, including highly hindered and heteroatom-rich ones, were efficiently oxidized into their corresponding carbonyl compounds under mild conditions with lower amounts of the catalysts.

  1. Factors influencing catalytic wet peroxide oxidation of maleic acid in aqueous phase over copper/micelle templated silica-3-aminopropyltrimethoxysilane catalyst.

    Science.gov (United States)

    Daniel, Lilian; Katima, Jamidu H Y

    2009-01-01

    Catalytic wet peroxide oxidation (CWPO) of initial maleic acid feed concentration (0.005 to 0.03 M) was carried out in a temperature range of 20-50 degrees Celsius, on micelle templated silica-3-aminopropyltrimethoxysilane (MTS-AMP) supported copper catalyst. The influence of various operating parameters such as initial feed concentration of maleic acid, temperature, catalyst loading and the stability of the catalyst were investigated. CWPO reactions were performed in a stirred batch reactor at an atmospheric pressure in the presence of H(2)O(2) as an oxidant. Total conversion of maleic acid into acetic acid was obtained under mild conditions (i.e. atmospheric pressure and 40 degrees Celsius). Blank experiments showed no measurable maleic acid conversion (i.e. only approximately 0.5% conversion of initial maleic acid), indicating that a significant oxidation reaction of maleic acid is enhanced by the presence of a catalyst. Copper on micelle templated silica-3-aminopropyltrimethoxysilane catalyst therefore was found to be suitable for aqueous phase oxidation of maleic acid with 100% of maleic acid conversion.

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

    Science.gov (United States)

    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.

  3. Catalyst for Ammonia Oxidation

    DEFF Research Database (Denmark)

    2015-01-01

    The present invention relates to a bimetallic catalyst for ammonia oxidation, a method for producing a bimetallic catalyst for ammonia oxidation and a method for tuning the catalytic activity of a transition metal. By depositing an overlayer of less catalytic active metal onto a more catalytic...

  4. Reducible oxide based catalysts

    Science.gov (United States)

    Thompson, Levi T.; Kim, Chang Hwan; Bej, Shyamal K.

    2010-04-06

    A catalyst is disclosed herein. The catalyst includes a reducible oxide support and at least one noble metal fixed on the reducible oxide support. The noble metal(s) is loaded on the support at a substantially constant temperature and pH.

  5. Synthesis and characterization of copper porphyrin into SBA-16 through "ship in a bottle" method: A catalyst for photo oxidation reaction under visible light

    Science.gov (United States)

    Najafian, Ahmad; Rabbani, Mahboubeh; Rahimi, Rahmatollah; Deilamkamar, Mehdi; Maleki, Ali

    2015-08-01

    In this study, the SBA-16 was synthesized and modified by 3-aminopropyltriethoxysilane. Then, the copper (II) meso-tetrakis(4-chlorophenyl)porphyrin (CuTClPP) was immobilized into SBA-16 (CuTClPP@SBA-16) by using ship in a bottle method. The synthesized mesoporous materials and heterogeneous catalyst were characterized by Fourier transform infrared (FT-IR), diffuse reflectance spectroscopy (DRS), X-Ray diffraction (XRD), N2 adsorption-desorption (BET), elemental analysis (CHN), electron disperse X-ray (EDX), inductively coupled plasma (ICP-AES) and scanning electron microscope (SEM). The catalytic activity of the obtained catalyst was examined in the oxidation of cyclohexene with t-butyl hydroperoxide (TBHP) and hydrogen peroxide (H2O2) as oxidants. The obtained products were determined by using gas chromatography (GC). The effect of visible light on oxidation efficiency was evaluated and results showed that the activity of catalyst increased under visible light. In addition, leaching and recycling experiments revealed that the catalyst can be repeatedly applied for cyclohexene oxidation for three successive cycles.

  6. Reduction reaction analysis of nanoparticle copper oxide for copper direct bonding using formic acid

    Science.gov (United States)

    Fujino, Masahisa; Akaike, Masatake; Matsuoka, Naoya; Suga, Tadatomo

    2017-04-01

    Copper direct bonding is required for electronics devices, especially power devices, and copper direct bonding using formic acid is expected to lower the bonding temperature. In this research, we analyzed the reduction reaction of copper oxide using formic acid with a Pt catalyst by electron spin resonance analysis and thermal gravimetry analysis. It was found that formic acid was decomposed and radicals were generated under 200 °C. The amount of radicals generated was increased by adding the Pt catalyst. Because of these radicals, both copper(I) oxide and copper(II) oxide start to be decomposed below 200 °C, and the reduction of copper oxide is accelerated by reactants such as H2 and CO from the decomposition of formic acid above 200 °C. The Pt catalyst also accelerates the reaction of copper oxide reduction. Herewith, it is considered that the copper surface can be controlled more precisely by using formic acid to induce direct bonding.

  7. Photodeposition of copper and chromia on gallium oxide: the role of co-catalysts in photocatalytic water splitting.

    Science.gov (United States)

    Busser, G Wilma; Mei, Bastian; Pougin, Anna; Strunk, Jennifer; Gutkowski, Ramona; Schuhmann, Wolfgang; Willinger, Marc-Georg; Schlögl, Robert; Muhler, Martin

    2014-04-01

    Split second: The photocatalytic activity of gallium oxide (β-Ga2 O3) depends strongly on the co-catalysts CuOx and chromia, which can be efficiently deposited in a stepwise manner by photoreduction of Cu(2+) and CrO4 (2-). The water-splitting activity can be tuned by varying the Cu loading in the range 0.025-1.5 wt %, whereas the Cr loading is not affecting the rate as long as small amounts (such as 0.05 wt %) are present. Chromia is identified as highly efficient co-catalyst in the presence of CuOx : it is essential for the oxidation of water.

  8. Synthesis and characterization of mononuclear copper(II) complexes of pyridine 2-carboxamide: Their application as catalyst in peroxidative oxidation and antimicrobial agents

    Indian Academy of Sciences (India)

    Suvendu Samanta; Shounak Ray; Sutapa Joardar; Supriya Dutta

    2015-08-01

    Four water soluble copper(II) complexes, [Cu(HL)2 (H2O)2]Cl2 (1), [Cu(HL) 2 (ClO4)2 ] (2), [Cu(HL)2 (SCN)2] (3) and [CuL 2 ]·8H 2 O (4), where HL is pyridine 2–carboxamide, have been synthesized and characterized by various spectroscopic techniques. Structures have been determined by single crystal X-ray crystallography. The pH induced inter-conversion of Cu(HL)2 (H2O)2 ]Cl2 (1) and [CuL2]·8H2O (4) through co-ordination mode switching was investigated thoroughly with the help of absorption spectroscopy. Complexes 1–3 were found to be active catalysts for the oxidation of toluene, ethyl benzene and cyclohexane in the presence of hydrogen peroxide as the oxidant under mild conditions. Toluene was oxidized to benzyl alcohol and benzaldehyde, ethyl benzene was oxidized to 1-phenylethanol and acetophenone and cyclohexane was oxidized to yield cyclohexanol and cyclohexanone Antimicrobial activities have been investigated with these copper(II) complexes against gram + ve bacteria, gram − ve bacterial and fungal species.

  9. Greener Route for Synthesis of aryl and alkyl-14H-dibenzo [a.j] xanthenes using Graphene Oxide-Copper Ferrite Nanocomposite as a Recyclable Heterogeneous Catalyst

    Science.gov (United States)

    Kumar, Aniket; Rout, Lipeeka; Achary, Lakkoji Satish Kumar; Dhaka, Rajendra. S.; Dash, Priyabrat

    2017-01-01

    A facile, efficient and environmentally-friendly protocol for the synthesis of xanthenes by graphene oxide based nanocomposite (GO-CuFe2O4) has been developed by one-pot condensation route. The nanocomposite was designed by decorating copper ferrite nanoparticles on graphene oxide (GO) surface via a solution combustion route without the use of template. The as-synthesized GO-CuFe2O4 composite was comprehensively characterized by XRD, FTIR, Raman, SEM, EDX, HRTEM with EDS mapping, XPS, N2 adsorption-desorption and ICP-OES techniques. This nanocomposite was then used in an operationally simple, cost effective, efficient and environmentally benign synthesis of 14H-dibenzo xanthene under solvent free condition. The present approach offers several advantages such as short reaction times, high yields, easy purification, a cleaner reaction, ease of recovery and reusability of the catalyst by a magnetic field. Based upon various controlled reaction results, a possible mechanism for xanthene synthesis over GO-CuFe2O4 catalyst was proposed. The superior catalytic activity of the GO-CuFe2O4 nanocomposite can be attributed to the synergistic interaction between GO and CuFe2O4 nanoparticles, high surface area and presence of small sized CuFe2O4 NPs. This versatile GO-CuFe2O4 nanocomposite synthesized via combustion method holds great promise for applications in wide range of industrially important catalytic reactions. PMID:28233832

  10. Greener Route for Synthesis of aryl and alkyl-14H-dibenzo [a.j] xanthenes using Graphene Oxide-Copper Ferrite Nanocomposite as a Recyclable Heterogeneous Catalyst

    Science.gov (United States)

    Kumar, Aniket; Rout, Lipeeka; Achary, Lakkoji Satish Kumar; Dhaka, Rajendra. S.; Dash, Priyabrat

    2017-02-01

    A facile, efficient and environmentally-friendly protocol for the synthesis of xanthenes by graphene oxide based nanocomposite (GO-CuFe2O4) has been developed by one-pot condensation route. The nanocomposite was designed by decorating copper ferrite nanoparticles on graphene oxide (GO) surface via a solution combustion route without the use of template. The as-synthesized GO-CuFe2O4 composite was comprehensively characterized by XRD, FTIR, Raman, SEM, EDX, HRTEM with EDS mapping, XPS, N2 adsorption-desorption and ICP-OES techniques. This nanocomposite was then used in an operationally simple, cost effective, efficient and environmentally benign synthesis of 14H-dibenzo xanthene under solvent free condition. The present approach offers several advantages such as short reaction times, high yields, easy purification, a cleaner reaction, ease of recovery and reusability of the catalyst by a magnetic field. Based upon various controlled reaction results, a possible mechanism for xanthene synthesis over GO-CuFe2O4 catalyst was proposed. The superior catalytic activity of the GO-CuFe2O4 nanocomposite can be attributed to the synergistic interaction between GO and CuFe2O4 nanoparticles, high surface area and presence of small sized CuFe2O4 NPs. This versatile GO-CuFe2O4 nanocomposite synthesized via combustion method holds great promise for applications in wide range of industrially important catalytic reactions.

  11. Single-step immobilization of cell adhesive peptides on a variety of biomaterial substrates via tyrosine oxidation with copper catalyst and hydrogen peroxide.

    Science.gov (United States)

    Kakinoki, Sachiro; Yamaoka, Tetsuji

    2015-04-15

    Immobilization of biologically active peptides which were isolated from extracellular matrix proteins is a powerful strategy for the design and functionalization of biomaterial substrates. However, the method of peptide immobilization was restricted, that is, peptide is often immobilized through the reactive groups inherent in substrates with multistep reactions. Here, we report a single-step immobilization of fibronectin-derived cell adhesive peptide (Arg-Glu-Asp-Val; REDV) onto polymer materials by use of tyrosine oxidation with copper catalyst and hydrogen peroxide. REDV peptide was successfully immobilized on tissue culture polystyrene, poly(ethylene terephthalate), poly(vinyl chloride), expanded-poly(tetrafluoroethylene), and poly(l-lactic acid), resulting in enhanced adhesion of human umbilical vein endothelial cells. This method is a single-step reaction under very mild conditions and is available for the biological functionalization of various medical devices.

  12. Second-Order Biomimicry: In Situ Oxidative Self-Processing Converts Copper(I)/Diamine Precursor into a Highly Active Aerobic Oxidation Catalyst.

    Science.gov (United States)

    McCann, Scott D; Lumb, Jean-Philip; Arndtsen, Bruce A; Stahl, Shannon S

    2017-04-26

    A homogeneous Cu-based catalyst system consisting of [Cu(MeCN)4]PF6, N,N'-di-tert-butylethylenediamine (DBED), and p-(N,N-dimethylamino)pyridine (DMAP) mediates efficient aerobic oxidation of alcohols. Mechanistic study of this reaction shows that the catalyst undergoes an in situ oxidative self-processing step, resulting in conversion of DBED into a nitroxyl that serves as an efficient cocatalyst for aerobic alcohol oxidation. Insights into this behavior are gained from kinetic studies, which reveal an induction period at the beginning of the reaction that correlates with the oxidative self-processing step, EPR spectroscopic analysis of the catalytic reaction mixture, which shows the buildup of the organic nitroxyl species during steady state turnover, and independent synthesis of oxygenated DBED derivatives, which are shown to serve as effective cocatalysts and eliminate the induction period in the reaction. The overall mechanism bears considerable resemblance to enzymatic reactivity. Most notable is the "oxygenase"-type self-processing step that mirrors generation of catalytic cofactors in enzymes via post-translational modification of amino acid side chains. This higher-order function within a synthetic catalyst system presents new opportunities for the discovery and development of biomimetic catalysts.

  13. Effects of copper-precursors on the catalytic activity of Cu/graphene catalysts for the selective catalytic oxidation of ammonia

    Science.gov (United States)

    Li, Jingying; Tang, Xiaolong; Yi, Honghong; Yu, Qingjun; Gao, Fengyu; Zhang, Runcao; Li, Chenlu; Chu, Chao

    2017-08-01

    Different copper-precursors were used to prepare Cu/graphene catalysts by an impregnation method. XRD, Raman spectra, TEM, BET, XPS, H2-TPR, NH3-TPD, DRIFTS and catalytic activity test were used to characterize and study the effect of precursors on the catalytic activity of Cu/graphene catalysts for NH3-SCO reaction. The large specific surface area of Cu/graphene catalysts and high dispersion of the metal particles on the graphene caused the well catalytic activity of NH3-SCO reaction. Compared to Cu/GE(AC), Cu/GE(N) showed better catalytic performance, and the complete NH3 removal efficiency was obtained at 250 °C with N2 selectivity of 85%. The copper-precursors had influence on the distribution of surface Cu species and further affected the catalytic activity of Cu/GE catalysts. The more amount of surface Cu species and highly dispersed CuO particles on the graphene surface formed by using copper nitrate as precursor could significantly improve the reducibility of catalysts and enhance NH3 adsorption, thereby improving the catalytic activity of Cu/graphene catalyst.

  14. Bimetallic Oxidation Catalysts. Oxygen Insertion into an Aryl–Hydrogen Bond of a Binuclear Copper(I) Complex

    NARCIS (Netherlands)

    Gelling, O.J.; Bolhuis, F. van; Meetsma, A.; Feringa, Bernard

    1988-01-01

    The binuclear copper(I) complex of 1,3-bis[N-(2-pyridylethyl)formimidoyl]benzene reacts with molecular oxygen to give a phenoxy- and hydroxy-bridged binuclear copper(II) complex; the structures of both complexes have been determined by X-ray crystallography.

  15. Hydrogenation of CO2 to methanol using copper/zinc oxide-based catalyst: Effect of active metal ratio

    Science.gov (United States)

    Zabidi, Noor Asmawati Mohd; Tasfy, Sara; Shaharun, Maizatul Shima

    2016-11-01

    Effects of Cu:Zn ratio on the catalytic performance of synthesized SBA-15 supported Cu/ZnO-based (CZS) catalyst for the hydrogenation of CO2 to methanol was investigated in a fixed bed reactor. The physicochemical properties of the synthesized CZS catalyst in terms of textural properties, morphological and reducibility are presented. Methanol productivity was found to be influenced by the ratio of Cu and Zn in the catalyst formulation. Methanol selectivity of 92.1 % and CO2 conversion of 14.2 % was achieved over CZS catalyst with active metal ratio of 70 %Cu:30% Zn in CO2 hydrogenation reaction performed at 250°C, 2.25 MPa, and H2/CO2 ratio of 3.

  16. A supported copper hydroxide on titanium oxide as an efficient reusable heterogeneous catalyst for 1,3-dipolar cycloaddition of organic azides to terminal alkynes.

    Science.gov (United States)

    Yamaguchi, Kazuya; Oishi, Takamichi; Katayama, Tatsuyori; Mizuno, Noritaka

    2009-10-12

    An easily prepared supported copper hydroxide on titanium oxide (Cu(OH)(x)/TiO(2)) showed high catalytic performance for the 1,3-dipolar cycloaddition of organic azides to terminal alkynes in non-polar solvents under anaerobic conditions. The reactions of various combinations of organic azides (four examples, including aromatic and aliphatic ones) and terminal alkynes (eleven examples, including aromatic, aliphatic, and double bond-containing ones) exclusively proceeded to give the corresponding 1,4-disubstituted-1,2,3-triazole derivatives in a completely regioselective manner. For the transformation of benzyl azide and ethynylbenzene with 0.12 mol % of Cu(OH)(x)/TiO(2), the turnover frequency was 505 h(-1) and the turnover number reached up to 800. These values were the highest among those with previously reported heterogeneous catalysts including Cu(OH)(x)/Al(2)O(3). The observed catalysis was truly heterogeneous and the retrieved catalyst after the reaction could be reused at least three times with retention of its high catalytic performance. It was confirmed by the UV/Vis spectrum of Cu(OH)(x)/TiO(2) and the amount of diyne formed that the Cu(II) species in Cu(OH)(x)/TiO(2) were reduced to Cu(I) species by the alkyne-alkyne homocoupling at the initial stage of the reaction (during the pretreatment of Cu(OH)(x)/TiO(2) with an alkyne). The catalytic reaction rate for the 1,3-dipolar cycloaddition linearly increased with an increase in the amount of in situ generated Cu(I) species. Therefore, the in situ generated Cu(I) species would be the catalytically active species for the present 1,3-dipolar cycloaddition.

  17. A novel dinuclear schiff base copper complex as an efficient and cost effective catalyst for oxidation of alcohol: Synthesis, crystal structure and theoretical studies

    Indian Academy of Sciences (India)

    Atena Naeimi; Samira Saeednia; Mehdi Yoosefian; Hadi Amiri Rudbari; Viviana Mollica Nardo

    2015-07-01

    An environmentally friendly protocol is described for an economic, practical laboratory-scale oxidation of primary and secondary alcohols to aldehydes and ketones, using a bis-chloro-bridged binuclear Cu(II) complex [(HL)Cu(2-Cl)2Cu(HL)]*1.5 CH3OH as catalyst. The catalyst was prepared in situ from commercially available reagents and is characterized by single crystal X-ray analysis, FT-IR, UV-visible spectra, mass spectrometry, and powder x-ray diffraction (PXRD). The geometry of the complex has been optimized using the B3LYP level of theory confirming the experimental data. Our results demonstrated well the efficiency, selectivity and stability of this new catalyst in the oxidation of alcohols in ethanol and tert-butyl hydroperoxide (tBuOOH) as a green solvent and oxidant, respectively. Turnover number and reusability have proven the high efficiency and relative stability of the catalyst.

  18. Preparation of copper-manganese composite oxide catalysts for phenol oxidation by hydrogen peroxide%过氧化氢氧化苯酚铜锰复合氧化物催化剂的制备

    Institute of Scientific and Technical Information of China (English)

    刘长虹; 吴树新

    2011-01-01

    The novel copper-manganese composite oxide catalysts were prepared by the solid reaction method. The catalytic performance of the catalysts was evaluated using phenol oxidation by hydrogen peroxide as the probe reaction, phenol conversion and diphenol yield as the evaluation index, and HPLC chromatography as the analysis method. The results showed that the catalytic properties of the catalyst were enhanced and then reduced with the increase of molar ratio of copper to manganese, calcination temperature,calcination time and grinding time, and influenced by reducing properties of the complexing agent. The optimum condition for the catalyst preparation was that Cu2 (OH)2 CO3, MnCO3 (molar ratio of copper to manganese 1:2) and proper H2C2O4 · 2H20 were put into a mortar and grinded at room temperature for 10 min, and then calcined at 400 ℃ for 2 h. Under the optimum condition, phenol conversion and diphenol yield reached 63.7% and 59.1% ,respectively.%采用固相法制备了新型催化剂铜锰复合氧化物催化剂.利用高效液相色谱法对苯酚过氧化氢氧化反应产物进行分析,以苯酚转化率和苯二酚收率为评价指标,对催化剂进行了评价.结果表明,催化剂性能随铜与锰物质的量比、焙烧温度、焙烧时间和研磨时间等因素的增大呈先升高再降低的趋势,并与络合剂的还原性有关.确定最佳工艺条件为:室温下,按锰与铜物质的量比1:2将Cu(OH)CO、MnCO和适量HCO·2HO混匀,置于研钵匀速研磨10 min,马弗炉400℃焙烧2 h.最佳条件下,苯酚转化率为63.7%,苯二酚收率为59.1%.

  19. Effect of Precipitation Method and Ce Doping on the Catalytic Activity of Copper Manganese Oxide Catalysts for CO Oxidation%沉淀方法及铈掺杂对铜锰氧化物催化剂催化氧化CO性能的影响

    Institute of Scientific and Technical Information of China (English)

    张学彬; 马扩颜; 张灵辉; 雍国平; 戴亚; 刘少民

    2011-01-01

    The influence of Ce doping and the precipitation method on structural properties and the catalytic activity of copper manganese oxides for CO oxidation at ambient temperature have been investigated. The catalysts were characterized by means of the powder X-ray diffraction and N2 adsorption-desorption, the inductively coupled plasma atomic emission spectrometry, the temperature programmed reduction, diffuse reflectance UV-Vis spectra,and the X-ray photoelectron spectroscopy. It was found that after doping little amount of Ce in copper manganese oxide, CeO2 phase was highly dispersed and could prevent sintering and aggregating of the catalyst, the size of the catalytic material was decreased, the reducibility was enhanced, the specific surface area was increased and the formation of the active sites for the oxidation of CO was improved significantly. Therefore, the activity of the rare earth promoted catalyst was enhanced remarkably.

  20. Copper Complex in Poly(vinyl chloride) as a Nitric Oxide-Generating Catalyst for the Control of Nitrifying Bacterial Biofilms.

    Science.gov (United States)

    Wonoputri, Vita; Gunawan, Cindy; Liu, Sanly; Barraud, Nicolas; Yee, Lachlan H; Lim, May; Amal, Rose

    2015-10-14

    In this study, catalytic generation of nitric oxide by a copper(II) complex embedded within a poly(vinyl chloride) matrix in the presence of nitrite (source of nitric oxide) and ascorbic acid (reducing agent) was shown to effectively control the formation and dispersion of nitrifying bacteria biofilms. Amperometric measurements indicated increased and prolonged generation of nitric oxide with the addition of the copper complex when compared to that with nitrite and ascorbic acid alone. The effectiveness of the copper complex-nitrite-ascorbic acid system for biofilm control was quantified using protein analysis, which showed enhanced biofilm suppression when the copper complex was used in comparison to that with nitrite and ascorbic acid treatment alone. Confocal laser scanning microscopy (CLSM) and LIVE/DEAD staining revealed a reduction in cell surface coverage without a loss of viability with the copper complex and up to 5 mM of nitrite and ascorbic acid, suggesting that the nitric oxide generated from the system inhibits proliferation of the cells on surfaces. Induction of nitric oxide production by the copper complex system also triggered the dispersal of pre-established biofilms. However, the addition of a high concentration of nitrite and ascorbic acid to a pre-established biofilm induced bacterial membrane damage and strongly decreased the metabolic activity of planktonic and biofilm cells, as revealed by CLSM with LIVE/DEAD staining and intracellular adenosine triphosphate measurements, respectively. This study highlights the utility of the catalytic generation of nitric oxide for the long-term suppression and removal of nitrifying bacterial biofilms.

  1. Performance evaluation of commercial copper chromites as burning rate catalyst for solid propellants

    Directory of Open Access Journals (Sweden)

    Milton Faria Diniz

    2010-09-01

    Full Text Available Copper chromites are well known as burning rate catalysts for the combustion of composite solid propellants, used as a source of energy for rocket propulsion. The propellant burning rate depends upon the catalyst characteristics such as chemical composition and specific surface area. In this work, copper chromite samples from different suppliers were characterized by chemical analysis, FT-IR spectroscopy and by surface area measurement (BET. The samples were then evaluated as burning rate catalyst in a typical composite propellant formulation based on HTPB binder, ammonium perchlorate and aluminum. The obtained surface area values are very close to those informed by the catalyst suppliers. The propellant processing as well as its mechanical properties were not substantially affected by the type of catalyst. Some copper chromite catalysts caused an increase in the propellant burning rate in comparison to the iron oxide catalyst. The results show that in addition to the surface area, other parameters like chemical composition, crystalline structure and the presence of impurities might be affecting the catalyst performance. All evaluated copper chromite samples may be used as burning rate catalyst in composite solid propellant formulations, with slight advantages for the SX14, Cu-0202P and Cu-1800P samples, which led to the highest burning rate propellants.

  2. Low-Temperature CO Oxidation over a Ternary Oxide Catalyst with High Resistance to Hydrocarbon Inhibition.

    Science.gov (United States)

    Binder, Andrew J; Toops, Todd J; Unocic, Raymond R; Parks, James E; Dai, Sheng

    2015-11-02

    Platinum group metal (PGM) catalysts are the current standard for control of pollutants in automotive exhaust streams. Aside from their high cost, PGM catalysts struggle with CO oxidation at low temperatures (oxide catalyst composed of copper oxide, cobalt oxide, and ceria (dubbed CCC) that outperforms synthesized and commercial PGM catalysts for CO oxidation in simulated exhaust streams while showing no signs of inhibition by propene. Diffuse reflectance IR (DRIFTS) and light-off data both indicate low interaction between propene and the CO oxidation active site on this catalyst, and a separation of adsorption sites is proposed as the cause of this inhibition resistance. This catalyst shows great potential as a low-cost component for low temperature exhaust streams that are expected to be a characteristic of future automotive systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Copper atoms embedded in hexagonal boron nitride as potential catalysts for CO oxidation: A first-principles investigation

    KAUST Repository

    Liu, Xin

    2014-01-01

    We addressed the electronic structure of Cu atoms embedded in hexagonal boron nitride (h-BN) and their catalytic role in CO oxidation by first-principles-based calculations. We showed that Cu atoms prefer to bind directly with the localized defects on h-BN, which act as strong trapping sites for Cu atoms and inhibit their clustering. The strong binding of Cu atoms at boron vacancy also up-shifts the energy level of Cu-d states to the Fermi level and promotes the formation of peroxide-like intermediate. CO oxidation over Cu atoms embedded in h-BN would proceed through the Langmuir-Hinshelwood mechanism with the formation of a peroxide-like complex by reaction of coadsorbed CO and O2, with the dissociation of which the a CO2 molecule and an adsorbed O atom are formed. Then, the embedded Cu atom is regenerated by the reaction of another gaseous CO with the remnant O atom. The calculated energy barriers for the formation and dissociation of peroxide complex and regeneration of embedded Cu atoms are as low as 0.26, 0.11 and 0.03 eV, respectively, indicating the potential high catalytic performance of Cu atoms embedded in h-BN for low temperature CO oxidation. © the Partner Organisations 2014.

  4. ANALYSIS AND DEVELOPMENT OF COPPER RECYCLING OF DEAD COPPER-CONTAINING CATALYSTS

    OpenAIRE

    O. S. Komarov; I. V. Provorova; V. I. Volosatikov; D. O. Komarov; N. I. Urbanovich

    2009-01-01

    The technology of processing of copper-bearing dead catalysts, which includes leaching and deposition of copper by means of electrolysis and also their application in composition of the mixture for alloy doping is offered.

  5. ANALYSIS AND DEVELOPMENT OF COPPER RECYCLING OF DEAD COPPER-CONTAINING CATALYSTS

    Directory of Open Access Journals (Sweden)

    O. S. Komarov

    2009-01-01

    Full Text Available The technology of processing of copper-bearing dead catalysts, which includes leaching and deposition of copper by means of electrolysis and also their application in composition of the mixture for alloy doping is offered.

  6. Synthesis of carbon-supported copper catalyst and its catalytic performance in methanol dehydrogenation

    Science.gov (United States)

    Shelepova, Ekaterina V.; Vedyagin, Aleksey A.; Ilina, Ludmila Yu.; Nizovskii, Alexander I.; Tsyrulnikov, Pavel G.

    2017-07-01

    Carbon-supported copper catalyst was prepared by incipient wetness impregnation of Sibunit with an aqueous solution of copper nitrate. Copper loading was 5 wt.%. Temperature of reductive pretreatment was varied within a range of 200-400 °C. The samples were characterized by transmission electron microscopy, X-ray diffraction analysis, X-ray photoelectron and X-ray absorption spectroscopies. Catalytic activity of the samples was studied in a reaction of methanol dehydrogenation. Silica-based catalyst with similar copper loading was used as a reference. It was found that copper is distributed over the surface of support in the form of metallic and partially oxidized particles of about 12-17 nm in size. Diminished interaction of copper with support was supposed to be responsible for high catalytic activity.

  7. An efficient oxidation of benzylic and alicylic compounds with water-soluble copper catalysts in t-butyl hydroperoxide at room temperature

    Institute of Scientific and Technical Information of China (English)

    Ateeq Rahman; S. M. Al Zahrani; Abdel Aziz Nait Ajjou

    2011-01-01

    The water soluble catalytic system comprising of CuCl2 and 2,2-biquinoline-4,4-dicarboxylic acid dipotassium salt (BQC) is highly efficient organic metallic catalysts for selective oxidation of benzylic and alicyclic compounds to the corresponding ketones, ex: indan to indanone, ethyl benzene to acetophenone.

  8. Oxidation Mechanism of Copper Selenide

    Science.gov (United States)

    Taskinen, Pekka; Patana, Sonja; Kobylin, Petri; Latostenmaa, Petri

    2014-09-01

    The oxidation mechanism of copper selenide was investigated at deselenization temperatures of copper refining anode slimes. The isothermal roasting of synthetic, massive copper selenide in flowing oxygen and oxygen - 20% sulfur dioxide mixtures at 450-550 °C indicate that in both atmospheres the mass of Cu2Se increases as a function of time, due to formation of copper selenite as an intermediate product. Copper selenide oxidises to copper oxides without formation of thick copper selenite scales, and a significant fraction of selenium is vaporized as SeO2(g). The oxidation product scales on Cu2Se are porous which allows transport of atmospheric oxygen to the reaction zone and selenium dioxide vapor to the surrounding gas. Predominance area diagrams of the copper-selenium system, constructed for selenium roasting conditions, indicate that the stable phase of copper in a selenium roaster gas with SO2 is the sulfate CuSO4. The cuprous oxide formed in decomposition of Cu2Se is further sulfated to CuSO4.

  9. Deactivation of Oxidation Catalysts

    Science.gov (United States)

    1991-05-01

    Levenspiel (Reference 10) have proposed an equivalent general expression of the form dS _KST (4) dtk to account for deactivation due to catalyst pore...Voorhies, A., IEC, 1954, vol. 37, p. 318. 10. Szepe, S., and 0. Levenspiel , Proc. 4th Europ. Symp. Chem. React. Eng., Pergamon Press, p. 265. 11. U.S

  10. Bridging the Time Gap: A Copper/Zinc Oxide/Aluminum Oxide Catalyst for Methanol Synthesis Studied under Industrially Relevant Conditions and Time Scales.

    Science.gov (United States)

    Lunkenbein, Thomas; Girgsdies, Frank; Kandemir, Timur; Thomas, Nygil; Behrens, Malte; Schlögl, Robert; Frei, Elias

    2016-10-01

    Long-term stability of catalysts is an important factor in the chemical industry. This factor is often underestimated in academic testing methods, which may lead to a time gap in the field of catalytic research. The deactivation behavior of an industrially relevant Cu/ZnO/Al2 O3 catalyst for the synthesis of methanol is reported over a period of 148 days time-on-stream (TOS). The process was investigated by a combination of quasi in situ and ex situ analysis techniques. The results show that ZnO is the most dynamic species in the catalyst, whereas only slight changes can be observed in the Cu nanoparticles. Thus, the deactivation of this catalyst is driven by the changes in the ZnO moieties. Our findings indicate that methanol synthesis is an interfacially mediated process between Cu and ZnO.

  11. Copper Replaces Tin: A Copper based Gelling Catalyst for Poly-Urethane from Discarded Motherboard

    OpenAIRE

    Parasar, Bibudha; Jing, Gao Wen; Yuan, Dandan; Kun, Wang; Wang, Peng; Dasgupta, Arijit; Sahasrabudhe, Atharva; Barman, Soumitra; Yuan, Rongxin; Roy, Soumyajit

    2013-01-01

    A discarded motherboard based eco-friendly copper catalyst has been programmed to replace the industrially used tin based catalyst DBTDL. The catalyst has been characterized by UV-Vis spectroscopy, FT-IR and TEM. Using the catalyst reaction conditions is optimized and under the optimized condition, both polyurethane and polyurethane foam are prepared, thus proving the generality of the catalyst to be used in industries. A possible mechanism has also been proposed.

  12. Copper Replaces Tin: A Copper based Gelling Catalyst for Poly-Urethane from Discarded Motherboard

    OpenAIRE

    Parasar, Bibudha; Jing, Gao Wen; Yuan, Dandan; Kun, Wang; Wang, Peng; Dasgupta, Arijit; Sahasrabudhe, Atharva; Barman, Soumitra; Yuan, Rongxin; Roy, Soumyajit

    2013-01-01

    A discarded motherboard based eco-friendly copper catalyst has been programmed to replace the industrially used tin based catalyst DBTDL. The catalyst has been characterized by UV-Vis spectroscopy, FT-IR and TEM. Using the catalyst reaction conditions is optimized and under the optimized condition, both polyurethane and polyurethane foam are prepared, thus proving the generality of the catalyst to be used in industries. A possible mechanism has also been proposed.

  13. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    Science.gov (United States)

    Ellis, Jr., Paul E.; Lyons, James E.

    1993-01-01

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

  14. Perovskite catalysts for oxidative coupling

    Science.gov (United States)

    Campbell, Kenneth D.

    1991-01-01

    Perovskites of the structure A.sub.2 B.sub.2 C.sub.3 O.sub.10 are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

  15. Handling of Copper and Copper Oxide Nanoparticles by Astrocytes.

    Science.gov (United States)

    Bulcke, Felix; Dringen, Ralf

    2016-02-01

    Copper is an essential trace element for many important cellular functions. However, excess of copper can impair cellular functions by copper-induced oxidative stress. In brain, astrocytes are considered to play a prominent role in the copper homeostasis. In this short review we summarise the current knowledge on the molecular mechanisms which are involved in the handling of copper by astrocytes. Cultured astrocytes efficiently take up copper ions predominantly by the copper transporter Ctr1 and the divalent metal transporter DMT1. In addition, copper oxide nanoparticles are rapidly accumulated by astrocytes via endocytosis. Cultured astrocytes tolerate moderate increases in intracellular copper contents very well. However, if a given threshold of cellular copper content is exceeded after exposure to copper, accelerated production of reactive oxygen species and compromised cell viability are observed. Upon exposure to sub-toxic concentrations of copper ions or copper oxide nanoparticles, astrocytes increase their copper storage capacity by upregulating the cellular contents of glutathione and metallothioneins. In addition, cultured astrocytes have the capacity to export copper ions which is likely to involve the copper ATPase 7A. The ability of astrocytes to efficiently accumulate, store and export copper ions suggests that astrocytes have a key role in the distribution of copper in brain. Impairment of this astrocytic function may be involved in diseases which are connected with disturbances in brain copper metabolism.

  16. A series of copper-free ternary oxide catalysts ZnAlCex used for hydrogen production via dimethyl ether steam reforming

    Science.gov (United States)

    Zhang, Lijie; Meng, Ming; Wang, Xiaojing; Zhou, Shuang; Yang, Lijuan; Zhang, Tianyong; Zheng, Lirong; Zhang, Jing; Hu, Tiandou

    2014-12-01

    Ce-substituted ternary oxide catalysts ZnAlCex were prepared and employed in dimethyl ether steam reforming (DME SR) to produce hydrogen. XRD, XAFS (XANES & EXAFS), H2O-TPD, CH3OH-TPD and TPSR techniques were used for catalyst characterization. It is found that the catalytic performance of these catalysts is dependent on Ce content. The catalyst containing 20 wt% CeO2 exhibits the best catalytic performance. Its calculated TOF (0.034 s-1) is nearly three times to that of ZnAlO. The kinetic results reveal that the addition of 20 wt% CeO2 to ZnAlCex greatly decreases the apparent activation energy (Ea) of DME SR, due to the formation of new reaction sites such as Ce4+-O-Zn2+ linkages. XRD and EXAFS analyses indicate that Ce addition can not only decrease the crystallite size of ZnO and ZnAl2O4, but also tune the relative contents of them. The results of H2O-TPD and CH3OH-TPD show that Ce addition can lower H2 desorption temperature, which accounts well for the better catalytic performance of ZnAlCex. It is worth noting that the Zn-based catalysts display much lower CO selectivity than the Cu-based one, especially the Ce-substituted ZnAlCex. Start-off durability tests demonstrate that this series of catalysts also possess high catalytic stability.

  17. Oxidation of Carbon Monoxide over Cu/CeO2 Catalysts Prepared by SMAI

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Supported Cu catalysts for low-temperature CO oxidation were prepared by solvated metal atom impregnation (SMAI). X-ray photoelectron spectroscopy (XPS) investigations indicated that the copper in all the samples was in a metallic state. XRD measurements showed that the mean diameters of Cu particles prepared by SMAI were small. Catalytical tests showed that the SMAI catalyst had high CO oxidation activity.

  18. Environmental friendly lubricants through selective hydrogenation of rapeseed oil over supported copper catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ravasio, Nicoletta; Zaccheria, Federica; Fusi, Achille; Poli, Nicola; Psaro, Rinaldo [Centro CNR CSSCMTBSO e Dip. Chimica Inorganica Metallorganica e Analitica, Universita degli Studi di Milano, Via Venezian 21, 20133 Milan (Italy); Gargano, Michele [Dipartimento di Chimica, Universita di Bari, Via Orabona 4, 70126 Bari (Italy); Recchia, Sandro [Dipartimento Scienze CCFFMM, Universita dell' Insubria, Via Lucini 3, 22100 Como (Italy)

    2002-07-10

    Different supported copper catalysts are compared in the selective hydrogenation of vegetable oils and their methylesters. The influence of parameters such as the catalysts preparation method, the support used and the activation treatment are critically evaluated in terms of catalytic activity and selectivity. All ex situ reduced catalysts prepared by the chemisorption-hydrolysis (CH) method show better performances than the ones prepared by incipient wetness technique. These data are directly matched up to the different morphology of the supported copper particles obtained with these two methods. By using a 8% Cu/SiO{sub 2} catalyst the trienic component C18:3 can be eliminated and the dienic one lowered from 22 to 3-5% without increasing the stearic C18:0 content and limiting the cis/trans-isomerisation process. These oils, with a C18:1 content up to 88% show remarkable oxidation stability and keep fluid down to -15C.

  19. Aerobic Alcohol Oxidation Using a Copper(I)/TEMPO Catalyst System: A Green, Catalytic Oxidation Reaction for the Undergraduate Organic Chemistry Laboratory

    Science.gov (United States)

    Hill, Nicholas J.; Hoover, Jessica M.; Stahl, Shannon S.

    2013-01-01

    Modern undergraduate organic chemistry textbooks provide detailed discussion of stoichiometric Cr- and Mn-based reagents for the oxidation of alcohols, yet the use of such oxidants in instructional and research laboratories, as well as industrial chemistry, is increasingly avoided. This work describes a laboratory exercise that uses ambient air as…

  20. Aerobic Alcohol Oxidation Using a Copper(I)/TEMPO Catalyst System: A Green, Catalytic Oxidation Reaction for the Undergraduate Organic Chemistry Laboratory

    Science.gov (United States)

    Hill, Nicholas J.; Hoover, Jessica M.; Stahl, Shannon S.

    2013-01-01

    Modern undergraduate organic chemistry textbooks provide detailed discussion of stoichiometric Cr- and Mn-based reagents for the oxidation of alcohols, yet the use of such oxidants in instructional and research laboratories, as well as industrial chemistry, is increasingly avoided. This work describes a laboratory exercise that uses ambient air as…

  1. Catastrophic Oxidation of Copper: A Brief Review

    Science.gov (United States)

    Belousov, V. V.; Klimashin, A. A.

    2012-10-01

    A brief review of the current understanding of copper accelerated oxidation in the presence of low-melting oxides (Bi2O3, MoO3, and V2O5) is given. Special attention is paid to the kinetics, thermodynamics, and mechanisms of accelerated oxidation of copper. The mechanisms of two stages (fast and superfast) of the copper accelerated oxidation are considered. It is shown that the fast oxidation of copper occurs by a diffusion mechanism. Oxygen diffusion along the liquid channels in the oxide scale is the rate-limiting step in the overall mechanism. The superfast oxidation of copper occurs by a fluxing mechanism. Realization of the particular mechanism depends on the mass ratio of low-melting oxide to the metal. The mass ratios of low-melting oxide to the metal and the oxygen partial pressures for superfast oxidation of copper are established. A model of the fast oxidation of copper is discussed.

  2. Dependence of copper species on the nature of the support for dispersed CuO catalysts.

    Science.gov (United States)

    Gervasini, Antonella; Manzoli, Maela; Martra, Gianmario; Ponti, Alessandro; Ravasio, Nicoletta; Sordelli, Laura; Zaccheria, Federica

    2006-04-20

    Copper catalysts prepared by chemisorption-hydrolysis technique over silica (Cu/Si) and silica-alumina (Cu/SiAl) supports were studied to understand the role of the support on the nature and surface properties of the copper species stabilized on their surfaces. The morphological and surface properties of the copper phases have been characterized by complementary techniques, such as HRTEM, EXAFS-XANES, EPR, XPS, and FTIR. For the FTIR investigation, molecular probes (CO and NO) were also adsorbed on the surfaces to test the reactivity of the copper species. Moreover, the catalytic performances of the two catalysts have been compared in the HC-SCR reaction (NO reduction by C(2)H(4)) performed in highly oxidant conditions. The superior activity and selectivity of the supported silica-alumina catalyst with respect to that supported on silica could be related with the different nature of the copper species stabilized on the two supports, as emerged from the results obtained from the spectroscopic investigations. Small and well-dispersed CuO particles were present on silica, whereas isolated copper ions predominated on silica-alumina, likely in regions rich in alumina that made some exchangeable sites available, as indicated by FTIR spectra of adsorbed CO. The less positive global charge of copper species on Cu/SiAl than in Cu/Si has been confirmed by EPR, XPS, and EXAFS-XANES analyses.

  3. Nanoparticular metal oxide/anatase catalysts

    DEFF Research Database (Denmark)

    2010-01-01

    The present invention concerns a method of preparation of nanoparticular metal oxide catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular metal oxide catalyst precursors comprising combustible crystallization seeds upon which...... the catalyst metai oxide is co-precipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step. The present invention also concerns processes wherein the nanoparticular metal oxide catalysts of the invention are used, such as SCR (deNOx) reactions...

  4. Partial oxidation of methane over bimetallic copper- and nickel-actinide oxides (Th, U)

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Ana C.; Goncalves, A.P.; Gasche, T. Almeida [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Estrada Nacional 10, 2686-953 Sacavem (Portugal); Ferraria, A.M.; Rego, A.M. Botelho do [Universidade Tecnica de Lisboa, IST, Centro de Quimica-Fisica Molecular and IN, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Correia, M.R.; Bola, A. Margarida [I3N-Universidade de Aveiro, Department Fisica, Aveiro (Portugal); Branco, J.B., E-mail: jbranco@itn.p [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Estrada Nacional 10, 2686-953 Sacavem (Portugal)

    2010-05-14

    The study of partial oxidation of methane (POM) over bimetallic nickel- or copper-actinide oxides was undertaken. Binary intermetallic compounds of the type AnNi{sub 2} (An = Th, U) and ThCu{sub 2} were used as precursors and the products (2NiO.UO{sub 3}, 2NiO.ThO{sub 2} and 2CuO.ThO{sub 2}) characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and temperature-programmed reduction. The catalysts were active and selective for the conversion of methane to H{sub 2} and CO and stable for a period of time of {approx}18 h on stream. The nickel catalysts were more active and selective than the copper catalyst and, under the same conditions, show a catalytic behaviour comparable to that of a platinum commercial catalyst, 5 wt% Pt/Al{sub 2}O{sub 3}. The catalytic activity increases when uranium replaces thorium and the selectivity of this type of materials is clearly different from that of single metal oxides and/or mechanical mixtures. The good catalytic behaviour of the bimetallic copper- and nickel-actinide oxides was attributed to an unusual interaction between copper or nickel oxide and the actinide oxide phase as showed by H{sub 2}-TPR, XPS and Raman analysis of the catalysts before and after reaction.

  5. Copper-Catalyzed Aerobic Oxidations of Organic Molecules: Pathways for Two-Electron Oxidation with a Four-Electron Oxidant and a One-Electron Redox-Active Catalyst.

    Science.gov (United States)

    McCann, Scott D; Stahl, Shannon S

    2015-06-16

    Selective oxidation reactions have extraordinary value in organic chemistry, ranging from the conversion of petrochemical feedstocks into industrial chemicals and polymer precursors to the introduction of heteroatom functional groups into pharmaceutical and agrochemical intermediates. Molecular oxygen (O2) would be the ideal oxidant for these transformations. Whereas many commodity-scale oxidations of simple hydrocarbon feedstocks employ O2 as an oxidant, methods for selective oxidation of more complex molecules bearing diverse functional groups are often incompatible with existing aerobic oxidation methods. The latter limitation provides the basis for our interest in the development of new catalytic transformations and the elucidation of mechanistic principles that underlie selective aerobic oxidation reactions. One challenge inherent in such methods is the incommensurate redox stoichiometry associated with the use of O2, a four-electron oxidant, in reactions that achieve two-electron oxidation of organic molecules. This issue is further complicated by the use of first-row transition-metal catalysts, which tend to undergo facile one-electron redox steps. In recent years, we have been investigating Cu-catalyzed aerobic oxidation reactions wherein the complexities just noted are clearly evident. This Account surveys our work in this area, which has emphasized three general classes of reactions: (1) single-electron-transfer reactions for oxidative functionalization of electron-rich substrates, such as arenes and heterocycles; (2) oxidative carbon-heteroatom bond-forming reactions, including C-H oxidations, that proceed via organocopper(III) intermediates; and (3) methods for aerobic oxidation of alcohols and amines that use Cu(II) in combination with an organic redox-active cocatalyst to dehydrogenate the carbon-heteroatom bond. These reaction classes demonstrate three different pathways to achieve two-electron oxidation of organic molecules via the cooperative

  6. Evaluation of nickel and copper catalysts in biogas reforming for hydrogen production in SOFC

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Leonardo Alves; Martins, Andre Rosa; Rangel, Maria do Carmo, E-mail: mcarmov@ufba.br [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Grupo de Estudos em Cinetica e Catalise; Ballarini, Adriana; Maina, Silvia [Instituto de Investigaciones en Catalisis Y Petroquimica Ing. Jose Miguel Parera (INCAPE), Santa Fe (Argentina)

    2017-01-15

    The solid oxide fuel cells (SOFC) enable the efficient generation of clean energy, fitting the current requirements of the growing demand for electricity and for the environment preservation. When powered with biogas (from digesters of municipal wastes), the SOFCs also contribute to reduce the environmental impact of these wastes. The most suitable route to produce hydrogen inside SOFC from biogas is through dry reforming but the catalyst is easily deactivated by coke, because of the high amounts of carbon in the stream. A promising way to overcome this drawback is by adding a second metal to nickel-based catalysts. Aiming to obtain active, selective and stable catalysts for biogas dry reforming, solids based on nickel (15%) and copper (5%) supported on aluminum and magnesium oxide were studied in this work. Samples were prepared by impregnating the support with nickel and copper nitrate, followed by calcination at 500, 600 and 800 deg C. It was noted that all solids were made of nickel oxide, nickel aluminate and magnesium aluminate but no copper compound was found. The specific surface areas did not changed with calcination temperature but the nickel oxide average particles size increased. The solids reducibility decreased with increasing temperature. All catalysts were active in methane dry reforming, leading to similar conversions but different selectivities to hydrogen and different activities in water gas shift reaction (WGSR). This behavior was assigned to different interactions between nickel and copper, at different calcination temperatures. All catalysts were active in WGSR, decreasing the hydrogen to carbon monoxide molar ratio and producing water. The catalyst calcined at 500 deg C was the most promising one, leading to the highest hydrogen yield, besides the advantage of being produced at the lowest calcination temperature, requiring less energy in its preparation. (author)

  7. Oxidation catalysts on alkaline earth supports

    Science.gov (United States)

    Mohajeri, Nahid

    2017-03-21

    An oxidation catalyst includes a support including particles of an alkaline earth salt, and first particles including a palladium compound on the support. The oxidation catalyst can also include precious metal group (PMG) metal particles in addition to the first particles intermixed together on the support. A gas permeable polymer that provides a continuous phase can completely encapsulate the particles and the support. The oxidation catalyst may be used as a gas sensor, where the first particles are chemochromic particles.

  8. Oxidation catalysts on alkaline earth supports

    Energy Technology Data Exchange (ETDEWEB)

    Mohajeri, Nahid

    2017-03-21

    An oxidation catalyst includes a support including particles of an alkaline earth salt, and first particles including a palladium compound on the support. The oxidation catalyst can also include precious metal group (PMG) metal particles in addition to the first particles intermixed together on the support. A gas permeable polymer that provides a continuous phase can completely encapsulate the particles and the support. The oxidation catalyst may be used as a gas sensor, where the first particles are chemochromic particles.

  9. Catalytic conversion of carbon dioxide into dimethyl carbonate using reduced copper-cerium oxide catalysts as low as 353 K and 1.3 MPa and the reaction mechanism

    Directory of Open Access Journals (Sweden)

    Seiki eWada

    2013-06-01

    Full Text Available Synthesis of dimethyl carbonate (DMC from CO2 and methanol under milder reaction conditions was performed using reduced cerium oxide catalysts and reduced copper-promoted Ce oxide catalysts. Although the conversion of methanol was low (0.005–0.11% for 2 h of reaction, DMC was synthesized as low as 353 K and at total pressure of as low as 1.3 MPa using reduced Cu–CeO2 catalyst (0.5 wt% of Cu. The apparent activation energy was 120 kJ mol–1 and the DMC synthesis rates were proportional to the partial pressure of CO2. An optimum amount of Cu addition to CeO2 was 0.1 wt% for DMC synthesis under the conditions at 393 K and total pressure of 1.3 MPa for 2 h (conversion of methanol: 0.15% due to the compromise of two effects of Cu: the activation of H2 during reduction prior to the kinetic tests and the block (cover of the surface active site. The reduction effects in H2 were monitored through the reduction of Ce4+ sites to Ce3+ based on the shoulder peak intensity at 5727 eV in the Ce L3-edge X-ray absorption near-edge structure (XANES. The Ce3+ content was 10% for reduced CeO2 catalyst whereas it increased to 15% for reduced Cu–CeO2 catalyst (0.5wt% of Cu. Moreover, the content of reduced Ce3+ sites (10% associated with the surface O vacancy (defect sites decreased to 5% under CO2 at 290 K for reduced Cu–CeO2 catalyst (0.1wt% of Cu. The adsorption step of CO2 on the defect sites might be the key step in DMC synthesis and thus the DMC synthesis rate dependence on the partial pressure of CO2 was proportional. Subsequent H atom subtraction steps from methanol at the neighboring surface Lewis base sites should combine two methoxy species to the adsorbed CO2 to form DMC, water, and restore the surface O vacancy.

  10. Catalyst for Carbon Monoxide Oxidation

    Science.gov (United States)

    Davis, Patricia; Brown, Kenneth; VanNorman, John; Brown, David; Upchurch, Billy; Schryer, David; Miller, Irvin

    2010-01-01

    In many applications, it is highly desirable to operate a CO2 laser in a sealed condition, for in an open system the laser requires a continuous flow of laser gas to remove the dissociation products that occur in the discharge zone of the laser, in order to maintain a stable power output. This adds to the operating cost of the laser, and in airborne or space applications, it also adds to the weight penalty of the laser. In a sealed CO2 laser, a small amount of CO2 gas is decomposed in the electrical discharge zone into corresponding quantities of CO and O2. As the laser continues to operate, the concentration of CO2 decreases, while the concentrations of CO and O2 correspondingly increase. The increasing concentration of O2 reduces laser power, because O2 scavenges electrons in the electrical discharge, thereby causing arcing in the electric discharge and a loss of the energetic electrons required to boost CO2 molecules to lasing energy levels. As a result, laser power decreases rapidly. The primary object of this invention is to provide a catalyst that, by composition of matter alone, contains chemisorbed water within and upon its structure. Such bound moisture renders the catalyst highly active and very long-lived, such that only a small quantity of it needs to be used with a CO2 laser under ambient operating conditions. This object is achieved by a catalyst that consists essentially of about 1 to 40 percent by weight of one or more platinum group metals (Pt, Pd, Rh, Ir, Ru, Os, Pt being preferred); about 1 to 90 percent by weight of one or more oxides of reducible metals having multiple valence states (such as Sn, Ti, Mn, Cu, and Ce, with SnO2 being preferred); and about 1 to 90 percent by weight of a compound that can bind water to its structure (such as silica gel, calcium chloride, magnesium sulfate, hydrated alumina, and magnesium perchlorate, with silica gel being preferred). Especially beneficial results are obtained when platinum is present in the

  11. Selective Alcohol Oxidation by a Copper TEMPO Catalyst: Mechanistic Insights by Simultaneously Coupled Operando EPR/UV-Vis/ATR-IR Spectroscopy.

    Science.gov (United States)

    Rabeah, Jabor; Bentrup, Ursula; Stößer, Reinhard; Brückner, Angelika

    2015-09-28

    The first coupled operando EPR/UV-Vis/ATR-IR spectroscopy setup for mechanistic studies of gas-liquid phase reactions is presented and exemplarily applied to the well-known copper/TEMPO-catalyzed (TEMPO=(2,2,6,6-tetramethylpiperidin-1-yl)oxyl) oxidation of benzyl alcohol. In contrast to previous proposals, no direct redox reaction between TEMPO and Cu(I) /Cu(II) has been detected. Instead, the role of TEMPO is postulated to be the stabilization of a (bpy)(NMI)Cu(II) -O2 (⋅-) -TEMPO (bpy=2,2'-bipyridine, NMI=N-methylimidazole) intermediate formed by electron transfer from Cu(I) to molecular O2 .

  12. Fabrication and Characterization of Metallic Copper and Copper Oxide Nanoflowers

    Directory of Open Access Journals (Sweden)

    *H. S. Virk

    2011-12-01

    Full Text Available Copper nanoflowers have been fabricated using two different techniques; electro-deposition of copper in polymer and anodic alumina templates, and cytyltrimethal ammonium bromide (CTAB-assisted hydrothermal method. Scanning Electron Microscope (SEM images record some interesting morphologies of metallic copper nanoflowers. Field Emission Scanning Electron Microscope (FESEM has been used to determine morphology and composition of copper oxide nanoflowers. X-ray diffraction (XRD pattern reveals the monoclinic phase of CuO in the crystallographic structure of copper oxide nanoflowers. There is an element of random artistic design of nature, rather than science, in exotic patterns of nanoflowers fabricated in our laboratory.

  13. Applications and Preparation Methods of Copper Chromite Catalysts: A Review

    Directory of Open Access Journals (Sweden)

    Ram Prasad

    2011-11-01

    Full Text Available In this review article various applications and preparation methods of copper chromite catalysts have been discussed. While discussing it is concluded that copper chromite is a versatile catalyst which not only catalyses numerous processes of commercial importance and national program related to defence and space research but also finds applications in the most concerned problem worldwide i.e. environmental pollution control. Several other very useful applications of copper chromite catalysts are in production of clean energy, drugs and agro chemicals, etc. Various preparation methods about 15 have been discussed which depicts clear idea about the dependence of catalytic activity and selectivity on way of preparation of catalyst. In view of the globally increasing interest towards copper chromite catalysis, reexamination on the important applications of such catalysts and their useful preparation methods is thus the need of the time. This review paper encloses 369 references including a well-conceivable tabulation of the newer state of the art. Copyright © 2011 by BCREC UNDIP. All rights reserved.(Received: 19th March 2011, Revised: 03rd May 2011, Accepted: 23rd May 2011[How to Cite: R. Prasad, and P. Singh. (2011. Applications and Preparation Methods of Copper Chromite Catalysts: A Review. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2: 63-113. doi:10.9767/bcrec.6.2.829.63-113][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.2.829.63-113 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/829 ] | View in 

  14. CuO/CeO2 Catalysts for Selective Oxidation of Carbon Monoxide in Excess Hydrogen

    Institute of Scientific and Technical Information of China (English)

    刘春涛; 史鹏飞; 张菊香

    2004-01-01

    CuO/CeO2 catalysts were prepared by a coprecipitation method and tested for CO removal from reformed fuels via selective oxidation. The influence of the calcination temperature on the chemical compositions and catalytic performance of CuO/CeO2 catalysts were studied. It was found that CuO/CeO2 catalysts exhibit excellent CO oxidation activity and selectivity,and the complete removal of CO is attained when the catalysts are calcined at appropriate temperatures. XRD, TPR and XPS results indicate that CuO/CeO2 catalysts exhibit higher catalytic performance in CO selective oxidation due to the strong interaction between copper oxide and cerium dioxide, which promotes the dispersion and hydrogen reduction activity of copper.

  15. Multi-functional reactively-sputtered copper oxide electrodes for supercapacitor and electro-catalyst in direct methanol fuel cell applications

    Science.gov (United States)

    Pawar, Sambhaji M.; Kim, Jongmin; Inamdar, Akbar I.; Woo, Hyeonseok; Jo, Yongcheol; Pawar, Bharati S.; Cho, Sangeun; Kim, Hyungsang; Im, Hyunsik

    2016-02-01

    This work reports on the concurrent electrochemical energy storage and conversion characteristics of granular copper oxide electrode films prepared using reactive radio-frequency magnetron sputtering at room temperature under different oxygen environments. The obtained films are characterized in terms of their structural, morphological, and compositional properties. X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscope studies reveal that granular, single-phase Cu2O and CuO can be obtained by controlling the oxygen flow rate. The electrochemical energy storage properties of the films are investigated by carrying out cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy tests. The electrochemical analysis reveals that the Cu2O and CuO electrodes have high specific capacitances of 215 and 272 F/g in 6 M KOH solution with a capacity retention of about 80% and 85% after 3000 cycles, respectively. Cyclic voltammetry and chronoamperometry are used to study the electrochemical energy conversion properties of the films via methanol electro-oxidation. The results show that the Cu2O and CuO electrodes are electro-catalytically active and highly stable.

  16. Ozone Decomposition on the Surface of Metal Oxide Catalyst

    Directory of Open Access Journals (Sweden)

    Batakliev Todor Todorov

    2014-12-01

    Full Text Available The catalytic decomposition of ozone to molecular oxygen over catalytic mixture containing manganese, copper and nickel oxides was investigated in the present work. The catalytic activity was evaluated on the basis of the decomposition coefficient which is proportional to ozone decomposition rate, and it has been already used in other studies for catalytic activity estimation. The reaction was studied in the presence of thermally modified catalytic samples operating at different temperatures and ozone flow rates. The catalyst changes were followed by kinetic methods, surface measurements, temperature programmed reduction and IR-spectroscopy. The phase composition of the metal oxide catalyst was determined by X-ray diffraction. The catalyst mixture has shown high activity in ozone decomposition at wet and dry O3/O2 gas mixtures. The mechanism of catalytic ozone degradation was suggested.

  17. Kinetics study on catalytic wet air oxidation of phenol by several metal oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    WAN Jia-feng; FENG Yu-jie; CAI Wei-min; YANG Shao-xia; SUN Xiao-jun

    2004-01-01

    Four metal oxide catalysts composed of copper (Cu), stannum (Sn), copper-stannum (Cu-Sn) and copper-cerium(Cu-Ce) respectively were prepared by the co-impregnation method, and γ-alumina(γ-Al2O3) is selected as support. A first-order kinetics model was established to study the catalytic wet air oxidation of phenol at different temperature when these catalysts were used. The model simulations are good agreement with present experimental data. Results showed that the reaction rate constants can be significantly increased when catalysts were used, and the catalyst of 6% Cu-10%Ce/γ-Al2O3 showed the best catalytic activity. This is consistent with the result of catalytic wet air oxidation of phenol and the COD removal can be arrived at 98.2% at temperature 210℃, oxygen partial pressure 3 MPa and reaction time 30 min. The activation energies of each reaction with different catalysts are nearly equal, which is found to be about 42 kJ/mol and the reaction in this study is proved to be kinetics control.

  18. Selective oxidation of alcohols over copper zirconium phosphate

    Institute of Scientific and Technical Information of China (English)

    Abdol R.Hajipour; Hirbod Karimi

    2014-01-01

    The catalytic activity of copper zirconium phosphate (ZPCu) in the selective oxidation of alcohols to their corresponding ketones or aldehydes, using H2O2 as an oxidizing agent, was studied. The oxida-tion reaction was performed without any organic solvent, phase-transfer catalyst, or additive. Steric factors associated with the substrates influenced the reaction. The catalyst was characterized using X-ray diffraction, inductively coupled plasma atomic emission spectroscopy, energy-dispersive X-ray spectroscopy, and scanning electron microscopy. It was shown that the interlayer distance increased from 0.74 to 0.80 nm and the crystallinity was reduced after Cu2+intercalation into the layers. This catalyst can be recovered and reused three times without significant loss of activity and selectivity.

  19. Heterogeneous Metal Catalysts for Oxidation Reactions

    Directory of Open Access Journals (Sweden)

    Md. Eaqub Ali

    2014-01-01

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

  20. Catalysts for complete oxidation of gaseous fuels

    Energy Technology Data Exchange (ETDEWEB)

    Neyestanaki, A.K.

    1995-12-31

    This thesis presents a study on the complete oxidation of propane, natural gas and the conversion of car exhaust gases over two types of catalysts: (a) knitted silica-fibre supported catalysts and (b) metal-modified ZSM zeolite catalysts. A hybrid textile made up of an organic-inorganic hybrid fibre containing 70 % cellulose and 30 % silicic acid was used as the raw material for preparation of the fibre support for combustion catalysts. The hybrid textile was burnt to obtain a knitted silica-fibre. The changes in the surface area, pore volume and the crystallinity of the obtained support were studied as a function of burning temperature. The stability of the support in steam-rich atmospheres was tested. The knitted silica-fibre obtained by burning the hybrid textile at 1223 K was found to have sufficient strength and high BET specific surface area (140 m{sub 2}/g) to be used as a catalyst support. A series of knitted silica-fibre supported metal oxides (oxides of Co, Ni, Mn, Cr and Cu) and combinations of them, platinum-activated metal oxides (Pt-Co{sub 3}O{sub 4}, Pt-NiO, Pt-MnO{sub 2} and Pt-Cr{sub 2}O{sub 3}) as well as noble metal (Pt, Pd) catalysts were prepared. The location of the metal oxides on the catalyst was studied by SEM equipped with EDXA. The metal oxide was found to be located mostly inside the pores rather than on the exterior surface of the silica-fibre. The catalysts were characterized by XRD, N{sub 2}-physisorption, O{sub 2}-TPD and the chemisorption of propane, carbon monoxide and hydrogen. The activity of the catalysts was tested in the combustion of propane, natural gas and in the conversion of automobile exhaust gases. The effect of residence time and stoichiometry on the conversion behaviour of the catalysts was studied

  1. Copper-catalyzed aerobic oxidative synthesis of aryl nitriles from benzylic alcohols and aqueous ammonia.

    Science.gov (United States)

    Tao, Chuanzhou; Liu, Feng; Zhu, Youmin; Liu, Weiwei; Cao, Zhiling

    2013-05-28

    Copper-catalyzed direct conversion of benzylic alcohols to aryl nitriles was realized using NH3(aq.) as the nitrogen source, O2 as the oxidant and TEMPO as the co-catalyst. Furthermore, copper-catalyzed one-pot synthesis of primary aryl amides from alcohols was also achieved.

  2. Chemical engineering design of CO oxidation catalysts

    Science.gov (United States)

    Herz, Richard K.

    1987-01-01

    How a chemical reaction engineer would approach the challenge of designing a CO oxidation catalyst for pulsed CO2 lasers is described. CO oxidation catalysts have a long history of application, of course, so it is instructive to first consider the special requirements of the laser application and then to compare them to the characteristics of existing processes which utilize CO oxidation catalysts. All CO2 laser applications require a CO oxidation catalyst with the following characteristics: (1) active at stoichiometric ratios of O2 and CO, (2) no inhibition by CO2 or other components of the laser environment, (3) releases no particulates during vibration or thermal cycling, and (4) long lifetime with a stable activity. In all applications, low consumption of power is desirable, a characteristic especially critical in aerospace applications and, thus, catalyst activity at low temperatures is highly desirable. High power lasers with high pulse repetition rates inherently require circulation of the gas mixture and this forced circulation is available for moving gas past the catalyst. Low repetition rate lasers, however, do not inherently require gas circulation, so a catalyst that did not require such circulation would be favorable from the standpoint of minimum power consumption. Lasers designed for atmospheric penetration of their infrared radiation utilize CO2 formed from rare isotopes of oxygen and this application has the additional constraint that normal abundance oxygen isotopes in the catalyst must not exchange with rare isotopes in the gas mixture.

  3. Theory of Copper Oxide Superconductors

    CERN Document Server

    Kamimura, Hiroshi; Shunichi Matsuno; Tsuyoshi Hamada

    2005-01-01

    This is an advanced textbook for graduate students and researchers wishing to learn about high temperature superconductivity in copper oxides, in particular the Kamimura-Suwa (K-S) model. Because a number of models have been proposed since the discovery of high temperature superconductivity by Bednorz and Müller in 1986, the book first explains briefly the historical development that led to the K-S model. It then focuses on the physical background necessary to understand the K-S model and on the basic principles behind various physical phenomena such as electronic structures, electrical, thermal and optical properties, and the mechanism of high temperature superconductivity.

  4. Selective Synthesis of Gasoline-Ranged Hydrocarbons from Syngas over Hybrid Catalyst Consisting of Metal-Loaded ZSM-5 Coupled with Copper-Zinc Oxide

    Directory of Open Access Journals (Sweden)

    Ting Ma

    2014-04-01

    Full Text Available The conversion of syngas (CO + H2 to gasoline-ranged hydrocarbons was carried out using a hybrid catalyst consisting of metal-loaded ZSM-5 coupled with Cu-ZnO in a near-critical n-hexane solvent. Methanol was synthesized from syngas over Cu-ZnO; subsequently, was converted to hydrocarbons through the formation of dimethyl ether (DME over the metal-loaded ZSM-5. When 0.5 wt% Pd/ZSM-5 and 5 wt% Cu/ZSM-5 among the metal-loaded ZSM-5 catalysts with Pd, Co, Fe or Cu were employed as a portion of the hybrid catalyst, the gasoline-ranged hydrocarbons were selectively produced (the gasoline-ranged hydrocarbons in all hydrocarbons: 59% for the hybrid catalyst with Pd/ZSM-5 and 64% for that with Cu/ZSM-5 with a similar CO conversion during the reaction. An increase in the Cu loading on ZSM-5 resulted in increasing the yield of the gasoline-ranged hydrocarbons, and in decreasing the yield of DME. Furthermore, the hybrid catalyst with Cu/ZSM-5 exhibited no deactivation for 30 h of the reaction. It was revealed that a hybrid catalyst containing Cu/ZSM-5 was efficient in the selective synthesis of gasoline-ranged hydrocarbons from syngas via methanol in the near-critical n-hexane fluid.

  5. Nitrogen oxides storage catalysts containing cobalt

    Science.gov (United States)

    Lauterbach, Jochen; Snively, Christopher M.; Vijay, Rohit; Hendershot, Reed; Feist, Ben

    2010-10-12

    Nitrogen oxides (NO.sub.x) storage catalysts comprising cobalt and barium with a lean NO.sub.x storage ratio of 1.3 or greater. The NO.sub.x storage catalysts can be used to reduce NO.sub.x emissions from diesel or gas combustion engines by contacting the catalysts with the exhaust gas from the engines. The NO.sub.x storage catalysts can be one of the active components of a catalytic converter, which is used to treat exhaust gas from such engines.

  6. Selective oxidation of cyclohexane on a novel catalyst Mg-Cu/SBA-15 by molecular oxygen.

    Science.gov (United States)

    Duan, Xiaogang; Liu, Weimin; Yue, Lumin; Fu, Wei; Ha, Minh Ngoc; Li, Jun; Lu, Guanzhong

    2015-10-21

    The novel catalysts xMg-2.3Cu/SBA-15 with copper and magnesium oxide co-supported on mesoporous silica were synthesized by an impregnation method. The newly synthesized catalysts were characterized using a series of techniques such as BET, XRD, H2-TPR, UV-vis, XPS, EDS and TEM. The catalytic performance was evaluated by using selective oxidation of cyclohexane with molecular oxygen as the oxidant in a solvent free system. The incorporation of magnesium improved the dispersion of copper oxide and prevented the deep oxidation of cyclohexanol and cyclohexanone. The selectivity of K/A oil was up to 99.3% with 12% conversion of cyclohexane over the 1.2Mg-2.3Cu/SBA-15 catalyst. To our knowledge, this is the best result for the heterogeneous oxidation of cyclohexane by O2.

  7. Support Functionalization To Retard Ostwald Ripening in Copper Methanol Synthesis Catalysts

    NARCIS (Netherlands)

    van den Berg, Roy|info:eu-repo/dai/nl/358212049; Parmentier, Tanja E.; Elkjaer, Christian F.; Gommes, Cedric J.; Sehested, Jens; Helveg, Stig; de Jongh, Petra E.|info:eu-repo/dai/nl/186125372; de Jong, Krijn P.|info:eu-repo/dai/nl/06885580X

    2015-01-01

    A main reason for catalyst deactivation in supported catalysts for methanol synthesis is copper particle growth. We have functionalized the support surface in order to suppress the formation and/or transport of mobile copper species and thereby catalyst deactivation. A Stober silica support was func

  8. Support Functionalization To Retard Ostwald Ripening in Copper Methanol Synthesis Catalysts

    NARCIS (Netherlands)

    van den Berg, Roy|info:eu-repo/dai/nl/358212049; Parmentier, Tanja E.; Elkjaer, Christian F.; Gommes, Cedric J.; Sehested, Jens; Helveg, Stig; de Jongh, Petra E.|info:eu-repo/dai/nl/186125372; de Jong, Krijn P.|info:eu-repo/dai/nl/06885580X

    2015-01-01

    A main reason for catalyst deactivation in supported catalysts for methanol synthesis is copper particle growth. We have functionalized the support surface in order to suppress the formation and/or transport of mobile copper species and thereby catalyst deactivation. A Stober silica support was func

  9. NO_x-assisted soot oxidation over K/CuCe catalyst

    Institute of Scientific and Technical Information of China (English)

    翁端; 李佳; 吴晓东; 司知蠢

    2010-01-01

    CeO2 and CuOx-CeO2 supported potassium catalysts were synthesized by wetness impregnation method. The catalysts were characterized by BET, NO-TPO, NOx-TPD and soot-TPO measurements. By the decoration of potassium and copper, the maximum soot combustion temperature of the ceria-based catalyst decreased to 338 and 379 °C in the presence and absence of NO under a loose contact mode, re- spectively. The pronouncedly enhanced NO oxidation ability by copper introduction and NOx storage capacity by potassium modif...

  10. Selective Synthesis of Gasoline-Ranged Hydrocarbons from Syngas over Hybrid Catalyst Consisting of Metal-Loaded ZSM-5 Coupled with Copper-Zinc Oxide

    National Research Council Canada - National Science Library

    Ting Ma; Hiroyuki Imai; Manami Yamawaki; Kazusa Terasaka; Xiaohong Li

    2014-01-01

      The conversion of syngas (CO + H2) to gasoline-ranged hydrocarbons was carried out using a hybrid catalyst consisting of metal-loaded ZSM-5 coupled with Cu-ZnO in a near-critical n-hexane solvent...

  11. Preparation and characterization of Cu-Ce-La mixed oxide as water-gas shift catalyst for fuel cells application

    Institute of Scientific and Technical Information of China (English)

    ZHI Keduan; LIU Quansheng; ZHAO Ruigang; HE Runxia; ZHANG Lifeng

    2008-01-01

    Cu-Ce-La mixed oxides were prepared by three precipitation methods (coprecipitation, homogeneous precipitation, and deposition precipitation) with variable precipitators and characterized using X-ray diffraction, BET, temperature-programmed reduction, and catalytic reaction for the water-gas shift. The Cu-Ce-La mixed oxide prepared by coprecipitation method with NaOH as precipitator presented the highest activity and thermal stability. Copper ion substituted quadrevalent ceria entered CeO2 (111) framework was in favor of activity and thermal stability of catalyst. The crystallinity of fresh catalysts increased with the reduction process. La3+ or Ce4+ substituted copper ion entered the CeO2 framework during reduction process. The coexistence of surface copper oxide (crystalline) and pure bulk crystalline copper oxide both contributed to the high activity and thermal stability of Cu-Ce-La mixes oxide catalyst.

  12. [Copper in methane oxidation: a review].

    Science.gov (United States)

    Su, Yao; Kong, Jiao-Yan; Zhang, Xuan; Xia, Fang-Fang; He, Ruo

    2014-04-01

    Methane bio-oxidation plays an important role in the global methane balance and warming mitigation, while copper has a crucial function in methane bio-oxidation. On one side, copper is known to be a key factor in regulating the expression of the genes encoding the two forms of methane monooxygenases (MMOs) and is the essential metal element of the particulate methane monooxygenase (pMMO). On the other side, the content and fractionation of copper in the environment have great effects on the distribution of methanotrophs and their metabolic capability of methane and non-methane organic compounds, as well as on the copper-specific uptake systems in methanotrophs. Thus, it is meaningful to know the role of copper in methane bio-oxidation for comprehensive understanding of this process and is valuable for guiding the application of methanotrophs in greenhouse gas removal and pollution remediation. In this paper, the roles of copper in methane oxidation were reviewed, including the effect of copper on methanotrophic community structure and activity, the expression and activity of MMOs as well as the copper uptake systems in methanotrophs. The future studies of copper and methane oxidation were also discussed.

  13. Homogeneous and heterogenized iridium water oxidation catalysts

    Science.gov (United States)

    Macchioni, Alceo

    2014-10-01

    The development of an efficient catalyst for the oxidative splitting of water into molecular oxygen, protons and electrons is of key importance for producing solar fuels through artificial photosynthesis. We are facing the problem by means of a rational approach aimed at understanding how catalytic performance may be optimized by the knowledge of the reaction mechanism of water oxidation and the fate of the catalytic site under the inevitably harsh oxidative conditions. For the purposes of our study we selected iridium water oxidation catalysts, exhibiting remarkable performance (TOF > 5 s-1 and TON > 20000). In particular, we recently focused our attention on [Cp*Ir(N,O)X] (N,O = 2-pyridincarboxylate; X = Cl or NO3) and [IrCl(Hedta)]Na water oxidation catalysts. The former exhibited a remarkable TOF whereas the latter showed a very high TON. Furthermore, [IrCl(Hedta)]Na was heterogenized onto TiO2 taking advantage of the presence of a dandling -COOH functionality. The heterogenized catalyst maintained approximately the same catalytic activity of the homogeneous analogous with the advantage that could be reused many times. Mechanistic studies were performed in order to shed some light on the rate-determining step and the transformation of catalysts when exposed to "oxidative stress". It was found that the last oxidative step, preceding oxygen liberation, is the rate-determining step when a small excess of sacrificial oxidant is used. In addition, several intermediates of the oxidative transformation of the catalyst were intercepted and characterized by NMR, X-Ray diffractometry and ESI-MS.

  14. (Non) formation of methanol by direct hydrogenation of formate on copper catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yong; Mims, Charles A.; Disselkamp, Robert S.; Kwak, Ja Hun; Peden, Charles HF; Campbell, C. T.

    2010-10-14

    We have attempted to hydrogenate adsorbed formate species on copper catalysts to probe the importance of this postulated mechanistic step in methanol synthesis. Surface formate coverages up to 0.25 were produced at temperatures between 413K and 453K on supported (Cu/SiO2) copper and unsupported copper catalysts. The adlayers were produced by various methods including (1) steady state catalytic conditions in CO2-H2 (3:1, 6 bar) atmospheres, and (2) by exposure of the catalysts to formic acid. As reported in earlier work, the catalytic surface at steady state contains bidentate formate species with coverages up to saturation levels of ~ 0.25 at the low temperatures of this study. The reactivity of these formate adlayers was investigated at relevant reaction temperatures in atmospheres containing up to 6 bar H2 partial pressure by simultaneous mass spectrometry (MS) and infrared (IR) spectroscopy measurements. The yield of methanol during the attempted hydrogenation (“titration”) of these adlayers was insignificant (<0.2 mol % of the formate adlayer) even in dry hydrogen partial pressures up to 6 bar. Hydrogen titration of formate species produced from formic acid also failed to produce significant quantities of methanol, and attempted titration in gases consisting of CO-hydrogen mixtures or dry CO2 were also unproductive. The formate decomposition kinetics, measured by IR, were also unaffected by these changes in the gas composition. Similar experiments on unsupported copper also failed to show any methanol. From these results, we conclude that methanol synthesis on copper cannot result from the direct hydrogenation of (bidentate) formate species in simple steps involving adsorbed H species alone. Furthermore, experiments performed on both supported (Cu/SiO2) and unsupported copper catalysts gave similar results implying that the methanol synthesis reaction mechanism only involves metal surface chemistry. Pre-exposure of the bidentate formate adlayer to oxidation

  15. Synthesis of copper/copper oxide nanoparticles by solution plasma

    Science.gov (United States)

    Saito, Genki; Hosokai, Sou; Tsubota, Masakatsu; Akiyama, Tomohiro

    2011-07-01

    This paper describes the synthesis of copper/copper oxide nanoparticles via a solution plasma, in which the effect of the electrolyte and electrolysis time on the morphology of the products was mainly examined. In the experiments, a copper wire as a cathode was immersed in an electrolysis solution of a K2CO3 with the concentration from 0.001 to 0.50 M or a citrate buffer (pH = 4.8), and was melted by the local-concentration of current. The results demonstrated that by using the K2CO3 solution, we obtained CuO nanoflowers with many sharp nanorods, the size of which decreased with decreasing the concentration of the solution. Spherical particles of copper with/without pores formed when the citrate buffer was used. The pores in the copper nanoparticles appeared when the applied voltage changed from 105 V to 130 V, due to the dissolution of Cu2O.

  16. Catalysts for the Selective Oxidation of Methanol

    Directory of Open Access Journals (Sweden)

    Catherine Brookes

    2016-06-01

    Full Text Available In industry, one of the main catalysts typically employed for the selective oxidation of methanol to formaldehyde is a multi-component oxide containing both bulk Fe2(MoO43 and excess MoO3. It is thought that the excess MoO3 primarily acts to replace any molybdenum lost through sublimation at elevated temperatures, therefore preventing the formation of an unselective Fe2O3 phase. With both oxide phases present however, debate has arisen regarding the active component of the catalyst. Work here highlights how catalyst surfaces are significantly different from bulk structures, a difference crucial for catalyst performance. Specifically, Mo has been isolated at the surface as the active surface species. This leaves the role of the Fe in the catalyst enigmatic, with many theories postulated for its requirement. It has been suggested that the supporting Fe molybdate phase enables lattice oxygen transfer to the surface, to help prevent the selectivity loss which would occur in the resulting oxygen deficit environment. To assess this phenomenon in further detail, anaerobic reaction with methanol has been adopted to evaluate the performance of the catalyst under reducing conditions.

  17. Electrochromism in copper oxide thin films

    Energy Technology Data Exchange (ETDEWEB)

    Richardson, T.J.; Slack, J.L.; Rubin, M.D.

    2000-08-15

    Transparent thin films of copper(I) oxide prepared on conductive SnO2:F glass substrates by anodic oxidation of sputtered copper films or by direct electrodeposition of Cu2O transformed reversibly to opaque metallic copper films when reduced in alkaline electrolyte. In addition, the same Cu2O films transform reversibly to black copper(II) oxide when cycled at more anodic potentials. Copper oxide-to-copper switching covered a large dynamic range, from 85% and 10% photopic transmittance, with a coloration efficiency of about 32 cm2/C. Gradual deterioration of the switching range occurred over 20 to 100 cycles. This is tentatively ascribed to coarsening of the film and contact degradation caused by the 65% volume change on conversion of Cu to Cu2O. Switching between the two copper oxides (which have similar volumes) was more stable and more efficient (CE = 60 cm2/C), but covered a smaller transmittance range (60% to 44% T). Due to their large electrochemical storage capacity and tolerance for alkaline electrolytes, these cathodically coloring films may be useful as counter electrodes for anodically coloring electrode films such as nickel oxide or metal hydrides.

  18. Selective propene oxidation on mixed metal oxide catalysts

    CERN Document Server

    James, D W

    2002-01-01

    Selective catalytic oxidation processes represent a large segment of the modern chemical industry and a major application of these is the selective partial oxidation of propene to produce acrolein. Mixed metal oxide catalysts are particularly effective in promoting this reaction, and the two primary candidates for the industrial process are based on iron antimonate and bismuth molybdate. Some debate exists in the literature regarding the operation of these materials and the roles of their catalytic components. In particular, iron antimonate catalysts containing excess antimony are known to be highly selective towards acrolein, and a variety of proposals for the enhanced selectivity of such materials have been given. The aim of this work was to provide a direct comparison between the behaviour of bismuth molybdate and iron antimonate catalysts, with additional emphasis being placed on the component single oxide phases of the latter. Studies were also extended to other antimonate-based catalysts, including coba...

  19. Raney copper catalysts for the water-gas shift reaction - II. Initial catalyst optimisation

    CSIR Research Space (South Africa)

    Mellor, JR

    1997-12-23

    Full Text Available -Zn-A1 catalyst. During the controlled passivation Table 2 Crystalline phase of alloys B, C and D and their product Raney copper catalysts before and after reaction Alloy Precursor alloy phases Cat. phases before reaction a Cat. phases after reaction a... L; dry gas composition=10% CO/90% N2; CO : H20=I : 22.5; catalyst volume=2i0.1 ml): (O)=Cat. A Cu(69.3)Zn(6.9)Al( 19.5); (~)=cat. B Cu(73.6)Zn(10.9)AI(14.8); (W1)=cat. C Cu(72.4)Zn(13.3)Al(12.9); ({))=cat. D Cu(61.5)Zn(15.1)AI(19.1). It can...

  20. Smelting Oxidation Desulfurization of Copper Slags

    Institute of Scientific and Technical Information of China (English)

    LI Lei; HU Jian-hang; WANG Hua

    2012-01-01

    According to the mechanism of sulfur removal easily through oxidation, the process of smelting oxidation desulfurization of copper slags is studied, which supplies a new thinking for obtaining the molten iron of lower sulfur content by smelting reduction of copper slags. Special attention is given to the effects of the holding temperature, the holding time and CaF2, CaO addition amounts on the desulfurization rate of copper slags. The results indicate that the rate of copper slags smelting oxidation desulfurization depends on the matte mass transfer rate through the slag phase. After the oxidation treatment, sulfur of copper slags can be removed as SO2 efficiently. Amount of Ca2+ of copper slags affects the desulfurization rate greatly, and the slag desulfurization rate is reduced by adding a certain amount of CaF2 and CaO. Compared with CaF2, CaO is negative to slags sulfur removal with equal Ca2+ addition. Under the air flow of 0.3 U/min, the sulfur content of copper slags can be reduced to 0. 004 67% in the condition of the holding time of 3 min and the holding temperature of 1 500 ℃. The sulfur content of molten iron is reduced to 0. 000 8 % in the smelting reduction of treated slags, and the problem of high sulfur content of molten iron obtained by smelting reduction with copper slag has been successively solved.

  1. Water gas shift reaction over Cu catalyst supported by mixed oxide materials for fuel cell application

    Directory of Open Access Journals (Sweden)

    Tepamatr Pannipa

    2016-01-01

    Full Text Available The water gas shift activities of Cu on ceria and Gd doped ceria have been studied for the further enhancement of hydrogen purity [1] after the steam reforming of ethanol. The catalytic properties of commercial catalysts were also studied to compare with the as-prepared catalysts. Copper-containing cerium oxide materials are shown in this work to be suitable for the high temperature. Copper-ceria is a stable high-temperature shift catalyst, unlike iron-chrome catalysts that deactivate severely in CO2-rich gases. We found that 5%Cu/10%GDC(D has much higher activity than other copper ceria based catalysts. The finely dispersed CuO species is favorable to the higher activity, which explained the activity enhancement of this catalyst. The kinetics of the WGS reaction over Cu catalysts supported by mixed oxide materials were measured in the temperature range 200-400 °C. An independence of the CO conversion rate on CO2 and H2 was found.

  2. Raney copper catalysts for the water-gas shift reaction: I. Preparation, activity and stability

    CSIR Research Space (South Africa)

    Mellor, JR

    1997-12-23

    Full Text Available at the stated conditions compared favourably to the co-precipitated and industrial catalyst alternatives due to a similar active phase composition and high metallic copper surface areas. Raney copper catalyst deactivation in a poison-free environment...

  3. The Revovery of Copper and Cobalt from Oxidized Copper Ore and Converter Slag

    OpenAIRE

    ZİYADANOĞULLARI, Berrin; ZİYADANOĞULLARI, Recep

    1999-01-01

    The aim of this study was to develop a method for obtaining copper and cobalt from oxidized copper ore and converter slag. In order to convert the copper and cobalt into sulfate compounds the main step was to roast the samples obtained by sulfurization and transfer the samples into solution. First the oxidized copper ore was roasted, followed by the mixture of converter slag and oxidized copper ore. Since the levels of copper and cobalt were low, the sulfurization process was carri...

  4. Adsorption and oxidation of SO₂in a fixed-bed reactor using activated carbon produced from oxytetracycline bacterial residue and impregnated with copper.

    Science.gov (United States)

    Zhou, Baohua; Yu, Lei; Song, Hanning; Li, Yaqi; Zhang, Peng; Guo, Bin; Duan, Erhong

    2015-02-01

    The SO₂removal ability (including adsorption and oxidation ability) of activated carbon produced from oxytetracycline bacterial residue and impregnated with copper was investigated. The activated carbon produced from oxytetracycline bacterial residue and modified with copper was characterized by x-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. The effects of the catalysts, SO₂concentration, weight hourly space velocity, and temperature on the SO₂adsorption and oxidation activity were evaluated. Activated carbon produced from oxytetracycline bacterial residue and used as catalyst supports for copper oxide catalysts provided high catalytic activity for the adsorbing and oxidizing of SO₂from flue gases.

  5. Nitrated metalloporphyrins as catalysts for alkane oxidation

    Science.gov (United States)

    Ellis, Jr., Paul E.; Lyons, James E.

    1992-01-01

    Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been replaced with one or more nitro groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

  6. An improved method of preparation of nanoparticular metal oxide catalysts

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention concerns an improved method of preparation of nanoparticular vanadium oxide/anatase titania catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular vanadium oxide/anatase titania catalyst precursors comprising...... combustible crystallization seeds upon which the catalyst metal oxide is coprecipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step.......The present invention concerns an improved method of preparation of nanoparticular vanadium oxide/anatase titania catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular vanadium oxide/anatase titania catalyst precursors comprising...

  7. Studies on dehydrogenation of cyclohexanol to cyclohexanone over mesoporous SiO₂ supported copper catalysts

    Indian Academy of Sciences (India)

    B SRIDEVI; P NAGAIAH; A H PADMASRI; B DAVID RAJU; K S RAMA RAO

    2017-05-01

    SBA-15, KIT-6, SiO₂ supported catalysts with 10% Cu loading have been prepared by impregnation techniques. The prepared catalysts have been characterized by BET technique, X-ray diffraction, Temperature programmed reduction (TPR), XPS and N₂O pulse chemisorption techniques. Dehydrogenation of cyclohexanol has been performed over these catalysts in vapour phase at 523 K. SBA-15 and KIT-6 supported copper catalystsshowed higher activity than SiO₂ supported Cu catalyst in dehydrogenation of cyclohexanol, which can be attributed to better Cu dispersion, small copper particle size and more number of Cu active species presented on the surface of mesoporous supported catalysts.

  8. Carbon Xerogel Catalyst for NO Oxidation

    Directory of Open Access Journals (Sweden)

    Manuel F. R. Pereira

    2012-10-01

    Full Text Available Carbon xerogels were prepared by the polycondensation of resorcinol and formaldehyde using three different solution pH values and the gels were carbonized at three different temperatures. Results show that it is possible to tailor the pore texture of carbon xerogels by adjusting the pH of the initial solution and the carbonization temperature. Materials with different textural properties were obtained and used as catalysts for NO oxidation at room temperature. The NO conversions obtained with carbon xerogels were quite high, showing that carbon xerogels are efficient catalysts for NO oxidation. A maximum of 98% conversion for NO was obtained at initial concentration of NO of 1000 ppm and 10% of O2. The highest NO conversions were obtained with the samples presenting the highest surface areas. The temperature of reaction has a strong influence on NO oxidation: the conversion of NO decreases with the increase of reaction temperature.

  9. [Copper leaching in catalytic wet oxidation of phenol with Cu-containing spinel].

    Science.gov (United States)

    Xu, Ai-hua; He, Song-bo; Yang, Min; Du, Hong-zhang; Sun, Cheng-lin

    2008-09-01

    The Cu0.10, Zn0.90 Al1.90 Fe0.10 O4 spinel type catalyst prepared by sol-gel method was tested for catalytic wet air oxidation of phenol. The performances of Cu0.10 Zn0.90 Al1.90 Fe0.10 O4 catalyst in TPR experiment, the influence of phenol as reducer, reaction temperature and phenol-to-catalyst mass ratio on copper leaching were checked respectively. According to the experimental results, it is suggested that the reduced active species can not be easily re-oxidized under low reaction temperature and high phenol-to-catalyst mass ratio are the main reasons for copper leaching. Under high enough reaction temperature and low phenol-to-catalyst mass ratio, the copper leaching reduces remarkably. At 190 degrees C in the presence of 100 mL aqueous solution of 4.29 g x L(-1) of phenol and 2.5 g catalyst, the copper leaching was only 0.96 mg x L(-1) after 2 h of reaction.

  10. Total oxidation of toluene over calcined trimetallic hydrotalcites type catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Palacio, Luz A. [Instituto Superior Tecnico, IBB - Centro de Engenharia Biologica e Quimica, Universidade Tecnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Grupo Catalizadores y Adsorbentes, Universidad de Antioquia 1-317, A.A. 1226 Medellin (Colombia); Velasquez, Juliana; Echavarria, Adriana [Grupo Catalizadores y Adsorbentes, Universidad de Antioquia 1-317, A.A. 1226 Medellin (Colombia); Faro, Arnaldo [Departamento de Fisicoquimica, Instituto de Quimica, Universidade Federal do Rio de Janeiro, Ilha do Fundao, CT bloco A, Rio de Janeiro (Brazil); Ramoa Ribeiro, F. [Instituto Superior Tecnico, IBB - Centro de Engenharia Biologica e Quimica, Universidade Tecnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Ribeiro, M. Filipa, E-mail: filipa.ribeiro@ist.utl.pt [Instituto Superior Tecnico, IBB - Centro de Engenharia Biologica e Quimica, Universidade Tecnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa (Portugal)

    2010-05-15

    Two trimetallic ZnCuAl and MnCuAl hydrotalcites have been successfully synthesized by a co-precipitation method. The manganese based material was identified as a new hydrotalcite phase. Both lamellar precursors were calcined at 450 and 600 deg. C and the resulting catalysts were tested on reaction of total oxidation of toluene. The solids were characterized by X-ray diffraction, thermal analysis, atomic absorption spectroscopy, Fourier transformed infrared spectroscopy, N{sub 2} adsorption and H{sub 2} temperature-programmed reduction. It was found that ZnCuAl materials are composed of copper and zinc oxides supported on alumina; while MnCuAl ones comprise basically spinel phases, which were not completely identified. The catalytic behavior of the calcined samples showed that Mn hydrotalcite calcined at 450 deg. C exhibited the best catalytic performance that corresponds to 100% toluene conversion into CO{sub 2} at about 300 deg. C.

  11. High catalytic activity of oriented 2.0.0 copper(I) oxide grown on graphene film

    Science.gov (United States)

    Primo, Ana; Esteve-Adell, Ivan; Blandez, Juan F.; Dhakshinamoorthy, Amarajothi; Álvaro, Mercedes; Candu, Natalia; Coman, Simona M.; Parvulescu, Vasile I.; García, Hermenegildo

    2015-10-01

    Metal oxide nanoparticles supported on graphene exhibit high catalytic activity for oxidation, reduction and coupling reactions. Here we show that pyrolysis at 900 °C under inert atmosphere of copper(II) nitrate embedded in chitosan films affords 1.1.1 facet-oriented copper nanoplatelets supported on few-layered graphene. Oriented (1.1.1) copper nanoplatelets on graphene undergo spontaneous oxidation to render oriented (2.0.0) copper(I) oxide nanoplatelets on few-layered graphene. These films containing oriented copper(I) oxide exhibit as catalyst turnover numbers that can be three orders of magnitude higher for the Ullmann-type coupling, dehydrogenative coupling of dimethylphenylsilane with n-butanol and C-N cross-coupling than those of analogous unoriented graphene-supported copper(I) oxide nanoplatelets.

  12. Activity of Cu-activated carbon fiber catalyst in wet oxidation of ammonia solution.

    Science.gov (United States)

    Hung, Chang-Mao

    2009-07-30

    Aqueous solutions of 200-1000 mg/L of ammonia were oxidized in a trickle-bed reactor using Cu-activated carbon fiber (ACF) catalysts, which were prepared by incipient wet impregnation with aqueous solutions of copper nitrate that was deposited on ACF substrates. The results reveal that the conversion of ammonia by wet oxidation in the presence of Cu-ACF catalysts was a function of the metal loading weight ratio of the catalyst. The total conversion efficiency of ammonia was 95% during wet oxidation over the catalyst at 463 K at an oxygen partial pressure of 3.0 MPa. Moreover, the effect of the initial concentration of ammonia and the reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid space velocity of less than 3.0 h(-1).

  13. Preferential oxidation of CO in excess H2 over CuO/CeO2 catalysts: Performance as a function of the copper coverage and exposed face present in the CeO2 support

    DEFF Research Database (Denmark)

    Monte, M.; Gamarra, D.; López Cámara, A.

    2014-01-01

    CuO/CeO2 catalysts where the support has different nanoparticle shapes exposing different lattice planes are examined for the preferential oxidation of CO in the presence of excess H2 (CO-PROX reaction) in operando DRIFTS conditions. Even for catalysts with same surface concentration of Cu...... and selectivity, so that they are fully reduced at higher temperature in agreement with TPR data. DFT calculations show that CuO nanoparticles interact more strongly (distorting more their structure) with the CeO2 (001) surface than with the (111) surface, while XRD indicates that the formation of well developed...

  14. Effects of copper(II) and copper oxides on THMs formation in copper pipe.

    Science.gov (United States)

    Li, Bo; Qu, Jiuhui; Liu, Huijuan; Hu, Chengzhi

    2007-08-01

    Little is known about how the growth of trihalomethanes (THMs) in drinking water is affected in copper pipe. The formation of THMs and chlorine consumption in copper pipe under stagnant flow conditions were investigated. Experiments for the same water held in glass bottles were performed for comparison. Results showed that although THMs levels firstly increased in the presence of chlorine in copper pipe, faster decay of chlorine as compared to the glass bottle affected the rate of THMs formation. The analysis of water phase was supplemented by surface analysis of corrosion scales using X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and energy dispersive spectroscopy (EDX). The results showed the scales on the pipe surface mainly consisted of Cu(2)O, CuO and Cu(OH)(2) or CuCO(3). Designed experiments confirmed that the fast depletion of chlorine in copper pipe was mainly due to effect of Cu(2)O, CuO in corrosion scales on copper pipe. Although copper(II) and copper oxides showed effect on THMs formation, the rapid consumption of chlorine due to copper oxide made THM levels lower than that in glass bottles after 4h. The transformations of CF, DCBM and CDBM to BF were accelerated in the presence of copper(II), cupric oxide and cuprous oxide. The effect of pH on THMs formation was influenced by effect of pH on corrosion of copper pipe. When pH was below 7, THMs levels in copper pipe was higher as compared to glass bottle, but lower when pH was above 7.

  15. Aqueous aerobic oxidation of alkyl arenes and alcohols catalyzed by copper(II) phthalocyanine supported on three-dimensional nitrogen-doped graphene at room temperature.

    Science.gov (United States)

    Mahyari, Mojtaba; Laeini, Mohammad Sadegh; Shaabani, Ahmad

    2014-07-25

    Copper(ii) tetrasulfophthalocyanine supported on three-dimensional nitrogen-doped graphene-based frameworks was synthesized and introduced as a bifunctional catalyst for selective aerobic oxidation of alkyl arenes and alcohols to the corresponding carbonyl compounds. The ease of catalyst separation, high turnover, low catalyst loading and recyclability could potentially render it applicable in industrial setting.

  16. Novel, benign, solid catalysts for the oxidation of hydrocarbons.

    Science.gov (United States)

    Ratnasamy, Paul; Raja, Robert; Srinivas, Darbha

    2005-04-15

    The catalytic properties of two classes of solid catalysts for the oxidation of hydrocarbons in the liquid phase are discussed: (i) microporous solids, encapsulating transition metal complexes in their cavities and (ii) titanosilicate molecular sieves. Copper acetate dimers encapsulated in molecular sieves Y, MCM-22 and VPI-5 use dioxygen to regioselectively ortho-hydroxylate L-tyrosine to L-dopa, phenol to catechol and cresols to the corresponding o-dihydroxy and o-quinone compounds. Monomeric copper phthalocyanine and salen complexes entrapped in zeolite-Y oxidize methane to methanol, toluene to cresols, naphthalene to naphthols, xylene to xylenols and phenol to diphenols. Trimeric mu3-oxo-bridged Co/Mn cluster complexes, encapsulated inside Y-zeolite, oxidize para-xylene, almost quantitatively, to terephthalic acid. In almost all cases, the intrinsic catalytic activity (turnover frequency) of the metal complex is enhanced very significantly, upon encapsulation in the porous solids. Spectroscopic and electrochemical studies suggest that the geometric distortions of the complex on encapsulation change the electron density at the metal ion site and its redox behaviour, thereby influencing its catalytic activity and selectivity in oxidation reactions. Titanosilicate molecular sieves can oxidize hydrocarbons using dioxygen when loaded with transition metals like Pd, Au or Ag. The structure of surface Ti ions and the type of oxo-Ti species generated on contact with oxidants depend on several factors including the method of zeolite synthesis, zeolite structure, solvent, temperature and oxidant. Although, similar oxo-Ti species are present on all the titanosilicates, their relative concentrations vary among different structures and determine the product selectivity.

  17. Stabilized tin-oxide-based oxidation/reduction catalysts

    Science.gov (United States)

    Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony Neal (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor)

    2008-01-01

    The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

  18. An infrared spectroscopic study of the adsorption of carbon monoxide on silica-supported copper oxide

    NARCIS (Netherlands)

    Jong, K.P. de; Geus, John W.; Joziasse, J.

    1980-01-01

    Adsorption of carbon monoxide at room temperature (0.1–50 Torr) on silica-supported copper oxide was studied by infrared spectroscopy. Catalysts were prepared by deposition-precipitation or impregnation. After calcination two types of adsorbed CO were identified showing absorption bands at 2136 ± 3

  19. Determination of kjeldahl nitrogen in fertilizers by AOAC official methods 978.02: effect of copper sulfate as a catalyst.

    Science.gov (United States)

    Abrams, Dean; Metcalf, David; Hojjatie, Michael

    2014-01-01

    In AOAC Official Method 955.04, Nitrogen (Total) in Fertilizers, Kjeldahl Method, fertilizer materials are analyzed using mercuric oxide or metallic mercury HgO or Hg) as a catalyst. AOAC Official Methods 970.02, Nitrogen (Total) in Fertilizers is a comprehensive total nitrogen (including nitrate nitrogen) method adding chromium metal. AOAC Official Method 978.02, Nitrogen (Total) in Fertilizers is a modified comprehensive nitrogen method used to measure total nitrogen in fertilizers with two types of catalysts. In this method, either copper sulfate or chromium metal is added to analyze for total Kjeldahl nitrogen. In this study, the part of AOAC Official Method 978.02 that is for nitrate-free fertilizer products was modified. The objective was to examine the necessity of copper sulfate as a catalyst for the nitrate-free fertilizer products. Copper salts are not environmentally friendly and are considered pollutants. Products such as ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea-containing fertilizers such as isobutylene diurea (IBDU), and urea-triazone fertilizer solutions were examined. The first part of the study was to measure Kjeldahl nitrogen as recommended by AOAC Official Method 978.02. The second part of the study was to exclude the addition of copper sulfate from AOAC Official Method 978.02 to examine the necessity of copper sulfate as a catalyst in nitrate-free fertilizers, which was the primary objective. Our findings indicate that copper sulfate can be eliminated from the method with no significant difference in the results for the nitrogen content of the fertilizer products.

  20. on THICKNESS OF COPPER (|) OXIDE (Cu2"O) SOLAR CELL

    African Journals Online (AJOL)

    thickness of copper oxides solar ce[[s prepared 63/ thermaf oxidation method The sampfes were oxidized at di_';§'erent oxidation temperatures and time. The diflerent oxidation ... observed that the later was relatively high. Adrianus (1978).

  1. Inkjet catalyst printing and electroless copper deposition for low-cost patterned microwave passive devices on paper

    Science.gov (United States)

    Cook, Benjamin S.; Fang, Yunnan; Kim, Sangkil; Le, Taoran; Goodwin, W. Brandon; Sandhage, Kenneth H.; Tentzeris, Manos M.

    2013-09-01

    A scalable, low-cost process for fabricating copper-based microwave components on flexible, paper-based substrates is demonstrated. An inkjet printer is used to deposit a catalyst-bearing solution (tailored for such printing) in a desired pattern on commercially-available, recyclable, non-toxic (Teslin®) paper. The catalystbearing paper is then immersed in an aqueous copper-bearing solution to allow for electroless deposition of a compact and conformal layer of copper in the inkjet-derived pattern. Meander monopole antennas comprised of such electroless-deposited copper patterns on paper exhibited comparable performance as for antennas synthesized via inkjet printing of a commercially-available silver nanoparticle ink. However, the solution-based patterning and electroless copper deposition process avoids nozzle-clogging problems and costs associated with noble metal particle-based inks. This process yields compact conductive copper layers without appreciable oxidation and without the need for an elevated temperature, post-deposition thermal treatment commonly required for noble metal particle-based ink processes. This low-cost copper patterning process is readily scalable on virtually any substrate and may be used to generate a variety of copper-based microwave devices on flexible, paper-based substrates.

  2. Copper on activated carbon for catalytic wet air oxidation

    Directory of Open Access Journals (Sweden)

    Nora Dolores Martínez

    2009-03-01

    Full Text Available Textile industry is an important source of water contamination. Some of the organic contaminants cannot be eliminated by nature in a reasonable period. Heterogeneous catalytic wet air oxidation is one of the most effective methods to purify wastewater with organic contaminants. In this work, catalysts based on copper supported on activated carbon were synthesized. The activated carbons were obtained from industrial wastes (apricot core and grape stalk of San Juan, Argentina. These were impregnated with a copper salt and thermically treated in an inert atmosphere. Analysis of specific surface, pore volume, p zc, acidity, basicity and XRD patterns were made in order to characterize the catalysts. The catalytic activity was tested in the oxidation of methylene blue (MB and polyvinyl alcohol (PVA in aqueous phase with pure oxygen. Reaction tests were carried out in a Parr batch reactor at different temperatures, with a 0.2 MPa partial pressure of oxygen. The amount of unconverted organics was measured by spectrophotometry. Higher temperatures were necessary for the degradation of PVA compared to those for methylene blue.

  3. Thief carbon catalyst for oxidation of mercury in effluent stream

    Science.gov (United States)

    Granite, Evan J.; Pennline, Henry W.

    2011-12-06

    A catalyst for the oxidation of heavy metal contaminants, especially mercury (Hg), in an effluent stream is presented. The catalyst facilitates removal of mercury through the oxidation of elemental Hg into mercury (II) moieties. The active component of the catalyst is partially combusted coal, or "Thief" carbon, which can be pre-treated with a halogen. An untreated Thief carbon catalyst can be self-promoting in the presence of an effluent gas streams entrained with a halogen.

  4. Heterogeneous catalysis of mixed oxides perovskite and heteropoly catalysts

    CERN Document Server

    Misono, M

    2014-01-01

    Mixed oxides are the most widely used catalyst materials for industrial catalytic processes. The principal objective of this book is to describe systematically the mixed oxide catalysts, from their fundamentals through their practical applications.  After describing concisely general items concerning mixed oxide and mixed oxide catalysts, two important mixed oxide catalyst materials, namely, heteropolyacids and perovskites, are taken as typical examples and discussed in detail. These two materials have several advantages: 1. They are, respectively, typical examples of salts of oxoacids an

  5. Synthesis and electrocatalytic water oxidation by electrode-bound helical peptide chromophore-catalyst assemblies.

    Science.gov (United States)

    Ryan, Derek M; Coggins, Michael K; Concepcion, Javier J; Ashford, Dennis L; Fang, Zhen; Alibabaei, Leila; Ma, Da; Meyer, Thomas J; Waters, Marcey L

    2014-08-01

    Artificial photosynthesis based on dye-sensitized photoelectrosynthesis cells requires the assembly of a chromophore and catalyst in close proximity on the surface of a transparent, high band gap oxide semiconductor for integrated light absorption and catalysis. While there are a number of approaches to assemble mixtures of chromophores and catalysts on a surface for use in artificial photosynthesis based on dye-sensitized photoelectrosynthesis cells, the synthesis of discrete surface-bound chromophore-catalyst conjugates is a challenging task with few examples to date. Herein, a versatile synthetic approach and electrochemical characterization of a series of oligoproline-based light-harvesting chromophore-water-oxidation catalyst assemblies is described. This approach combines solid-phase peptide synthesis for systematic variation of the backbone, copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) as an orthogonal approach to install the chromophore, and assembly of the water-oxidation catalyst in the final step. Importantly, the catalyst was found to be incompatible with the conditions both for amide bond formation and for the CuAAC reaction. The modular nature of the synthesis with late-stage assembly of the catalyst allows for systematic variation in the spatial arrangement of light-harvesting chromophore and water-oxidation catalyst and the role of intrastrand distance on chromophore-catalyst assembly properties. Controlled potential electrolysis experiments verified that the surface-bound assemblies function as water-oxidation electrocatalysts, and electrochemical kinetics data demonstrate that the assemblies exhibit greater than 10-fold rate enhancements compared to the homogeneous catalyst alone.

  6. Effect of the addition of rare earths on the activity of alumina supported copper cobaltite in CO oxidation, CH4 oxidation and NO decomposition

    Institute of Scientific and Technical Information of China (English)

    B Ivanov; I Spassova; M Milanova; G Tyuliev; M Khristova

    2015-01-01

    The effect of the addition of small amounts of rare earths (Ln=La, Ce, Nd and Gd) to alumina supported copper-cobalt spinel oxide on the catalysts efficiency in CO and CH4 oxidation and in NO decomposition was investigated. Samples of Ln/CuCo/Al catalyst were prepared and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic absorption spectroscopy (AAS), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), H2-temperature-programmed reduc-tion (H2-TPR), electron paramagnetic resonance (EPR) spectroscopy and low temperature nitrogen adsorption. The results showed that the addition of rare earths changed the surface state of the alumina supported copper-cobalt spinel catalyst. As a result, partial re-duction of copper species was observed as well as migration of these species between the surface and the bulk. The Ln/CuCo/Al catalysts behaved differently in oxidation and reduction processes. In oxidation processes where oxide structure was important, Ce/CuCo/Al and Nd/CuCo/Al were the most active catalysts. The catalyst Ce/CuCo/Al was the most active in the oxidation reactions because of the availability and favorable surface distribution of the redox couples Cu+/Cu2+ and Ce3+/Ce4+. In NO decompostion, Ln-modified catalysts significantly improved the selectivity of the process to N2.

  7. Copper Oxide Nanoparticles Synthesis by Electrochemical Method

    Directory of Open Access Journals (Sweden)

    Nitin DIGHORE

    2016-05-01

    Full Text Available Copper oxide nanoparticles were prepared by electrochemical reduction method which is environmental benign. Tetra ethyl ammonium bromide (TEAB, tetra propyl ammonium bromide (TPAB, tetra butyl ammonium bromide (TBAB were used as stabilizing agent in an organic medium viz. tetra hydro furan (THF and acetonitrile (ACN in 4:1 ratio by optimizing current density. The reduction process takes place under atmospheric condition over a period of 2 h. Such nanoparticles were prepared using simple electrolysis cell in which the sacrificial anode was a commercially available copper metal sheet and platinum (inert sheet acted as a cathode. The stabilizers were used to control the size of a nanoparticles. The synthesized copper oxide nanoparticles were characterized by using UV-Visible, FT-IR, XRD, SEM-EDS and TEM analysis techniques.DOI: http://dx.doi.org/10.5755/j01.ms.22.2.7501

  8. Catalyst for reduction of nitrogen oxides

    Science.gov (United States)

    Ott, Kevin C.

    2010-04-06

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  9. Reversible-Deactivation Radical Polymerization of Methyl Methacrylate Induced by Photochemical Reduction of Various Copper Catalysts

    Directory of Open Access Journals (Sweden)

    Jaroslav Mosnáček

    2014-11-01

    Full Text Available Photochemically mediated reversible-deactivation radical polymerization of methyl methacrylate was successfully performed using 50–400 ppm of various copper compounds such as CuSO4·5H2O, copper acetate, copper triflate and copper acetylacetonate as catalysts. The copper catalysts were reduced in situ by irradiation at wavelengths of 366–546 nm, without using any additional reducing agent. Bromopropionitrile was used as an initiator. The effects of various solvents and the concentration and structure of ligands were investigated. Well-defined polymers were obtained when at least 100 or 200 ppm of any catalyst complexed with excess tris(2-pyridylmethylamine as a ligand was used in dimethyl sulfoxide as a solvent.

  10. Nano copper ferrite: A reusable catalyst for the synthesis of , -unsaturated ketones

    Indian Academy of Sciences (India)

    Y L N Murthy; B S Diwakar; B Govindh; K Nagalakshmi; I V Kasi Viswanath; Rajendra Singh

    2012-05-01

    Copper ferrite nano material as reusable heterogeneous initiator in the synthesis of , -unsaturated ketones and allylation to acid chlorides are presented. The reaction of allylichalides with various acid chlorides is achieved in the presence of copper ferrite nano powders at room temperature in tetrahydrofuran (THF). The present method is first of its kind in the synthesis of title compounds without any additive/co-catalyst. The nano catalyst is easily recovered and its reusability is recorded.

  11. Antistatic Polycarbonate/Copper Oxide Composite

    Science.gov (United States)

    Kovich, Michael; Rowland, George R., Jr.

    2003-01-01

    A composite material consisting of polycarbonate filled with copper oxide has been found to be suitable as an antistatic material. This material was developed to satisfy a requirement for an antistatic material that has a mass density less than that of aluminum and that exhibits an acceptably low level of outgassing in a vacuum.

  12. Application of Heterogeneous Copper Catalyst in a Continuous Flow Process: Dehydrogenation of Cyclohexanol

    Science.gov (United States)

    Glin´ski, Marek; Ulkowska, Urszula; Iwanek, Ewa

    2016-01-01

    In this laboratory experiment, the synthesis of a supported solid catalyst (Cu/SiO2) and its application in the dehydrogenation of cyclohexanol performed under flow conditions was studied. The experiment was planned for a group of two or three students for two 6 h long sessions. The copper catalyst was synthesized using incipient wetness…

  13. Polyol Synthesis of Cobalt–Copper Alloy Catalysts for Higher Alcohol Synthesis from Syngas

    DEFF Research Database (Denmark)

    Mendes, Laiza V.P.; Snider, Jonathan L.; Fleischman, Samuel D.

    2017-01-01

    Novel catalysts for the selective production of higher alcohols from syngas could offer improved pathways towards synthetic fuels and chemicals. Cobalt–copper alloy catalysts have shown promising results for this reaction. To improve control over particle properties, a liquid phase nanoparticle s...

  14. Copper on Chitosan: A Recyclable Heterogeneous Catalyst for Azide-alkyne Cycloaddition Reactions in Water

    Science.gov (United States)

    Copper sulfate is immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with copper sulfate; the ensuing catalyst has been utilized for the azide-alkyne cycloaddition in aqueous media and it can be recycled and reused many time without loosing it...

  15. Oxidation-reduction catalyst and its process of use

    Science.gov (United States)

    Jordan, Jeffrey D. (Inventor); Watkins, Anthony Neal (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor)

    2008-01-01

    This invention relates generally to a ruthenium stabilized oxidation-reduction catalyst useful for oxidizing carbon monoxide, and volatile organic compounds, and reducing nitrogen oxide species in oxidizing environments, substantially without the formation of toxic and volatile ruthenium oxide species upon said oxidizing environment being at high temperatures.

  16. Moessbauer study of function of magnesium in iron oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    YangJie-Xin; MaoLian-Sheng; 等

    1997-01-01

    Moessbauer spectroscopy has been utilized for studying the action of Mg element in iron oxide catalysts used for the dehydrogenation of ethylbenzene to sytrene.The experimental results show that the presence of opportune amount of Mg can enhance the stability and dispersion of catalysts,i.e.Mg is an sueful structure promoter in this kind of catalysts.

  17. Identification of Active Phase for Selective Oxidation of Benzyl Alcohol with Molecular Oxygen Catalyzed by Copper-Manganese Oxide Nanoparticles

    Directory of Open Access Journals (Sweden)

    Roushown Ali

    2013-01-01

    Full Text Available Catalytic activity of copper-manganese mixed oxide nanoparticles (Cu/Mn = 1 : 2 prepared by coprecipitation method has been studied for selective oxidation of benzyl alcohol using molecular oxygen as an oxidizing agent. The copper-manganese (CuMn2 oxide catalyst exhibited high specific activity of 15.04 mmolg−1 h−1 in oxidation of benzyl alcohol in toluene as solvent. A 100% conversion of the benzyl alcohol was achieved with >99% selectivity to benzaldehyde within a short reaction period at 102°C. It was found that the catalytic performance is dependent on calcination temperature, and best activity was obtained for the catalyst calcined at 300°C. The high catalytic performance of the catalyst can be attributed to the formation of active MnO2 phase or absence of less active Mn2O3 phase in the mixed CuMn2 oxide. The catalyst has been characterized by powder X-ray diffraction (XRD, thermogravimetric analysis (TGA, scanning electron microscopy (SEM, transmission electron microscopy (TEM, Brunauer Emmett-Teller (BET surface area measurement, and Fourier transform infrared (FT-IR spectroscopies.

  18. Marine sponge skeleton photosensitized by copper phthalocyanine: A catalyst for Rhodamine B degradation

    Directory of Open Access Journals (Sweden)

    Norman Małgorzata

    2016-01-01

    Full Text Available We present a combined approach to photo-assisted degradation processes, in which a catalyst, H2O2 and UV irradiation are used together to enhance the oxidation of Rhodamine B (RB. The heterogeneous photocatalyst was made by the process of adsorption of copper phthalocyanine tetrasulfonic acid (CuPC onto purified spongin-based Hippospongia communis marine sponge skeleton (HcS. The product obtained, CuPC-HcS, was investigated by a variety of spectroscopic (carbon-13 nuclear magnetic resonance 13C NMR, Fourier transform infrared spectroscopy FTIR, energy-dispersive X-ray spectroscopy EDS and microscopic techniques (scanning electron microscopy SEM, fluorescent and optical microscopy, as well as thermal analysis. The study confirms the stable combination of the adsorbent and adsorbate. For a 10 mg/L RB solution, the percentage degradation reached 95% using CuPC-HcS as a heterocatalyst. The mechanism of RB removal involves adsorption and photodegradation simultaneously.

  19. Mordenite - Type Zeolite SCR Catalysts with Iron or Copper

    DEFF Research Database (Denmark)

    2012-01-01

    Cu/mordenite catalysts were found to be highly active for the SCR of NO with NH3 and exhibited high resistance to alkali poisoning. Redox and acidic properties of Cu/mordenite were well preserved after poisoning with potassium unlike that of vanadium catalysts. Fe-mordenite catalysts also reveale...... to be essential requirements for the high alkali resistance. Mordenite-type zeolite based catalysts could therefore be attractive alternatives to conventional SCR catalysts for biomass fired power plant flue gas treatment....

  20. Performance of silica-supported copper oxide sorbents for SO@#x@#/NO@#x@#-removal from flue gas II. Selective catalytic reduction of nitric oxide by ammonia

    NARCIS (Netherlands)

    Kiel, J.H.A.; Kiel, J.H.A.; Edelaar, A.C.S.; Prins, W.; van Swaaij, Willibrordus Petrus Maria

    1992-01-01

    The selective catalytic reduction (SCR) of nitric oxide by ammonia was studied for silica-supported copper oxide particles to be used as a sorbent/catalyst in a continuous process for the simultaneous removal of SOx and NOx from flue gases. The SCR-behaviour was determined as a function of the

  1. Iron Oxide-Supported Copper Oxide Nanoparticles (Nanocat-Fe-CuO): Magnetically Recyclable Catalysts for the Synthesis of Pyrazole Derivatives, 4-Methoxyaniline, and Ullmann-type Condensation Reactions

    Science.gov (United States)

    An efficient and benign protocol is reported for the synthesis of 4-methoxyaniline, medicinally important pyrazole derivatives, and Ullmann-type condensation reaction using magnetically separable and reusable magnetite-supported copper (nanocat-Fe-CuO) nanoparticles under mild co...

  2. Iron Oxide-Supported Copper Oxide Nanoparticles (Nanocat-Fe-CuO): Magnetically Recyclable Catalysts for the Synthesis of Pyrazole Derivatives, 4-Methoxyaniline, and Ullmann-type Condensation Reactions

    Science.gov (United States)

    An efficient and benign protocol is reported for the synthesis of 4-methoxyaniline, medicinally important pyrazole derivatives, and Ullmann-type condensation reaction using magnetically separable and reusable magnetite-supported copper (nanocat-Fe-CuO) nanoparticles under mild co...

  3. Catalytic incineration of CO and VOC emissions over supported metal oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Larsson, Per-Olof

    1999-05-01

    Catalytic incineration is one of the methods to reduce the emissions of CO and VOCs. Low operation temperature and low catalyst cost are essential parameters for catalytic incinerators. Pt/Al{sub 2}O{sub 3} catalysts are frequently used today, but the cheaper metal oxide catalysts can be very competitive if comparable overall activity is obtained. This thesis concerns how it is possible to decrease the operation temperature for supported metal oxide catalysts by using different supports, active metal oxides and additives. In the thesis it is demonstrated that different copper oxide based catalysts have the best activity and durability for complete oxidation among several tested metal oxide catalysts. CuO{sub x} supported on TiO{sub 2} and Al{sub 2}O{sub 3} showed increased activity with the CuO{sub x} loading up to the threshold coverage for formation of crystalline CuO particles, which is 12 {mu}mol/m{sup 2} on TiO{sub 2} and 6 {mu}mol/m{sup 2} on Al{sub 2}O{sub 3}. Up to the threshold coverage for CuO formation, well dispersed copper oxide species were formed on TiO{sub 2}, and a dispersed copper aluminate surface phase was formed on Al{sub 2}O{sub 3}. Durability tests showed accelerated sintering of TiO{sub 2} by copper, but stabilisation was possible by modification of the TiO{sub 2} with CeO{sub x} before the deposition of CuO{sub x}. The stabilisation was obtained by formation of a Ce-O-Ti surface phase. Addition of CeO{sub x} also enhanced the activity of the copper oxide species thanks to favourable interaction between the active copper oxide species and the CeO{sub x} on the support, which could be seen as increased reducibility in TPR experiments. The increased activity and reducibility was also observed for CuO{sub x} supported on ceria modified Al{sub 2}O{sub 3}. In this regard it was shown that CuO{sub x} deposited on CeO{sub 2}(001) surfaces was substantially more active for CO oxidation than copper oxide deposited on CeO{sub 2}(111) Surfaces. This

  4. Propene metathesis over silica-supported tungsten oxide catalyst-catalyst induction mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Basrur, A.G.; Patwardhan, S.R.; Vyas, S.N. (Indian Inst. of Tech., Bombay (India))

    1991-01-01

    The propene metathesis reaction was studied from the point of view of elucidating the mechanism of catalyst induction and establishing conditions for maximum activity. Instrumental techniques such as ESR, IR, and TPD were used to study the various aspects. During catalyst induction, trace quantities of acetone and acetaldehyde were detected in the product stream, indicating that lattice oxygen from tungsten oxide might be responsible for these products. Induction appeared to proceed via two steps since pretreatment of the catalyst with nitrogen and hydrogen yielded a decreased amount of acetone in the latter case whereas acetaldehyde remained unaffected. ESR studies indicated some interaction between tungsten oxide and silica at the catalyst preparatory stage as well as stabilization of reduced tungsten species on the catalyst after its use and regeneration. Catalyst activity appeared to depend on conditions of pretreatment. Change in nitrogen pretreatment temperature from 500 to 600{sup o}C resulted in transition from strong to negligible external mass transfer behavior of the catalyst. TPD studies in this context showed possible loss of lattice oxygen from tungsten oxide under the above-mentioned conditions of catalyst pretreatment. ESR studies indicated the reduction of WO{sub 3} to a nonstoichiometric oxidation state. Hence catalytic activity appears to be related to the nonstoichiometric state of tungsten oxide, which may be WO{sub 2.9} (as deduced from the blue-violet color of the used catalyst).

  5. Influence of Ce/Zr ratio on CO oxidation activity of ceria-zirconia supported Cu catalyst

    Science.gov (United States)

    Hattori, Masatomo; Haneda, Masaaki; Ozawa, Masakuni

    2016-01-01

    The influence of Ce/Zr ratios in the cerium-rich region on the dispersibility and reduction property of Cu catalysts supported on ceria-zirconia composite oxides was investigated. In the catalysts, the dispersibility of copper oxide species on ceria-zirconia supports was different depending on Ce/Zr ratio. The particle size of copper oxide species on Ce0.7Zr0.3O2 was smaller than that on Ce0.5Zr0.5O2. CO oxidation activity of 1.0 wt % Cu/Ce0.7Zr0.3O2 was higher than that of 1.0 wt % Cu/Ce0.5Zr0.5O2. Temperature programmed reduction by CO (CO-TPR) measurement revealed that the reducibility of Cu/Ce0.7Zr0.3O2 was higher than that of Cu/Ce0.5Zr0.5O2. The temperature of the first peak in CO-TPR profiles for both catalysts was in good agreement with the temperature at which the conversion of CO reached 50% (T50). It is suggested that the copper oxide species — ceria-zirconia interaction influences the activation of oxygen at the interface between copper oxide species and ceria-zirconia, resulting in different catalytic performance for CO oxidation.

  6. Mordenite - Type Zeolite SCR Catalysts with Iron or Copper

    DEFF Research Database (Denmark)

    2012-01-01

    Cu/mordenite catalysts were found to be highly active for the SCR of NO with NH3 and exhibited high resistance to alkali poisoning. Redox and acidic properties of Cu/mordenite were well preserved after poisoning with potassium unlike that of vanadium catalysts. Fe-mordenite catalysts also reveale...... to be essential requirements for the high alkali resistance. Mordenite-type zeolite based catalysts could therefore be attractive alternatives to conventional SCR catalysts for biomass fired power plant flue gas treatment.......Cu/mordenite catalysts were found to be highly active for the SCR of NO with NH3 and exhibited high resistance to alkali poisoning. Redox and acidic properties of Cu/mordenite were well preserved after poisoning with potassium unlike that of vanadium catalysts. Fe-mordenite catalysts also revealed...

  7. Surface Chemistry and Properties of Oxides as Catalyst Supports

    Energy Technology Data Exchange (ETDEWEB)

    DeBusk, Melanie Moses [ORNL; Narula, Chaitanya Kumar [ORNL; Contescu, Cristian I [ORNL

    2015-01-01

    Heterogeneous catalysis relies on metal-oxides as supports for the catalysts. Catalyst supports are an indispensable component of most heterogeneous catalysts, but the role of the support is often minimized in light of the one played by the catalytically active species it supports. The active species of supported catalysts are located on the surface of the support where their contact with liquid or gas phase reactants will be greatest. Considering that support plays a major role in distribution and stability of active species, the absorption and retention of reactive species, and in some cases in catalytic reaction, the properties and chemistry that can occur at the surface of an oxide support are important for understanding their impact on the activity of a supported catalyst. This chapter examines this rich surface chemistry and properties of oxides used as catalyst supports, and explores the influence of their interaction with the active species.

  8. Acid monolayer functionalized iron oxide nanoparticle catalysts

    Science.gov (United States)

    Ikenberry, Myles

    Superparamagnetic iron oxide nanoparticle functionalization is an area of intensely active research, with applications across disciplines such as biomedical science and heterogeneous catalysis. This work demonstrates the functionalization of iron oxide nanoparticles with a quasi-monolayer of 11-sulfoundecanoic acid, 10-phosphono-1-decanesulfonic acid, and 11-aminoundecanoic acid. The carboxylic and phosphonic moieties form bonds to the iron oxide particle core, while the sulfonic acid groups face outward where they are available for catalysis. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectrometry (XPS), and dynamic light scattering (DLS). The sulfonic acid functionalized particles were used to catalyze the hydrolysis of sucrose at 80° and starch at 130°, showing a higher activity per acid site than the traditional solid acid catalyst Amberlyst-15, and comparing well against results reported in the literature for sulfonic acid functionalized mesoporous silicas. In sucrose catalysis reactions, the phosphonic-sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic-sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. Between the two sulfonic ligands, the phosphonates produced a more tightly packed monolayer, which corresponded to a higher sulfonic acid loading, lower agglomeration, lower recoverability through application of an external magnetic field, and higher activity per acid site for the hydrolysis of starch. Functionalizations with 11-aminoundecanoic acid resulted in some amine groups binding to the surfaces of iron oxide nanoparticles. This amine binding is commonly ignored in iron oxide

  9. Biogenic nanoparticles: copper, copper oxides, copper sulphides, complex copper nanostructures and their applications.

    Science.gov (United States)

    Rubilar, Olga; Rai, Mahendra; Tortella, Gonzalo; Diez, Maria Cristina; Seabra, Amedea B; Durán, Nelson

    2013-09-01

    Copper nanoparticles have been the focus of intensive study due to their potential applications in diverse fields including biomedicine, electronics, and optics. Copper-based nanostructured materials have been used in conductive films, lubrification, nanofluids, catalysis, and also as potent antimicrobial agent. The biogenic synthesis of metallic nanostructured nanoparticles is considered to be a green and eco-friendly technology since neither harmful chemicals nor high temperatures are involved in the process. The present review discusses the synthesis of copper nanostructured nanoparticles by bacteria, fungi, and plant extracts, showing that biogenic synthesis is an economically feasible, simple and non-polluting process. Applications for biogenic copper nanoparticles are also discussed.

  10. Development of highly faceted reduced graphene oxide-coated copper oxide and copper nanoparticles on a copper foil surface

    Directory of Open Access Journals (Sweden)

    Rebeca Ortega-Amaya

    2016-07-01

    Full Text Available This work describes the formation of reduced graphene oxide-coated copper oxide and copper nanoparticles (rGO-Cu2ONPs, rGO-CuNPs on the surface of a copper foil supporting graphene oxide (GO at annealing temperatures of 200–1000 °C, under an Ar atmosphere. These hybrid nanostructures were developed from bare copper oxide nanoparticles which grew at an annealing temperature of 80 °C under nitrogen flux. The predominant phase as well as the particle size and shape strongly depend on the process temperature. Characterization with transmission electron microscopy and scanning electron microscopy indicates that Cu or Cu2O nanoparticles take rGO sheets from the rGO network to form core–shell Cu–rGO or Cu2O–rGO nanostructures. It is noted that such ones increase in size from 5 to 800 nm as the annealing temperature increases in the 200–1000 °C range. At 1000 °C, Cu nanoparticles develop a highly faceted morphology, displaying arm-like carbon nanorods that originate from different facets of the copper crystal structure.

  11. Development of highly faceted reduced graphene oxide-coated copper oxide and copper nanoparticles on a copper foil surface

    Science.gov (United States)

    Matsumoto, Yasuhiro; Espinoza-Rivas, Andrés M; Pérez-Guzmán, Manuel A; Ortega-López, Mauricio

    2016-01-01

    Summary This work describes the formation of reduced graphene oxide-coated copper oxide and copper nanoparticles (rGO-Cu2ONPs, rGO-CuNPs) on the surface of a copper foil supporting graphene oxide (GO) at annealing temperatures of 200–1000 °C, under an Ar atmosphere. These hybrid nanostructures were developed from bare copper oxide nanoparticles which grew at an annealing temperature of 80 °C under nitrogen flux. The predominant phase as well as the particle size and shape strongly depend on the process temperature. Characterization with transmission electron microscopy and scanning electron microscopy indicates that Cu or Cu2O nanoparticles take rGO sheets from the rGO network to form core–shell Cu–rGO or Cu2O–rGO nanostructures. It is noted that such ones increase in size from 5 to 800 nm as the annealing temperature increases in the 200–1000 °C range. At 1000 °C, Cu nanoparticles develop a highly faceted morphology, displaying arm-like carbon nanorods that originate from different facets of the copper crystal structure. PMID:27547618

  12. A clamp-like biohybrid catalyst for DNA oxidation

    Science.gov (United States)

    van Dongen, Stijn F. M.; Clerx, Joost; Nørgaard, Kasper; Bloemberg, Tom G.; Cornelissen, Jeroen J. L. M.; Trakselis, Michael A.; Nelson, Scott W.; Benkovic, Stephen J.; Rowan, Alan E.; Nolte, Roeland J. M.

    2013-11-01

    In processive catalysis, a catalyst binds to a substrate and remains bound as it performs several consecutive reactions, as exemplified by DNA polymerases. Processivity is essential in nature and is often mediated by a clamp-like structure that physically tethers the catalyst to its (polymeric) template. In the case of the bacteriophage T4 replisome, a dedicated clamp protein acts as a processivity mediator by encircling DNA and subsequently recruiting its polymerase. Here we use this DNA-binding protein to construct a biohybrid catalyst. Conjugation of the clamp protein to a chemical catalyst with sequence-specific oxidation behaviour formed a catalytic clamp that can be loaded onto a DNA plasmid. The catalytic activity of the biohybrid catalyst was visualized using a procedure based on an atomic force microscopy method that detects and spatially locates oxidized sites in DNA. Varying the experimental conditions enabled switching between processive and distributive catalysis and influencing the sliding direction of this rotaxane-like catalyst.

  13. Bimetallic ruthenium-copper nanoparticles embedded in mesoporous carbon as an effective hydrogenation catalyst.

    Science.gov (United States)

    Liu, Jiajia; Zhang, Li Li; Zhang, Jiatao; Liu, Tao; Zhao, X S

    2013-11-21

    Bimetallic ruthenium-copper nanoparticles embedded in the pore walls of mesoporous carbon were prepared via a template route and evaluated in terms of catalytic properties in D-glucose hydrogenation. The existence of bimetallic entities was supported by Ru L3-edge and Cu K-edge X-ray absorption results. The hydrogen spillover effect of the bimetallic catalyst on the hydrogenation reaction was evidenced by the results of both hydrogen and carbon monoxide chemisorptions. The bimetallic catalyst displayed a higher catalytic activity than the single-metal catalysts prepared using the same approach, namely ruthenium or copper nanoparticles embedded in the pore walls of mesoporous carbon. This improvement was due to the changes in the geometric and electronic structures of the bimetallic catalyst because of the presence of the second metal.

  14. Catalytic Oxidation of Phenol over Zeolite Based Cu/Y-5 Catalyst: Part 1: Catalyst Preparation and Characterization

    Directory of Open Access Journals (Sweden)

    K. Maduna Valkaj

    2015-01-01

    -Mead method of nonlinear regression. On the basis of the obtained results of characterization process and conducted catalytic tests, the following can be observed. Zeolite structure of the prepared catalyst was confirmed through powder X-ray diffraction, scanning electron microscopy and adsorption techniques. Their catalytic performance was monitored in terms of phenol and total organic carbon (TOC conversions, hydrogen peroxide decomposition, by-product distribution and degree of copper leached into the aqueous solution. The obtained experimental results indicate that in the space of 180 minutes, the use of these catalysts allows almost total elimination of phenol and significant removal of total organic carbon content with the use of small amounts of catalyst (0.1 g dm–3 and substoichiometric level (71.4 % of oxidant required for complete oxidation of organic pollutant. The main product among aromatics was catechol, followed by hydroquinone and benzoquinone, which exhibited the typical pattern for a series reaction scheme. The distribution of carboxylic acids was as follows: maleic, fumaric, acetic and oxalic acids. These low-molecular carboxylic acids and aromatic compounds were responsible for the TOC that remained after almost complete removal of phenol. Moreover, one of the most interesting options was to use CWPO as a pre-treatment prior to biological treatment, for simple organic acids that are highly biodegradable. During the reactions, destabilization of the catalyst was observed in terms of leaching of copper from zeolite into the reaction mixture, but the previous investigations of similar catalytic systems showed that the activity of the solid catalyst was not due to the homogeneous contribution of the copper leached from the catalyst, but was more likely due to the activity of the heterogeneous catalyst. Further investigations on the mechanism of catalyst destabilization and methods of stabilization are the subject of the following article in the series. The

  15. Bio-inspired multinuclear copper complexes covalently immobilized on reduced graphene oxide as efficient electrocatalysts for the oxygen reduction reaction.

    Science.gov (United States)

    Xi, Yue-Ting; Wei, Ping-Jie; Wang, Ru-Chun; Liu, Jin-Gang

    2015-05-01

    Inspired by the multicopper active site of laccase, which efficiently catalyzes the oxygen reduction reaction (ORR), herein we report a novel bio-inspired ORR catalyst composed of a multinuclear copper complex that was immobilized on the surface of reduced graphene oxide (rGO) via the covalently grafted triazole-dipyridine (TADPy) dinucleating ligand. This rGO-TADPyCu catalyst exhibited high ORR activity and superior long-term stability compared to Pt/C in alkaline media.

  16. CeO2 nanorods-supported transition metal catalysts for CO oxidation.

    Science.gov (United States)

    Mock, Samantha A; Sharp, Shannon E; Stoner, Thomas R; Radetic, Michael J; Zell, Elizabeth T; Wang, Ruigang

    2016-03-15

    A catalytically active oxide support in combination with metal catalysts is required in order to achieve better low temperature activity and selectivity. Here, we report that CeO2 nanorods with a superior surface oxygen release/storage capability were used as an active support of transition metal (TM) catalysts (Mn, Fe, Co, Ni, Cu) for CO oxidation reaction. The as-prepared CeO2 nanorods supported 10 wt% TM catalysts were highly active for CO oxidation at low temperature, except for the Fe sample. It is found that the 10%Cu-CeO2 catalyst performed best, and it provided a lower light-off temperature with T50 (50% conversion) at 75 °C and T100 (100% conversion) of CO to CO2 at 194 °C. The atomic level surface structure of CeO2 nanorods was investigated in order to understand the improved low temperature catalytic activity. The richness of surface roughness and various defects (voids, lattice distortion, bending, steps, twinning) on CeO2 nanorods could facilitate oxygen release and storage. According to XRD and Raman analysis, copper species migrate into the bulk CeO2 nanorods to a greater degree. Since CO adsorbed over the surface of the catalyst/support is detrimental to its catalytic activity, the surface defects on the CeO2 nanorods and CeO2-TM interactions were critical to the enhanced activity.

  17. A Nanoarchitecture Based on Silver and Copper Oxide with an Exceptional Response in the Chlorine-Promoted Epoxidation of Ethylene.

    Science.gov (United States)

    Ramirez, Adrian; Hueso, Jose L; Suarez, Hugo; Mallada, Reyes; Ibarra, Alfonso; Irusta, Silvia; Santamaria, Jesus

    2016-09-05

    The selective oxidation of ethylene to ethylene epoxide is highly challenging as a result of competing reaction pathways leading to the deep oxidation of both ethylene and ethylene oxide. Herein we present a novel catalyst based on silver and copper oxide with an excellent response in the selective oxidation pathway towards ethylene epoxide. The catalyst is composed of different silver nanostructures dispersed on a tubular copper oxide matrix. This type of hybrid nanoarchitecture seems to facilitate the accommodation of chlorine promoters, leading to high yields at low reaction temperatures. The stability after the addition of chlorine promoters implies a substantial improvement over the industrial practice: a single pretreatment step at ambient pressure suffices in contrast with the common practice of continuously feeding organochlorinated precursors during the reaction.

  18. Steam reforming of methanol over copper loaded anodized aluminum oxide (AAO) prepared through electrodeposition

    Science.gov (United States)

    Linga Reddy, E.; Karuppiah, J.; Lee, Hyun Chan; Kim, Dong Hyun

    2014-12-01

    In order to study the steam reforming of methanol (SRM) to produce hydrogen for fuel cells, porous γ-alumina support is developed on Al substrate using anodic oxidation process and copper catalyst particles are deposited homogeneously over anodic aluminum oxide (AAO) surface by electrodeposition method. We investigated the effect of electrodeposition time and hot water treatment (HWT) on the activity of catalysts for SRM reaction in the temperature range between 160 and 360 °C. The experimental results indicate that the SRM activity, CO2 and dimethyl ether (DME) selectivity's over Cu catalysts increased as the electrodeposition time increased from 30 to 120 s, further increment in deposition time of Cu have no significant effect on it. The rates of SRM conversion are found to be higher for the catalysts made from the supports obtained after HWT, which may be due to the enhancement in the surface area of AAO support. It is found that the SRM activity and CO2 selectivity strongly depended upon the free exposed copper sites available for methanol adsorption and reaction, and DME in products is mainly observed in the reaction temperature range between 300 and 350 °C and it is higher for the catalysts with low Cu content.

  19. Synthesis of copper hydroxide branched nanocages and their transformation to copper oxide

    KAUST Repository

    LaGrow, Alec P.

    2014-08-21

    Copper oxide nanostructures have been explored in the literature for their great promise in the areas of energy storage and catalysis, which can be controlled based on their shape. Herein we describe the synthesis of complex branched nanocages of copper hydroxide with an alternating stacked morphology. The size of the nanocages\\' core and the length of the branches can be controlled by the temperature and ratio of surfactant used, varying the length from 85 to 232 nm long, and varying the core size from 240 to 19 nm. The nanostructures\\' unique morphology forms by controlling the growth of an initial spherical seed, and the crystallization of the anisotropic arms. The Cu(OH)2 nanostructures can be converted to polycrystalline CuO branched nanocages and Cu2O nanoframes. We show that the branched nanocage morphology of CuO has markedly superior catalytic properties to previous reports with CuO nanomaterials, resulting in a rapid and efficient catalyst for C-S coupling. © 2014 American Chemical Society.

  20. Copper-cerium oxides supported on carbon nanomaterial for preferential oxidation of carbon monoxide

    Institute of Scientific and Technical Information of China (English)

    高美怡; 江楠; 赵宇宏; 徐长进; 苏海全; 曾尚红

    2016-01-01

    The CuxO-CeO2/Fe@CNSs, CuxO-CeO2/MWCNTs-Co and CuxO-CeO2/MWCNTs-Ni catalysts were prepared by the im-pregnation method and characterized by transmission electron microscopy, scanning electron microscopy, X-ray powder diffrac-tion, H2-temperature programmed reduction and N2 adsorption-desorption techniques. It was found that the Fe nanoparticles were encapsulated into the multi-layered carbon nanospheres (CNSs). However, the multi-wall carbon nanotubes (MWCNTS) were generated on the Co/Al2O3 and Ni/Al2O3 precursor. The addition of carbon nanomaterial as supports could improve structural properties and low-temperature activity of the CuO-CeO2 catalyst, and save the used amount of metal catalysts in the temperature range with high selectivity for CO oxidation. The copper-cerium oxides supported on carbon nanomaterial had good resistence to H2O and CO2.

  1. Copper complexes as catalyst precursors in the electrochemical hydrogen evolution reaction.

    Science.gov (United States)

    Kügler, Merle; Scholz, Julius; Kronz, Andreas; Siewert, Inke

    2016-04-28

    Herein, we report the synthesis and species distribution of copper(ii) complexes based on two different ligand scaffolds and the application of the two complexes in the electrochemical proton reduction catalysis. The ligands bind to one or two copper(II) ions and the pH-dependent mono/dinuclear equilibrium depends on the steric bulk of the ligands. The two water soluble copper(II) complexes were investigated for their activities in the electrochemical hydrogen evolution reaction (HER). In both complexes the copper(ii) ions have a N4-coordination environment composed of N-heterocycles, although in different coordination geometries (SPY-5 and TBPY-5). The solutions of the complexes were highly active catalysts in water at acidic pH but the complexes decompose under catalytic conditions. They act as precursors for highly active copper(0) and Cu2O deposits at the electrode surface, which are in turn the active catalysts. The absence or presence of the ligands has neither an influence on the catalytic activity of the solutions nor an influence on the activity of the deposit formed during controlled potential electrolysis. Finally, we can draw some conclusions on the stability of copper catalysts in the aqueous electrochemical HER.

  2. A dinuclear copper(II) electrocatalyst both water reduction and oxidation

    Science.gov (United States)

    Zhou, Ling-Ling; Fang, Ting; Cao, Jie-Ping; Zhu, Zhi-Hong; Su, Xiao-Ting; Zhan, Shu-Zhong

    2015-01-01

    Splitting water is a key challenge in the production of chemical fuels from electricity. Although several catalysts have been developed for these reactions, substantial challenges remain towards the ultimate goal of an efficient, inexpensive and robust electrocatalyst. Until now, there is as yet no report on both water oxidation and reduction by identical catalyst. Reported here is the first soluble copper-based catalyst, Cu(Me2oxpn)Cu(OH)2] 1 (Me2oxpn: N,N‧-bis(2,2‧-dimethyl-3-aminopropyl)oxamido) for both electrolytic water oxidation and reduction. Water oxidation occurs at an overpotential of 636 mV vs SHE to give O2 with a turnover frequency (TOF) of ∼2.14 s-1. Electrochemical studies also indicate that 1 is a soluble molecular species, that is among the most rapid homogeneous water reduction catalysts, with a TOF of 654 mol of hydrogen per mole of catalyst per hour at an overpotential of 789 mV vs SHE (pH 7.0). Sustained water reduction catalysis occurs at glassy carbon (GC) to give H2 over a 32 h electrolysis period with 95% Faradaic yield and no observable decomposition of the catalyst.

  3. An attempt to selectively oxidize methane over supported gold catalysts

    NARCIS (Netherlands)

    Hereijgers, B.P.C.; Weckhuysen, B.M.

    2011-01-01

    The potential of supported gold catalysts for the selective gas-phase oxidation of methane to methanol with molecular oxygen was investigated. A broad range of supported gold-based catalyst materials was synthesized using reducible and non-reducible support materials. Although the formation of small

  4. 介孔 TiO2担载 Cu(OH)2及其催化炔烃氧化偶联反应%Mesoporous Titania Supported Copper Hydroxide as an Efficient Heterogeneous Catalyst in Oxidative Homocoupling of Alkynes

    Institute of Scientific and Technical Information of China (English)

    张海鹏; 潘庆芝; 邹永存

    2014-01-01

    Ordered mesoporous titania supported copper hydroxide was used as catalysts in heterogeneous oxi-dative homocoupling of alkynes(Glaser reaction). The results showed high catalytic performance. Highly dis-persed copper hydroxide was regarded as the active site and mesoporous structure of TiO2 benefit the high dis-persion of active sites as well as the diffusion of the reactants and products in the reactions. 1,3-Dyne deriva-tive, the products of Glaser reaction, is an important class of compounds in chemistry and materials science. Thus, Cu(OH) 2 / TiO2 is of great importance in the industrial application.%在有序介孔 TiO2中原位担载了高分散的 Cu(OH)2,并将其应用于炔烃的氧化偶联(Glaser)多相催化反应,该催化剂表现出很高的催化活性。 Cu(OH)2为催化剂的主要活性组分, TiO2的有序介孔和较大的比表面积有利于 Cu(OH)2的分散以及反应物和产物的扩散,具有重要的应用前景。

  5. Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

    Science.gov (United States)

    Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.

    2011-01-01

    NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

  6. Fully Copper-Exchanged High-Silica LTA Zeolites as Unrivaled Hydrothermally Stable NH3 -SCR Catalysts.

    Science.gov (United States)

    Ryu, Taekyung; Ahn, Nak Ho; Seo, Seungwan; Cho, Jung; Kim, Hyojun; Jo, Donghui; Park, Gi Tae; Kim, Pyung Soon; Kim, Chang Hwan; Bruce, Elliott L; Wright, Paul A; Nam, In-Sik; Hong, Suk Bong

    2017-03-13

    Diesel engine technology is still the most effective solution to meet tighter CO2 regulations in the mobility and transport sector. In implementation of fuel-efficient diesel engines, the poor thermal durability of lean nitrogen oxides (NOx ) aftertreatment systems remains as one major technical hurdle. Divalent copper ions when fully exchanged into high-silica LTA zeolites are demonstrated to exhibit excellent activity maintenance for NOx reduction with NH3 under vehicle simulated conditions even after hydrothermal aging at 900 °C, a critical temperature that the current commercial Cu-SSZ-13 catalyst cannot overcome owing to thermal deactivation. Detailed structural characterizations confirm the presence of Cu(2+) ions only at the center of single 6-rings that act not only as a catalytically active center, but also as a dealumination suppressor. The overall results render the copper-exchanged LTA zeolite attractive as a viable substitute for Cu-SSZ-13.

  7. Molecular responses of mouse macrophages to copper and copper oxide nanoparticles inferred from proteomic analyses.

    Science.gov (United States)

    Triboulet, Sarah; Aude-Garcia, Catherine; Carrière, Marie; Diemer, Hélène; Proamer, Fabienne; Habert, Aurélie; Chevallet, Mireille; Collin-Faure, Véronique; Strub, Jean-Marc; Hanau, Daniel; Van Dorsselaer, Alain; Herlin-Boime, Nathalie; Rabilloud, Thierry

    2013-11-01

    The molecular responses of macrophages to copper-based nanoparticles have been investigated via a combination of proteomic and biochemical approaches, using the RAW264.7 cell line as a model. Both metallic copper and copper oxide nanoparticles have been tested, with copper ion and zirconium oxide nanoparticles used as controls. Proteomic analysis highlighted changes in proteins implicated in oxidative stress responses (superoxide dismutases and peroxiredoxins), glutathione biosynthesis, the actomyosin cytoskeleton, and mitochondrial proteins (especially oxidative phosphorylation complex subunits). Validation studies employing functional analyses showed that the increases in glutathione biosynthesis and in mitochondrial complexes observed in the proteomic screen were critical to cell survival upon stress with copper-based nanoparticles; pharmacological inhibition of these two pathways enhanced cell vulnerability to copper-based nanoparticles, but not to copper ions. Furthermore, functional analyses using primary macrophages derived from bone marrow showed a decrease in reduced glutathione levels, a decrease in the mitochondrial transmembrane potential, and inhibition of phagocytosis and of lipopolysaccharide-induced nitric oxide production. However, only a fraction of these effects could be obtained with copper ions. In conclusion, this study showed that macrophage functions are significantly altered by copper-based nanoparticles. Also highlighted are the cellular pathways modulated by cells for survival and the exemplified cross-toxicities that can occur between copper-based nanoparticles and pharmacological agents.

  8. Molecular Responses of Mouse Macrophages to Copper and Copper Oxide Nanoparticles Inferred from Proteomic Analyses*

    Science.gov (United States)

    Triboulet, Sarah; Aude-Garcia, Catherine; Carrière, Marie; Diemer, Hélène; Proamer, Fabienne; Habert, Aurélie; Chevallet, Mireille; Collin-Faure, Véronique; Strub, Jean-Marc; Hanau, Daniel; Van Dorsselaer, Alain; Herlin-Boime, Nathalie; Rabilloud, Thierry

    2013-01-01

    The molecular responses of macrophages to copper-based nanoparticles have been investigated via a combination of proteomic and biochemical approaches, using the RAW264.7 cell line as a model. Both metallic copper and copper oxide nanoparticles have been tested, with copper ion and zirconium oxide nanoparticles used as controls. Proteomic analysis highlighted changes in proteins implicated in oxidative stress responses (superoxide dismutases and peroxiredoxins), glutathione biosynthesis, the actomyosin cytoskeleton, and mitochondrial proteins (especially oxidative phosphorylation complex subunits). Validation studies employing functional analyses showed that the increases in glutathione biosynthesis and in mitochondrial complexes observed in the proteomic screen were critical to cell survival upon stress with copper-based nanoparticles; pharmacological inhibition of these two pathways enhanced cell vulnerability to copper-based nanoparticles, but not to copper ions. Furthermore, functional analyses using primary macrophages derived from bone marrow showed a decrease in reduced glutathione levels, a decrease in the mitochondrial transmembrane potential, and inhibition of phagocytosis and of lipopolysaccharide-induced nitric oxide production. However, only a fraction of these effects could be obtained with copper ions. In conclusion, this study showed that macrophage functions are significantly altered by copper-based nanoparticles. Also highlighted are the cellular pathways modulated by cells for survival and the exemplified cross-toxicities that can occur between copper-based nanoparticles and pharmacological agents. PMID:23882024

  9. Activity and deactivation of sulphated TiO2- and ZrO2-based V, Cu, and Fe oxide catalysts for NO abatement in alkali containing flue gases

    DEFF Research Database (Denmark)

    Kustov, Arkadii; Rasmussen, Søren Birk; Fehrmann, Rasmus

    2007-01-01

    Vanadia, copper and iron oxide catalysts supported on conventional TiO2, ZrO2, and sulphated-TiO2 and ZrO2 have been prepared. These catalysts were characterized by elemental analysis, N-2-BET, XRD, and NH3-TPD methods. The influence of potassium oxide additives on the acidity and activity in NO ...

  10. A photoreducible copper(II)-tren complex of practical value: generation of a highly reactive click catalyst.

    Science.gov (United States)

    Harmand, Lydie; Lambert, Romain; Scarpantonio, Luca; McClenaghan, Nathan D; Lastécouères, Dominique; Vincent, Jean-Marc

    2013-11-25

    A detailed study on the photoreduction of the copper(II) precatalyst 1 to generate a highly reactive cuprous species for the copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) click reaction is presented. For the photoactive catalyst described herein, the activation is driven by a photoinduced electron transfer (PET) process harnessing a benzophenone-like ketoprofenate chromophore as a photosensitizer, which is equally the counterion. The solvent is shown to play a major role in the Cu(II) to Cu(I) reduction process as the final electron source, and the influence of the solvent nature on the photoreduction efficiency has been studied. Particular attention was paid to the use of water as a potential solvent, aqueous media being particularly appealing for CuAAC processes. The ability to solubilize the copper-tren complexes in water through the formation of inclusion complexes with β-CDs is demonstrated. Data is also provided on the fate of the copper(I)-tren catalytic species when reacting with O2, O2 being used to switch off the catalysis. These data show that partial oxidation of the secondary benzylamine groups of the ligand to benzylimines occurs. Preliminary results show that when prolonged irradiation times are employed a Cu(I) to Cu(0) over-reduction process takes place, leading to the formation of copper nanoparticles (NPs). Finally, the main objective of this work being the development of photoactivable catalysts of practical value for the CuAAC, the catalytic, photolatent, and recycling properties of 1 in water and organic solvents are reported.

  11. Easy Access to Metallic Copper Nanoparticles with High Activity and Stability for CO Oxidation.

    Science.gov (United States)

    Gonçalves, Renato V; Wojcieszak, Robert; Wender, Heberton; Sato B Dias, Carlos; Vono, Lucas L R; Eberhardt, Dario; Teixeira, Sergio R; Rossi, Liane M

    2015-04-22

    Copper catalysts are very promising, affordable alternatives for noble metals in CO oxidation; however, the nature of the active species remains unclear and differs throughout previous reports. Here, we report the preparation of 8 nm copper nanoparticles (Cu NPs), with high metallic content, directly deposited onto the surface of silica nanopowders by magnetron sputtering deposition. The as-prepared Cu/SiO2 contains 85% Cu0 and 15% Cu2+ and was enriched in the Cu0 phase by H2 soft pretreatment (96% Cu0 and 4% Cu2+) or further oxidized after treatment with O2 (33% Cu0 and 67% Cu2+). These catalysts were studied in the catalytic oxidation of CO under dry and humid conditions. Higher activity was observed for the sample previously reduced with H2, suggesting that the presence of Cu-metal species enhances CO oxidation performance. Inversely, a poorer performance was observed for the sample previously oxidized with O2. The presence of water vapor caused only a small increase in the temperature require for the reaction to reach 100% conversion. Under dry conditions, the Cu NP catalyst was able to maintain full conversion for up to 45 h at 350 °C, but it deactivated with time on stream in the presence of water vapor.

  12. Fracture toughness for copper oxide superconductors

    Science.gov (United States)

    Goretta, Kenneth C.; Kullberg, Marc L.

    1993-01-01

    An oxide-based strengthening and toughening agent, such as tetragonal Zro.sub.2 particles, has been added to copper oxide superconductors, such as superconducting YBa.sub.2 Cu.sub.3 O.sub.x (123) to improve its fracture toughness (K.sub.IC). A sol-gel coating which is non-reactive with the superconductor, such as Y.sub.2 BaCuO.sub.5 (211) on the ZrO.sub.2 particles minimized the deleterious reactions between the superconductor and the toughening agent dispersed therethrough. Addition of 20 mole percent ZrO.sub.2 coated with 211 yielded a 123 composite with a K.sub.IC of 4.5 MPa(m).sup.0.5.

  13. Methanobactin-Mediated Synthesis of Gold Nanoparticles Supported over Al2O3 toward an Efficient Catalyst for Glucose Oxidation

    Directory of Open Access Journals (Sweden)

    Jia-Ying Xin

    2014-11-01

    Full Text Available Methanobactin (Mb is a copper-binding peptide that appears to function as an agent for copper sequestration and uptake in methanotrophs. Mb can also bind and reduce Au(III to Au(0. In this paper, Au/Al2O3 catalysts prepared by a novel incipient wetness-Mb-mediated bioreduction method were used for glucose oxidation. The catalysts were characterized, and the analysis revealed that very small gold nanoparticles with a particle size <4 nm were prepared by the incipient wetness-Mb-mediated bioreduction method, even at 1.0% Au loading (w/w. The influence of Au loading, calcination temperature and calcination time on the specific activity of Au/Al2O3 catalysts was systematically investigated. Experimental results showed that decomposing the Mb molecules properly by calcinations can enhance the specific activity of Au/Al2O3 catalysts, though they acted as reductant and protective agents during the catalyst preparation. Au/Al2O3 catalysts synthesized by the method exhibited optimum specific activity under operational synthesis conditions of Au loading of 1.0 wt % and calcined at 450 °C for 2 h. The catalysts were reused eight times, without a significant decrease in specific activity. To our knowledge, this is the first attempt at the preparation of Au/Al2O3 catalysts by Mb-mediated in situ synthesis of gold nanoparticles.

  14. Zeolite ZSM5 catalysts for abatement of nitrogen oxide

    Energy Technology Data Exchange (ETDEWEB)

    Ganemi, Bager

    1999-07-01

    Airborne pollutants from the combustion of fossil fuels are a global problem. Emission of nitrogen oxides (NO{sub x}) is increasing with the worldwide increase in the use of energy. Atmospheric and photochemical reactions link nitrogen oxides to hydrocarbons and tropospheric ozone. The emission of NO{sub x} has to be tackled urgently in order to limit the harmful effects of anthropogenic activity on the environment. The subject of this thesis is catalytic nitrogen oxide abatement through direct decomposition and reduction by methane over ion-exchanged zeolite ZSM5. The work covers catalytic conversion and surface intermediates, including correlations with the level of exchanged Cu{sup 2+} cations and Ni{sup 2+} or Pd{sup 2+} co-cations. Special attention is given to the aluminium content of the support and changes in structural parameters. It was found that NO{sub x} conversion over cation-exchanged ZSM5 is strongly influenced by the ion-exchange procedure and by the above material parameters. Characterization of Cu-ZSM5 reveals that approximately two molecules of water per Cu{sup 2+} ion desorb at temperatures between 150 and 350 Deg C, in addition to the conventional dehydration at lower temperatures. The desorbed water comes from the decomposition of Cu(OH){sub 2}. Decomposition of hydroxylated copper ions results in the formation Of Cu{sup 2+}-O-Cu{sup 2+} dimers, which are suggested to be the active sites for catalytic decomposition of NO. Acid sites are important for the dispersion of copper ions on the catalyst surface. Acid sites are also important for the interaction between copper species and the zeolite. Increased acidity leads to a stronger interaction between the exchanged cation and the framework, i.e. the exchanged cations become more resistant to mobility. The stronger bond between the exchanged cations and lattice oxygen also prevents dealumination of the catalyst and decreases the thermal expansion at higher temperatures. The temperature of

  15. Deactivation of diesel oxidation catalysts. Vehicle- and synthetic aging correlations

    Energy Technology Data Exchange (ETDEWEB)

    Andersson, Jonas; Skoglundh, Magnus [Competence Centre for Catalysis, Chalmers University of Technology, SE-412 96 Goeteborg (Sweden); Antonsson, Matilda [Volvo Car Corporation, Exhaust Gas Aftertreatment Diesel, SE-405 31 Goeteborg (Sweden); Eurenius, Lisa; Olsson, Eva [Microscopy and Microanalysis, Department of Applied Physics, Chalmers University of Technology, SE-412 96 Goeteborg (Sweden)

    2007-03-08

    Deactivation characteristics of a diesel oxidation catalyst subjected to controlled lab aging were compared to field-aged catalysts after 0, 80,000, and 160,000 km driving in order to establish the (dis)similarities between the two types of aging, and determine to what extent vehicle aging can be replaced by rapid synthetic aging. Emission tests confirmed the increasing deactivation of the field-aged catalysts and measurements of CO oxidation, Pt dispersion and hydrocarbon storage capacity were used together with XPS, TEM, and SEM-EDS to compare the performance with lab-aged catalysts. The synthetic aging was designed to account for a combination of thermal and chemical deactivation. A similar degree of Pt sintering was observed for both real and synthetic aging conditions, whereas differences arose from various contributions to the chemical deactivation. XPS showed that pre-oxidation and pre-reduction at 700 C was not sufficient to remove typical compounds of oil-derived catalyst poisons (P, Zn, Ca), which furthermore accumulated with mileage, on the vehicle-aged catalysts. The degree of sulfur poisoning of the lab-aged catalysts increased with the duration of low-temperature sulfur exposure and could not be recovered in atmospheres typical for normal driving conditions. The results show that synthetic aging can be used to simulate thermal aging and a general effect of irreversible chemical deactivation, and thereby accelerate durability test procedures of various catalysts where loss of catalytic activity by time of operation is of concern. (author)

  16. A One-Bead-One-Catalyst Approach to Aspartic Acid-Based Oxidation Catalyst Discovery

    Science.gov (United States)

    Lichtor, Phillip A.; Miller, Scott J.

    2011-01-01

    We report an approach to the high-throughput screening of asymmetric oxidation catalysts. The strategy is based on application of the one-bead-one-compound library approach, wherein each of our catalyst candidates is based on a peptide scaffold. For this purpose we rely on a recently developed catalytic cycle that employs an acid-peracid shuttle. In order to implement our approach, we developed a compatible linker and demonstrated that the library format is amenable to screening and sequencing of catalysts employing partial Edman degradation and MALDI mass spectrometry analysis. The system was applied to the discovery (and re-discovery) of catalysts for the enantioselective oxidation of a cyclohexene derivative. The system is now poised for application to unprecedented substrate classes for asymmetric oxidation reactions. PMID:21417485

  17. Catalyst Additives to Enhance Mercury Oxidation and Capture

    Energy Technology Data Exchange (ETDEWEB)

    Thomas K. Gale

    2006-06-30

    Catalysis is the key fundamental ingredient to convert elemental mercury in coal-fired power stations into its oxidized forms that are more easily captured by sorbents, ESPs, baghouses, and wet scrubbers, whether the catalyst be unburned carbon (UBC) in the ash or vanadium pentoxide in SCR catalysts. This project has investigated several different types of catalysts that enhance mercury oxidation in several different ways. The stated objective of this project in the Statement of Objectives included testing duct-injection catalysts, catalyst-sorbent hybrids, and coated low-pressure-drop screens. Several different types of catalysts were considered for duct injection, including different forms of iron and carbon. Duct-injection catalysts would have to be inexpensive catalysts, as they would not be recycled. Iron and calcium had been shown to catalyze mercury oxidation in published bench-scale tests. However, as determined from results of an on-going EPRI/EPA project at Southern Research, while iron and calcium did catalyze mercury oxidation, the activity of these catalysts was orders of magnitude below that of carbon and had little impact in the short residence times available for duct-injected catalysts or catalyst-sorbent hybrids. In fact, the only catalyst found to be effective enough for duct injection was carbon, which is also used to capture mercury and remove it from the flue gas. It was discovered that carbon itself is an effective catalyst-sorbent hybrid. Bench-scale carbon-catalyst tests were conducted, to obtain kinetic rates of mercury adsorption (a key step in the catalytic oxidation of mercury by carbon) for different forms of carbon. All carbon types investigated behaved in a similar manner with respect to mercury sorption, including the effect of temperature and chlorine concentration. Activated carbon was more effective at adsorbing mercury than carbon black and unburned carbon (UBC), because their internal surface area of activated carbon was

  18. Olefin polymerization over supported chromium oxide catalysts

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Schoonheydt, R.A.

    1999-01-01

    Cr/SiO2 or Phillips-type catalysts are nowadays responsible for a large fraction of all polyethylene (HDPE and LLDPE) worldwide produced. In this review, several key-properties of Cr/SiO2 catalysts will be discussed in relation to their polymerization characteristics. It will be shown how the polyol

  19. Supported Oxide Catalysts from Chelating Precursors

    Science.gov (United States)

    Prieto-Centurion, Dario

    Supported Fe catalysts and, in particular, Fe and substituted MFI zeolites have attracted industrial and academic attention due to their ability to promote selective catalytic reduction of NOx and selective partial oxidation of hydrocarbons. It is generally accepted that some form of highly dispersed, binuclear or atomically-isolated metal species are involved in the selective processes catalyzed these materials. Several studies have sought to reproduce the structures and reactivity of these substituted zeolites on dierent supports. Given that specialized reagents or preparation conditions that are required in some of these preparation methods, and that multiple surface structures are often formed, this dissertation aimed to develop a route to highly dispersed supported transition metals using commonly available reactants and synthesis routes. Described here is a straightforward and effective procedure to control dispersion and surface speciation of Fe on SiO2 and CeO2 through incipient wetness impregnation (IWI) of the support with aqueous, anionic complexes of Fe3+ and ethylenediaminetetraacetic acid (EDTA) followed by oxidative heat-treatment. On SiO2, this method preferentially creates isolated surface structures up to loading of 0.9 Fe nm-2 if using alkali counter-cations. This isolated species display classic 'single-site' behavior|constant turn over frequency (TOF) with increasing Fe surface density|in the oxidation of adamantane with H 2O2, indicating active sites are equally accessible and equally active within this range of surface density. Additionally, TOF increases linearly with electronegativity of the alkali counter-cation, suggesting electronic promotion. Conversely, IWI of unprotected Fe3+ produces agglomerates less active in this reaction. On CeO2, the sterics and negative charge imparted on Fe 3+ by EDTA4- inhibits incorporation of Fe into surface vacancies. Instead, formation of two-dimensional oligomeric structures which can undergo Fe3+-Fe2

  20. Role of copper oxides in contact killing of bacteria.

    Science.gov (United States)

    Hans, Michael; Erbe, Andreas; Mathews, Salima; Chen, Ying; Solioz, Marc; Mücklich, Frank

    2013-12-31

    The potential of metallic copper as an intrinsically antibacterial material is gaining increasing attention in the face of growing antibiotics resistance of bacteria. However, the mechanism of the so-called "contact killing" of bacteria by copper surfaces is poorly understood and requires further investigation. In particular, the influences of bacteria-metal interaction, media composition, and copper surface chemistry on contact killing are not fully understood. In this study, copper oxide formation on copper during standard antimicrobial testing was measured in situ by spectroscopic ellipsometry. In parallel, contact killing under these conditions was assessed with bacteria in phosphate buffered saline (PBS) or Tris-Cl. For comparison, defined Cu2O and CuO layers were thermally generated and characterized by grazing incidence X-ray diffraction. The antibacterial properties of these copper oxides were tested under the conditions used above. Finally, copper ion release was recorded for both buffer systems by inductively coupled plasma atomic absorption spectroscopy, and exposed copper samples were analyzed for topographical surface alterations. It was found that there was a fairly even growth of CuO under wet plating conditions, reaching 4-10 nm in 300 min, but no measurable Cu2O was formed during this time. CuO was found to significantly inhibit contact killing, compared to pure copper. In contrast, thermally generated Cu2O was essentially as effective in contact killing as pure copper. Copper ion release from the different surfaces roughly correlated with their antibacterial efficacy and was highest for pure copper, followed by Cu2O and CuO. Tris-Cl induced a 10-50-fold faster copper ion release compared to PBS. Since the Cu2O that primarily forms on copper under ambient conditions is as active in contact killing as pure copper, antimicrobial objects will retain their antimicrobial properties even after oxide formation.

  1. Copper oxide as a synergistic catalyst for the oxygen reduction reaction on La0.6Sr0.4Co0.2Fe0.8O3-δ perovskite structured electrocatalyst

    Science.gov (United States)

    Hong, Tao; Brinkman, Kyle; Xia, Changrong

    2016-10-01

    This work presents the effect of dispersed copper oxide (CuO) nanoparticles on the oxygen reduction reaction (ORR) on a typical solid oxide fuel cell (SOFC) electrocatalyst, La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF). The ORR kinetics were enhanced by a factor up to 4 at 750 °C as demonstrated by electrical conductivity relaxation measurements used to determine the chemical surface exchange coefficient, kchem. The value of kchem increased from 2.6 × 10-5 cm s-1 to 9.3 × 10-5 cm s-1 at 750 °C when the LSCF surface was coated with submicron CuO particles. The enhanced kchem was attributed to additional reactions that occur on the CuO surface and at the LSCF-CuO-gas three-phase boundaries (3PBs) as suggested by the kchem dependence on CuO coverage and 3PB length. This enhancement was further demonstrated by the introduction of CuO nanoparticles into LSCF electrodes. CuO infiltrated electrodes reduced the interfacial polarization resistance from 2.27 Ω cm2 to 1.5 Ω cm2 at 600 °C and increased the peak power density from 0.54 W cm-2 to 0.72 W cm-2 at 650 °C. Electrochemical impedance spectroscopy indicated that the reduced resistance was due to the shrinkage of the low frequency arc, which is associated with the electrochemical surface exchange reaction.

  2. Low-Temperature CO oxidation on multicomponent gold based catalysts

    Directory of Open Access Journals (Sweden)

    Tomas eRamirez Reina

    2013-09-01

    Full Text Available In this work the development of gold catalysts, essentially based on γ-alumina with small superficial fraction of Ce-Fe mixed oxides as support for the low temperature CO oxidation is proposed. Characterization results obtained by means of XPS, UV-Vis spectroscopy and H2-TPR are employed to correlate the activity data with the catalysts composition. The bare γ-alumina supported gold catalyst demonstrates the poorest activity within the series. The addition of CeO2 or FeOX improves the catalytic performance, especially observed for the CeO2-FeOx mixed oxide doped samples. This enhanced CO oxidation activity was related to the Ce-Fe interaction producing materials with promoted redox properties and therefore oxidation activity

  3. Supramolecular water oxidation with rubda-based catalysts

    KAUST Repository

    Richmond, Craig J.

    2014-11-05

    Extremely slow and extremely fast new water oxidation catalysts based on the Rubda (bda = 2,2′-bipyri-dine-6,6′-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycless"1, respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system p-stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts.

  4. Low-temperature CO oxidation on multicomponent gold based catalysts

    Science.gov (United States)

    Ramírez Reina, Tomás; Ivanova, Svetlana; Centeno, Miguel A.; Odriozola, José A.

    2013-01-01

    In this work the development of gold catalysts, essentially based on γ-alumina with small superficial fraction of Ce-Fe mixed oxides as support for the low temperature CO oxidation is proposed. Characterization results obtained by means of TEM, OSC, XPS, UV-Vis spectroscopy and H2-TPR are employed to correlate the activity data with the catalysts composition. The bare γ-alumina supported gold catalyst demonstrates the poorest activity within the series. The addition of CeO2 or FeOX improves the catalytic performance, especially observed for the CeO2-FeOx mixed oxide doped samples. This enhanced CO oxidation activity was related to the Ce-Fe interaction producing materials with promoted redox properties and therefore oxidation activity. PMID:24790941

  5. Oxides Catalysts of Rare Earth and Transient Metal for Catalytic Oxidation of Benzene

    Institute of Scientific and Technical Information of China (English)

    Liang Kun; Li Rong; Chen Jianjun; Ma Jiantai

    2004-01-01

    The catalysts of CeO2 and the mixture of CeO2 and CuO were prepared, and the activities of these catalysts for completely oxidizing benzene were studied.The results show that the optimal proportion of CeO2/CuO is 6: 4.The highest temperature at which benzene was completely oxidized on these catalysts at different airspeed was measured.Compared these catalysts with the noble metal used, our catalysts had superiority in the resources and the industrial cost besides good activities.

  6. Liquid phase conversion of Glycerol to Propanediol over highly active Copper/Magnesia catalysts

    Indian Academy of Sciences (India)

    Satyanarayana Murty Pudi; Abdul Zoeb; Prakash Biswas; Shashi Kumar

    2015-05-01

    In this work, a series of Cu/MgO catalysts with different copper metal loading were prepared by the precipitation-deposition method. Their catalytic behaviour was investigated for glycerol hydrogenolysis to 1,2-propanediol (1,2-PDO). The physico-chemical properties of the catalysts were characterized by various techniques such as BET surface area, X-ray diffraction (XRD), temperature programmed reduction (TPR), NH3-temperature programmed desorption (NH3-TPD) and scanning electron microscopy (SEM) methods. The characterization results showed that the copper metal was well-dispersed over MgO support and a new phase Cu-MgO was also identified from XRD results after calcination. The 25Cu/MgO (Cu:25 wt%) catalyst exhibited the highest glycerol conversion of 88.7% and 1,2-PDO selectivity of 91.7% at 210°C, 4.5MPa of hydrogen pressure after 12 h. The high glycerol conversion was mainly due to the Cu dispersion on MgO support and high acidic strength. Further, the effects of temperature, hydrogen pressure, catalyst loading and glycerol concentration were studied over 25Cu/MgO catalyst for optimization of reaction parameters. Kinetic study over highly active 25Cu/MgO catalyst showed that the reaction followed the pseudo second order rate with respect to glycerol and the apparent activation energy was found to be 28.7 ± 0.8 kcal/mol.

  7. Catalytic performance for CO{sub 2} conversion to methanol of gallium-promoted copper-based catalysts. Influence of metallic precursors

    Energy Technology Data Exchange (ETDEWEB)

    Toyir, Jamil; Ramirez de la Piscina, Pilar; Homs, Narcis [Departament de Quimica Inorganica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Fierro, Jose Luis G. [Instituto de Catalisis y Petroleoquimica, C.S.I.C., Cantoblanco, 28049 Madrid (Spain)

    2001-11-28

    This study reports new gallium-promoted copper-based catalysts prepared by co-impregnation of methoxide-acetylacetonate (acac) precursors from methanolic solutions onto silica and zinc oxide supports. Catalyst performance in the CO{sub 2} hydrogenation to methanol was investigated at 2MPa and temperatures between 523 and 543K. A high activity and selectivity for ZnO-supported catalysts was found, which also showed a high stability in terms of both activity and selectivity. The maximum value for the activity was 378gMeOH/kgcath at 543K, with a selectivity of 88% towards methanol production. The high performance of these materials in the CO{sub 2} hydrogenation is related to the presence of Ga{sub 2}O{sub 3} promoter and highly dispersed Cu{sup +} species on the surface, determined by XPS and Auger on used catalysts.

  8. Understanding the superconductivity in copper oxides

    CERN Document Server

    2016-01-01

    The aim of this book is to clarify the situation by adopting a very different approach from the above electronic/magnetic models, where explicitly local dynamical distortions are considered. These are distinctly different from conventional phonons which are a property of the infinite translational invariant symmetric lattice. The local dynamical distortions are shown to account for bulk properties and provide consistent and quantitative agreement with experimental data together with explicit predictions. Selected published experimental and theoretical papers are presented which support the above arguments, but have been ignored on purpose by the originators of the RVB/t-J bubble. To summarize the scope of this book, comprising nine chapters, it is shown, that the phenomenon of HTS in copper oxides is much better understood than publically claimed by RVB/t-J followers. Using the words of B. Laughlin, the presence of the antiferromagnetism in HTS masks the underlying physics where vibronic bipolarons with spin...

  9. A pentanuclear iron catalyst designed for water oxidation

    Science.gov (United States)

    Okamura, Masaya; Kondo, Mio; Kuga, Reiko; Kurashige, Yuki; Yanai, Takeshi; Hayami, Shinya; Praneeth, Vijayendran K. K.; Yoshida, Masaki; Yoneda, Ko; Kawata, Satoshi; Masaoka, Shigeyuki

    2016-02-01

    Although the oxidation of water is efficiently catalysed by the oxygen-evolving complex in photosystem II (refs 1 and 2), it remains one of the main bottlenecks when aiming for synthetic chemical fuel production powered by sunlight or electricity. Consequently, the development of active and stable water oxidation catalysts is crucial, with heterogeneous systems considered more suitable for practical use and their homogeneous counterparts more suitable for targeted, molecular-level design guided by mechanistic understanding. Research into the mechanism of water oxidation has resulted in a range of synthetic molecular catalysts, yet there remains much interest in systems that use abundant, inexpensive and environmentally benign metals such as iron (the most abundant transition metal in the Earth’s crust and found in natural and synthetic oxidation catalysts). Water oxidation catalysts based on mononuclear iron complexes have been explored, but they often deactivate rapidly and exhibit relatively low activities. Here we report a pentanuclear iron complex that efficiently and robustly catalyses water oxidation with a turnover frequency of 1,900 per second, which is about three orders of magnitude larger than that of other iron-based catalysts. Electrochemical analysis confirms the redox flexibility of the system, characterized by six different oxidation states between FeII5 and FeIII5; the FeIII5 state is active for oxidizing water. Quantum chemistry calculations indicate that the presence of adjacent active sites facilitates O-O bond formation with a reaction barrier of less than ten kilocalories per mole. Although the need for a high overpotential and the inability to operate in water-rich solutions limit the practicality of the present system, our findings clearly indicate that efficient water oxidation catalysts based on iron complexes can be created by ensuring that the system has redox flexibility and contains adjacent water-activation sites.

  10. Comparison of the Oxidation Rates of Some New Copper Alloys

    Science.gov (United States)

    Ogbuji, Linus U. J. Thomas; Humphrey, Donald L.

    2002-01-01

    Copper alloys were studied for oxidation resistance and mechanisms between 550 and 700 C, in reduced-oxygen environments expected in rocket engines, and their oxidation behaviors compared to that of pure copper. They included two dispersion-strengthened alloys (precipitation-strengthened and oxide-dispersion strengthened, respectively) and one solution-strengthened alloy. In all cases the main reaction was oxidation of Cu into Cu2O and CuO. The dispersion-strengthened alloys were superior to both Cu and the solution-strengthened alloy in oxidation resistance. However, factors retarding oxidation rates seemed to be different for the two dispersion-strengthened alloys.

  11. Certain aspects of the formation and identification of nanosized oxide components in heterogeneous catalysts prepared by different methods

    Energy Technology Data Exchange (ETDEWEB)

    Ellert, Ol' ga G; Novotortsev, Vladimir M [N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow (Russian Federation); Tsodikov, Mark V [A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow (Russian Federation)

    2010-10-19

    The results of studies into the relationship 'methods and synthesis conditions of a catalyst{yields}catalyst structure{yields}catalytic properties' in highly efficient crystallo-graphically amorphous copper- and iron-containing heterogeneous systems obtained by different chemical methods are generalized. Polymorphism of active phases and catalytic properties of nanostructured copper-containing zinc, zirconium, manganese and cerium oxides are discussed. Unusual transformations of nanosized Pt- and Pd-containing components on the {gamma}-Al{sub 2}O{sub 3} surface in nanostructured catalysts of ethanol steam reforming into synthesis gas and reductive dehydration of ethanol to alkanes are considered. The results of comparative studies on the crystallographically amorphous mixed iron oxide catalysts synthesized by either the alkoxy method or the deposition on various supports obtained by the Moessbauer and XAFS spectroscopy and magnetic susceptibility measurements are presented. These materials are shown to be efficient catalysts of important processes such as liquid-phase oxidation of hydrocarbons, synthesis of alkenes and alkylaromatic hydrocarbons from CO and H{sub 2}, hydrogenative transformation of brown coal organic mass to hydrocarbons.

  12. Bioavailable copper modulates oxidative phosphorylation and growth of tumors.

    Science.gov (United States)

    Ishida, Seiko; Andreux, Pénélope; Poitry-Yamate, Carole; Auwerx, Johan; Hanahan, Douglas

    2013-11-26

    Copper is an essential trace element, the imbalances of which are associated with various pathological conditions, including cancer, albeit via largely undefined molecular and cellular mechanisms. Here we provide evidence that levels of bioavailable copper modulate tumor growth. Chronic exposure to elevated levels of copper in drinking water, corresponding to the maximum allowed in public water supplies, stimulated proliferation of cancer cells and de novo pancreatic tumor growth in mice. Conversely, reducing systemic copper levels with a chelating drug, clinically used to treat copper disorders, impaired both. Under such copper limitation, tumors displayed decreased activity of the copper-binding mitochondrial enzyme cytochrome c oxidase and reduced ATP levels, despite enhanced glycolysis, which was not accompanied by increased invasiveness of tumors. The antiproliferative effect of copper chelation was enhanced when combined with inhibitors of glycolysis. Interestingly, larger tumors contained less copper than smaller tumors and exhibited comparatively lower activity of cytochrome c oxidase and increased glucose uptake. These results establish copper as a tumor promoter and reveal that varying levels of copper serves to regulate oxidative phosphorylation in rapidly proliferating cancer cells inside solid tumors. Thus, activation of glycolysis in tumors may in part reflect insufficient copper bioavailability in the tumor microenvironment.

  13. Strain-induced orientation of copper oxide nanoislands through decomposition of pre-organized copper nitrate

    Institute of Scientific and Technical Information of China (English)

    谷俐; 陈树大; 赵惠明

    2004-01-01

    By the decomposition of copper nitrate at 400 ℃, oriented islands of copperoxide crystals were successfully fabricated on the amorphous glass surface. X-ray diffraction (XRD), atom force microscope (AFM), and Xray photoelectron spectroscopy (XPS) confirm the presence of copper oxide islands. The formation of oriented island structures is attributed to the following reasons: 1) the mismatch between the glass substrate and the copper oxide crystals during the relaxation of thermal expansion leads to the formation of islands; 2) the preorganized copper nitrate particles in the voids of colloidal crystals determine their ordered spatial distribution; 3) the strain of the glass substrate developing during calcination provides the driven energy for the orientation of copper oxide crystals along the same direction.

  14. Oxidation Potentials in Matte Smelting of Copper and Nickel

    Science.gov (United States)

    Matousek, Jan W.

    2014-09-01

    The oxidation potential, given as the base-ten logarithm of the oxygen partial pressure in bars and the temperature [log pO2/ T, °C], defines the state of oxidation of pyrometallurgical extraction and refining processes. This property varies from copper making, [-6/1150]; to lead/zinc smelting, [-10/1200]; to iron smelting, [-13/1600]. The current article extends the analysis to the smelting of copper and nickel/copper sulfide concentrates to produce mattes of the type Cu(Ni)FeS(O) and iron silicate slags, FeOxSiO2—with oxidation potentials of [-7.5/1250].

  15. Kinetics and mechanisms of reactions between H2O2 and copper and copper oxides.

    Science.gov (United States)

    Björkbacka, Åsa; Yang, Miao; Gasparrini, Claudia; Leygraf, Christofer; Jonsson, Mats

    2015-09-28

    One of the main challenges for the nuclear power industry today is the disposal of spent nuclear fuel. One of the most developed methods for its long term storage is the Swedish KBS-3 concept where the spent fuel is sealed inside copper canisters and placed 500 meters down in the bedrock. Gamma radiation will penetrate the canisters and be absorbed by groundwater thereby creating oxidative radiolysis products such as hydrogen peroxide (H2O2) and hydroxyl radicals (HO˙). Both H2O2 and HO˙ are able to initiate corrosion of the copper canisters. In this work the kinetics and mechanism of reactions between the stable radiolysis product, H2O2, and copper and copper oxides were studied. Also the dissolution of copper into solution after reaction with H2O2 was monitored by ICP-OES. The experiments show that both H2O2 and HO˙ are present in the systems with copper and copper oxides. Nevertheless, these species do not appear to influence the dissolution of copper to the same extent as observed in recent studies in irradiated systems. This strongly suggests that aqueous radiolysis can only account for a very minor part of the observed radiation induced corrosion of copper.

  16. Hysteresis Phenomena in Sulfur Dioxide Oxidation over Supported Vanadium Catalysts

    DEFF Research Database (Denmark)

    Masters, Stephen G.; Eriksen, Kim Michael; Fehrmann, Rasmus

    1997-01-01

    Catalyst deactivation and hysteresis behavior in industrial SO2-oxidation catalysts have been studied in the temperature region 350-480 C by combined in situ EPR spectroscopy and catalytic activity measurements. The feed gas composition simulated sulfuric acid synthesis gas and wet/dry de......NOx'ed flue gas. The vanadium (IV) compound K4(VO)3(SO4)5 precipitated during all the investigated conditions hence causing catalyst deactivation. Hysteresis behavior of both the catalytic activity and the V(IV) content was observed during reheating....

  17. INVESTIGATION OF MIXED METAL SORBENT/CATALYSTS FOR THE SIMULTANEOUS REMOVAL OF SULFUR AND NITROGEN OXIDES

    Energy Technology Data Exchange (ETDEWEB)

    Ates Akyurtlu; Jale F. Akyurtle

    2001-08-01

    Simultaneous removal of SO{sub 2} and NO{sub x} using a regenerable solid sorbent will constitute an important improvement over the use of separate processes for the removal of these two pollutants from stack gases and possibly eliminate several shortcomings of the individual SO{sub 2} and NO{sub x} removal operations. The work done at PETC and the DOE-funded investigation of the investigators on the sulfation and regeneration of alumina-supported cerium oxide sorbents have shown that they can perform well at relatively high temperatures (823-900 K) as regenerable desulfurization sorbents. Survey of the recent literature shows that addition of copper oxide to ceria lowers the sulfation temperature of ceria down to 773 K, sulfated ceria-based sorbents can function as selective SCR catalysts even at elevated temperatures, SO{sub 2} can be directly reduced to sulfur by CO on CuO-ceria catalysts, and ceria-based catalysts may have a potential for selective catalytic reduction of NO{sub x} by methane. These observations indicate a possibility of developing a ceria-based sorbent/catalyst which can remove both SO{sub 2} and NO{sub x} from flue gases within a relatively wide temperature window, produce significant amounts of elemental sulfur during regeneration, and use methane for the selective catalytic reduction of NO{sub x}.

  18. Electrodeposited NiCu Alloy Catalysts for Glucose Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Lim, Jieun; Park, Hansoo; Kim, Sookil [Chung-Ang Univ., Seoul (Korea, Republic of); Ahn, Sang Hyun; Jang, Jong Hyun [Korea Institute of Science and Technology, Seoul (Korea, Republic of)

    2014-07-15

    NiCu alloys have been suggested as potential candidates for catalysts in glucose oxidation. In this study, NiCu alloys with different compositions were prepared on a glassy carbon substrate by changing the electrodeposition potential to examine the effect of Ni/Cu ratios in alloys on catalytic activity toward glucose oxidation. Cyclic voltammetry and chronoamperometry showed that NiCu alloys had higher catalytic activity than pure Ni and Cu catalysts. Especially, Ni{sub 59}Cu{sub 41} had superior catalytic activity, which was about twice that of Ni at a given oxidation potential. X-ray analyses showed that the oxidation state of Ni in NiCu alloys was increased with the content of Cu by lattice expansion. Ni components in alloys with higher oxidation state were more effective in the oxidation of glucose.

  19. Furfural Hydrogenation on Alloyed Copper Catalysts With Additives of Ferrosilicium

    Directory of Open Access Journals (Sweden)

    T. K. Akilov

    2015-12-01

    Full Text Available The present work is dedicated to the study of influence of ferrosilicium additives [FA*-ferroalloy containing (% mass: 46.8 Si, ~53,0 Fe, other are (C, P, S impurities] on the activity of alloyed Gu-Al = 50-50 catalyst in the reaction of furfural hydrogenation under hydrogen pressure. Components content varied (% mass: Cu- 40...49, aluminum- 50, FA* -1.0...10.0. The catalysts were prepared from 1g alloys by leaching it with 20% of aqueous solution of caustic soda in boiling water-bath during 1 hour. The phase composition and structure of alloys were investigated by means of roentgenographic and X-ray spectrum methods.

  20. Copper(I)-catalyzed azide-alkyne cycloadditions in microflow: catalyst activity, high-T operation, and an integrated continuous copper scavenging unit.

    Science.gov (United States)

    Varas, Alvaro Carlos; Noël, Timothy; Wang, Qi; Hessel, Volker

    2012-09-01

    AVOIDING THE COPPERS: A continuous-flow synthesis for the Cu(I) -catalyzed azide-alkyne cycloaddition reaction using [Cu(phenanthroline)(PPh₃)₂]NO₃ as a homogeneous catalyst is developed (up to 92 % isolated yield). Elevated temperatures allow achieving full conversions and using lower catalyst loadings. Residual copper in the triazole compound is efficiently removed via an inline extraction process, employing aqueous EDTA as a copper scavenger. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. A chameleon catalyst for nonheme iron-promoted olefin oxidation.

    Science.gov (United States)

    Iyer, Shyam R; Javadi, Maedeh Moshref; Feng, Yan; Hyun, Min Young; Oloo, Williamson N; Kim, Cheal; Que, Lawrence

    2014-11-18

    We report the chameleonic reactivity of two nonheme iron catalysts for olefin oxidation with H2O2 that switch from nearly exclusive cis-dihydroxylation of electron-poor olefins to the exclusive epoxidation of electron-rich olefins upon addition of acetic acid. This switching suggests a common precursor to the nucleophilic oxidant proposed to Fe(III)-η(2)-OOH and electrophilic oxidant proposed to Fe(V)(O)(OAc), and reversible coordination of acetic acid as a switching pathway.

  2. Research advances in the catalysts for the selective oxidation of ethane to aldehydes

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhe; ZHAO Zhen; XU Chunming

    2005-01-01

    Selective oxidation of ethane to aldehydes is one of the most difficult processes in the catalysis researches of low alkanes. The development of selective oxidation of ethane to aldehydes (formaldehyde, acetaldehyde and acrolein) is discussed. The latest progress of the catalysts, including bulk or supported metal oxide catalysts, highly dispersed and isolated active sites catalysts, and the photo-catalytic ethane oxidation catalysts, partial oxidation of ethane in the gas phase, and the proposed reaction pathways from ethane to aldehydes are involved.

  3. Catalytic destruction of dichloromethane using perovskite-type oxide catalysts.

    Science.gov (United States)

    Lou, Jie-Chung; Hung, Chang-Mao; Yang, Bor-Yu

    2004-06-01

    Dichloromethane (DCM, also known as methylene chloride [CH2Cl2]) is often present in industrial waste gas and is a valuable chemical product in the chemical industry. This study addresses the oxidation of airstreams that contain CH2Cl2 by catalytic oxidation in a tubular fixed-bed reactor over perovskite-type oxide catalysts. This work also considers how the concentration of influent CH2Cl2 (Co = 500-1000 ppm), the space velocity (GHSV = 5000-48,000 1/hr), the relative humidity (RH = 10-70%) and the concentration of oxygen (O2 = 5-21%) influence the operational stability and capacity for the removal of CH2Cl2. The surface area of lanthanum (La)-cobalt (Co) composite catalyst was the greatest of the five perovskite-type catalysts prepared in various composites of La, strontium, and Co metal oxides. Approximately 99.5% CH2Cl2 reduction was achieved by the catalytic oxidation over LaCoO3-based perovskite catalyst at 600 degrees C. Furthermore, the effect of the initial concentration and reaction temperature on the removal of CH2Cl2 in the gaseous phase was also monitored. This study also provides information that a higher humidity corresponds to a lower conversion. Carbon dioxide and hydrogen chloride were the two main products of the oxidation process at a relative humidity of 70%.

  4. Copper-free monomeric and dendritic palladium catalysts for the Sonogashira reaction: substituent effects, synthetic applications, and the recovery and re-use of the catalysts.

    Science.gov (United States)

    Heuzé, Karine; Méry, Denise; Gauss, Dominique; Blais, Jean-Claude; Astruc, Didier

    2004-08-20

    A series of bis(tert-butylphosphine)- and bis(cyclohexylphosphine)-functionalized Pd(II) monomers and polyamino (DAB) dendritic catalysts were synthesized and investigated for Sonogashira carbon-carbon coupling reactions in a copper-free procedure. The influence of phosphine substituents (tBu versus Cy) on the reaction kinetics was investigated by a GPC technique to monitor the reactions. The dendritic catalysts containing the cyclohexylphosphine ligands could be recovered and reused without loss of efficiency until the fifth cycle. The dendritic Pd(II) catalysts show a negative dendritic effect, that is, the catalyst efficiency decreases as the dendrimer generation increases.

  5. Characteristics of the oxygen evolution reaction on synthetic copper - cobalt - oxide electrodes for water electrolysis

    Science.gov (United States)

    Park, Yoo Sei; Park, Chan Su; Kim, Chi Ho; Kim, Yang Do; Park, Sungkyun; Lee, Jae Ho

    2016-10-01

    A nano-sized Cu0.7Co2.3O4 powder was prepared using a thermal decomposition method to achieve an efficient anode catalyst for an economical water electrolysis system for high-purity hydrogen-gas production without using a noble-metal catalyst. This study showed that the calcination temperature should be maintained under 400 °C to obtain a spinel copper - cobalt oxide structure without secondary oxide phases. The powder calcined at 250 °C showed the highest current density at the oxygen evolution reaction. This was due mainly to the increased number of available active sites and the active surface area of the powders. Further systematic analyses of the electrochemical characteristics of Cu x Co3- x O4 synthesized by using the fusion method were performed to assess it as potential anode material for use in alkaline-anion-exchange-membrane water electrolysis.

  6. A Molecular Copper Catalyst for Hydrogenation of CO­2 to Formate

    Energy Technology Data Exchange (ETDEWEB)

    Zall, Christopher M.; Linehan, John C.; Appel, Aaron M.

    2015-09-04

    There is widespread interest in the hydrogenation of CO2 to energy-rich products such as formate. However, first-row transition metal complexes that catalyze the hydrogenation of CO2 to formate remain rare. Copper phosphine complexes are widely used in the reduction of organic substrates but have not previously been used as catalysts for the conversion of H2 and CO2 to formate. Here we demonstrate that the triphosphine-ligated copper(I) complex LCu(MeCN)PF6 is an active catalyst for CO2 hydrogenation in the presence of a suitable base. Screening of bases and studies of catalytic reactions by in operando spectroscopy revealed important and unusual roles for the base in promoting H2 activation and turnover.

  7. Templating Routes to Supported Oxide Catalysts by Design

    Energy Technology Data Exchange (ETDEWEB)

    Notestein, Justin M. [Northwestern Univ., Evanston, IL (United States)

    2016-09-08

    The rational design and understanding of supported oxide catalysts requires at least three advancements, in order of increasing complexity: the ability to quantify the number and nature of active sites in a catalytic material, the ability to place external controls on the number and structure of these active sites, and the ability to assemble these active sites so as to carry out more complex functions in tandem. As part of an individual investigator research program that is integrated with the Northwestern University Institute for Catalysis in Energy Processes (ICEP) as of 2015, significant advances were achieved in these three areas. First, phosphonic acids were utilized in the quantitative assessment of the number of active and geometrically-available sites in MOx-SiO2 catalysts, including nanocrystalline composites, co-condensed materials, and grafted structures, for M=Ti, Zr, Hf, Nb, and Ta. That work built off progress in understanding supported Fe, Cu, and Co oxide catalysts from chelating and/or multinuclear precursors to maximize surface reactivity. Secondly, significant progress was made in the new area of using thin oxide overcoats containing ‘nanocavities’ from organic templates as a method to control the dispersion and thermal stability of subsequently deposited metal nanoparticles or other catalytic domains. Similar methods were used to control surface reactivity in SiO2-Al2O3 acid catalysts and to control reactant selectivity in Al2O3-TiO2 photocatalysts. Finally, knowledge gained from the first two areas has been combined to synthesize a tandem catalyst for hydrotreating reactions and an orthogonal tandem catalyst system where two subsequent reactions in a reaction network are independently controlled by light and heat. Overall, work carried out under this project significantly advanced the knowledge of synthesis-structure-function relationships in supported

  8. Formic acid oxidation at platinum-bismuth catalysts

    Directory of Open Access Journals (Sweden)

    Popović Ksenija Đ.

    2015-01-01

    Full Text Available The field of heterogeneous catalysis, specifically catalysis on bimetallic surfaces, has seen many advances over the past few decades. Bimetallic catalysts, which often show electronic and chemical properties that are distinct from those of their parent metals, offer the opportunity to obtain new catalysts with enhanced selectivity, activity, and stability. The oxidation of formic acid is of permanent interest as a model reaction for the mechanistic understanding of the electrooxidation of small organic molecules and because of its technical relevance for fuel cell applications. Platinum is one of the most commonly used catalysts for this reaction, despite the fact that it shows a few significant disadvantages: high cost and extreme susceptibility to poisoning by CO. To solve this problem, several approaches have been used, but generally, they all consist in the modification of platinum with a second element. Especially, bismuth has received significant attention as Pt modifier. According to the results presented in this survey dealing with the effects influencing the formic acid oxidation it was found that two types of Pt-Bi bimetallic catalysts (bulk and low loading deposits on GC showed superior catalytic activity in terms of the lower onset potential and oxidation current density, as well as exceptional stability compared to Pt. The findings in this report are important for the understanding of mechanism of formic acid electrooxidation on a bulk alloy and decorated surface, for the development of advanced anode catalysts for direct formic acid fuel cells, as well as for the synthesis of novel low-loading bimetallic catalysts. The use of bimetallic compounds as the anode catalysts is an effective solution to overcoming the problems of the formic acid oxidation current stability for long term applications. In the future, the tolerance of both CO poisoning and electrochemical leaching should be considered as the key factors in the development

  9. Pd oxides/hydrous oxides as highly efficient catalyst for formic acid electrooxidation

    Science.gov (United States)

    Yan, Liang; Yao, Shikui; Chang, Jinfa; Liu, Changpeng; Xing, Wei

    2014-03-01

    A novel Pd-based catalyst for formic acid electrooxidation (FAEO) was prepared by annealing commercial Pd/C catalyst under the O2 atmosphere at 100 °C, which exhibits excellent catalytic activity and stability for FAEO due to introduction of Pd oxides/hydrous oxides (POHOs). The catalytic activity of the as-prepared catalyst towards FAEO is 1.86 times of the commercial Pd/C catalyst in 0.5 M H2SO4 + 0.5 M HCOOH solution. Chronoamperometric curves show obvious improvement of the as-prepared catalyst electrocatalytic stability for FAEO. It is confirmed that POHOs can provide the required oxygen species for intermediate CO oxidation during the oxidation process of formic acid.

  10. Electrical Characterization of Spherical Copper Oxide Memristive Array Sensors

    Science.gov (United States)

    2014-03-27

    running, dinner-table debate etiquette, sailing, electric guitar, and the Seattle bus system, but only earned his Bachelor of Science in Electrical ... ELECTRICAL CHARACTERIZATION OF SPHERICAL COPPER OXIDE MEMRISTIVE ARRAY SENSORS THESIS James P. Orta, Second Lieutenant, USAF AFIT-ENP-14-M-40...not subject to copyright protection in the United States. AFIT-ENP-14-M-40 ELECTRICAL CHARACTERIZATION OF SPHERICAL COPPER OXIDE MEMRISTIVE ARRAY

  11. Unsupported single-atom-thick copper oxide monolayers

    Science.gov (United States)

    Yin, Kuibo; Zhang, Yu-Yang; Zhou, Yilong; Sun, Litao; Chisholm, Matthew F.; Pantelides, Sokrates T.; Zhou, Wu

    2017-03-01

    Oxide monolayers may present unique opportunities because of the great diversity of properties of these materials in bulk form. However, reports on oxide monolayers are still limited. Here we report the formation of single-atom-thick copper oxide layers with a square lattice both in graphene pores and on graphene substrates using aberration-corrected scanning transmission electron microscopy. First-principles calculations find that CuO is energetically stable and its calculated lattice spacing matches well with the measured value. Furthermore, free-standing copper oxide monolayers are predicted to be semiconductors with band gaps ∼3 eV. The new wide-bandgap single-atom-thick copper oxide monolayers usher a new frontier to study the highly diverse family of two-dimensional oxides and explore their properties and their potential for new applications.

  12. Extracting copper from copper oxide ore by a zwitterionic reagent and dissolution kinetics

    Institute of Scientific and Technical Information of China (English)

    Jiu-shuai Deng; Shu-ming Wen; Jian-ying Deng; Dan-dan Wu

    2015-01-01

    Sulfamic acid (SA), which possesses a zwitterionic structure, was applied as a leaching reagent for the first time for extracting copper from copper oxide ore. The effects of reaction time, temperature, particle size, reagent concentration, and stirring speed on this leach-ing were studied. The dissolution kinetics of malachite was illustrated with a three-dimensional diffusion model. A novel leaching effect of SA on malachite was eventually demonstrated. The leaching rate increased with decreasing particle size and increasing concentration, reac-tion temperature and stirring speed. The activation energy for SA leaching malachite was 33.23 kJ/mol. Furthermore, the effectiveness of SA as a new reagent for extracting copper from copper oxide ore was confirmed by experiment. This approach may provide a solution suitable for subsequent electrowinning. In addition, results reported herein may provide basic data that enable the leaching of other carbonate miner-als of copper, zinc, cobalt and so on in an SA system.

  13. Synthesis of 2-methylpyrazine from cyclocondensation of ethylene diamine and propylene glycol over promoted copper catalyst

    Institute of Scientific and Technical Information of China (English)

    Fang Li Jing; Wei Chu; Yuan Yuan Zhang; Ye Qiang Chen; Shi Zhong Luo

    2008-01-01

    The 2-methylpyrazine was synthesized by catalytic reaction of ethylene diamine and propylene glycol at 380℃. The alumina supported copper catalysts with promoter were prepared by impregnation method, characterized by ICP-AES, BET and TPR. The results demonstrated that the dehydrogenation was improved by addition of chromium promoter. The selectivity of 2-methylpyrazine reached 84.75%, while the conversions of reactants were also enhanced.

  14. Mechanism of copper selenide growth on copper-oxide selenium system

    Science.gov (United States)

    Ishikawa, Y.; Kido, O.; Kimura, Y.; Kurumada, M.; Suzuki, H.; Saito, Y.; Kaito, C.

    2004-01-01

    Transmission electron microscopy was used to study spontaneous copper selenide formation on Cu particles covered with an oxide layer. Even if the copper particle surface was covered with a Cu 2O layer, selenides were formed by diffusion through the metal oxide layer. For a particle size less than 50 nm, selenide was formed in Cu particles by the diffusion of Se atoms passing through the Cu 2O layer. For particles larger than 100 nm in size, selenide was formed in Se film. It was also found that the thickness of the Cu 2O layer on the surface of Cu particle accelerated diffusion of Se atoms to the copper particle.

  15. Modeling the ignition of a copper oxide aluminum thermite

    Science.gov (United States)

    Lee, Kibaek; Stewart, D. Scott; Clemenson, Michael; Glumac, Nick; Murzyn, Christopher

    2017-01-01

    An experimental "striker confinement" shock compression experiment was developed in the Glumac-group at the University of Illinois to study ignition and reaction in composite reactive materials. These include thermitic and intermetallic reactive powders. Sample of materials such as a thermite mixture of copper oxide and aluminum powders are initially compressed to about 80 percent full density. Two RP-80 detonators simultaneously push steel bars into the reactive material and the resulting compression causes shock compaction of the material and rapid heating. At that point one observes significant reaction and propagation of fronts. But the fronts are peculiar in that they are comprised of reactive events that can be traced to the reaction of the initially separated reactants of copper oxide and aluminum that react at their mutual interfaces, that nominally make copper liquid and aluminum oxide products. We discuss our model of the ignition of the copper oxide aluminum thermite in the context of the striker experiment and how a Gibbs formulation model [1], that includes multi-components for liquid and solid phases of aluminum, copper oxide, copper and aluminum oxide, can predict the events observed at the particle scale in the experiments.

  16. Cu exchanged microporous titanium silicalite (TS-1) coated on polycrystalline mullite fibres as catalyst for the CO and NO conversion

    Energy Technology Data Exchange (ETDEWEB)

    Petrov, L.; Soria, J.; Cataluna, R. [Instituto de Catalisis y Petroleoquimica, CSIC, Campus Universitario de Cantoblanco, Madrid, (Spain); Dimitrov, L.; Spasov, L.; Dimitrov, P. [Institute of Catalysis, Bulgarian Academy of Sciences, Sofia (Bulgaria)

    1996-02-29

    A surface coated with TS-1 mullite fibre was prepared. From this material, a copper containing zeolite catalyst was produced by ion exchange, that was more active for carbon monoxide oxidation reaction than the noble metal containing supported catalysts. By combining the copper containing catalyst with rhodium and ceria, a catalyst for carbon monoxide oxidation and nitric oxide reduction reactions, superior in activity to noble metals supported catalysts were prepared

  17. C-N Coupling of nitrogen nucleophiles with aryl and heteroaryl bromides using aminoarenethiolato-copper(I) (pre-)catalyst

    NARCIS (Netherlands)

    Sperotto, Elena; Klink, Gerard P.M. van; Vries, Johannes G. de; Koten, Gerard van

    2010-01-01

    The activity of a library of 2-aminoarenethiolato-copper(I) (CuSAr) (pre-)catalyst was explored in the arylation reaction of amines and N-containing heterocycles with aryl and heteroaryl bromides, respectively. These CuSAr pre-catalysts are thermally stable, are soluble in common organic solvents

  18. Evolution of Cu-Zn-Si oxide catalysts in the course of reduction and reoxidation as studied by in situ X-ray diffraction analysis, transmission electron microscopy, and magnetic susceptibility methods

    NARCIS (Netherlands)

    Minyukova, T.P.; Shtertser, N.V.; Khassin, A.A.; Plyasova, L.M.; Kustova, G.N.; Zaikovskii, V.I.; Shvedenkov, Y.G.; Baronskaya, N.A.; van den Heuvel, J.C.; Kuznetsova, A.V.; Davydova, L.P.; Yur'eva, T.M.

    2008-01-01

    The reduced and reoxidized Cu-Zn-Si oxide catalysts as layered copper-zinc hydroxo silicates with the zincsilite structure were studied using in situ and ex situ X-ray diffraction analysis, transmission electron microscopy, and the temperature dependence of magnetic susceptibility. The catalysts wer

  19. The Absorption of Benzotriazole on Copper and Cuprous Oxide

    Science.gov (United States)

    1988-07-01

    Cornell University, Ithaca INY, 14853 Copper surfaces are commonly treated with benzotriazole ( BTA ), 1. to inhibit cor- rosion. H1+ is thought to be...00 00 SIOFFICE OF NAVAL RESEARCH Contract N00014-82-K-0576 Technical Report No. 38 THE ADSORPTION OF BENZOTRIAZOLE ON COPPER AND CUPROUS OXIDE by M... Benzotriazole on Copper and Cuprous Oxide 12 7- `SONAL AUTHOR(S) M. C. Zonnevylle and R. Hoffmann 13a TYPE OF REPORT 13b TIME COVERED 14 DATE OF REPORT (Year

  20. Metal Phosphate-Supported Pt Catalysts for CO Oxidation

    Directory of Open Access Journals (Sweden)

    Xiaoshuang Qian

    2014-12-01

    Full Text Available Oxides (such as SiO2, TiO2, ZrO2, Al2O3, Fe2O3, CeO2 have often been used to prepare supported Pt catalysts for CO oxidation and other reactions, whereas metal phosphate-supported Pt catalysts for CO oxidation were rarely reported. Metal phosphates are a family of metal salts with high thermal stability and acid-base properties. Hydroxyapatite (Ca10(PO46(OH2, denoted as Ca-P-O here also has rich hydroxyls. Here we report a series of metal phosphate-supported Pt (Pt/M-P-O, M = Mg, Al, Ca, Fe, Co, Zn, La catalysts for CO oxidation. Pt/Ca-P-O shows the highest activity. Relevant characterization was conducted using N2 adsorption-desorption, inductively coupled plasma (ICP atomic emission spectroscopy, X-ray diffraction (XRD, transmission electron microscopy (TEM, CO2 temperature-programmed desorption (CO2-TPD, X-ray photoelectron spectroscopy (XPS, and H2 temperature-programmed reduction (H2-TPR. This work furnishes a new catalyst system for CO oxidation and other possible reactions.

  1. Final technical report. Bimetallic complexes as methanol oxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    McElwee-White, Lisa

    2002-01-21

    Our work on the electrocatalyzed oxidation of methanol was initially motivated by the interest in methanol as an anodic reactant in fuel cells. The literature on electrochemical oxidation of alcohols can be roughly grouped into two sets: fuel cell studies and inorganic chemistry studies. Work on fuel cells primarily focuses on surface-catalyzed oxidation at bulk metal anodes, usually Pt or Pt/Ru alloys. In the surface science/electrochemistry approach to these studies, single molecule catalysts are generally not considered. In contrast, the inorganic community investigates the electrooxidation of alcohols in homogeneous systems. Ruthenium complexes have been the most common catalysts in these studies. The alcohol substrates are typically either secondary alcohols (e.g., isopropanol) such that the reaction stops after 2 e{sup -} oxidation to the aldehyde and 4 e{sup -} oxidation to the carboxylic acid can be observed. Methanol, which can also undergo 6 e{sup -} oxidation to CO{sub 2}, rarely appears in the homogeneous catalysis studies. Surface studies have shown that two types of metal centers with different functions result in more effective catalysts than a single metal; however, application of this concept to homogeneous systems has not been demonstrated. The major thrust of the work is to apply this insight from the surface studies to homogeneous catalysis. Even though homogeneous systems would not be appropriate models for active sites on Pt/Ru anodes, it is possible that heterobimetallic catalysts could also utilize two metal centers for different roles. Starting from that perspective, this work involves the preparation and investigation of heterobinuclear catalysts for the electrochemical oxidation of methanol.

  2. Perovskite Catalysts—A Special Issue on Versatile Oxide Catalysts

    Directory of Open Access Journals (Sweden)

    Yu-Chuan Lin

    2014-08-01

    Full Text Available Perovskite-type catalysts have been prominent oxide catalysts for many years due to attributes such as flexibility in choosing cations, significant thermal stability, and the unique nature of lattice oxygen. Nearly 90% metallic elements of the Periodic Table can be stabilized in perovskite’s crystalline framework [1]. Moreover, by following the Goldschmidt rule [2], the A- and/or B-site elements can be partially substituted, making perovskites extremely flexible in catalyst design. One successful example is the commercialization of noble metal-incorporated perovskites (e.g., LaFe0.57Co0.38Pd0.05O3 for automotive emission control used by Daihatsu Motor Co. Ltd. [3]. Thus, growing interest in, and application of perovskites in the fields of material sciences, heterogeneous catalysis, and energy storage have prompted this Special Issue on perovskite catalysts. [...

  3. Heterogeneous Catalysts for VOC Oxidation from Red Mud and Bagasse Ash Carbon

    Science.gov (United States)

    Pande, Gaurav

    A range of VOC oxidation catalysts have been prepared in this study from agricultural and industrial waste as the starting point. The aim is to prepare catalysts with non-noble metal oxides as the active catalytic component (iron in red mud). The same active component was also supported on activated carbon obtained from unburned carbon in bagasse ash. Red mud which is an aluminum industry waste and rich in different phases of iron as oxide and hydroxide is used as the source for the catalytically active species. It is our aim to enhance the catalytic performance of red mud which though high in iron concentration has a low surface area and may not have the properties of an ideal catalyst by itself. In one of the attempts to enhance the catalytic performance, we have tried to leach red mud for which we have explored a range of leaching acids for effecting the leaching most efficiently and then precipitated the iron from the leachate as its hydroxide by precipitating with alkali solution followed by drying and calcination to give high surface area metal oxide material. Extensive surface characterization and VOC oxidation catalytic testing were performed for these solids. In a step to further enhance the catalytic activity towards oxidation, copper was introduced by taking another industrial waste from the copper tubing industry viz. the pickling acid. Copper has a more favourable redox potential making it catalytically more effective than iron. To make the mixed metal oxide, red mud leachate was mixed with the pickling acid in a pre-decided ratio before precipitating with alkali solution followed by drying and calcination as was done with the red mud leachate. The results from these experiments are encouraging. The temperature programmed reduction (TPR) of the solids show that the precipitate of red mud leachates show hydrogen uptake peak at a lower temperature than for just the calcined red mud. This could be due to the greatly enhanced surface area of the prepared

  4. Anticancer activity of Ficus religiosa engineered copper oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Sankar, Renu; Maheswari, Ramasamy; Karthik, Selvaraju [Department of Biochemistry, School of Life Sciences, Bharathidasan University, Tiruchirappalli 620 024, Tamilnadu (India); Shivashangari, Kanchi Subramanian, E-mail: shivashangari@gmail.com [Regional Forensic Science Laboratory, Tiruchirapalli, Tamilnadu (India); Ravikumar, Vilwanathan, E-mail: ravikumarbdu@gmail.com [Department of Biochemistry, School of Life Sciences, Bharathidasan University, Tiruchirappalli 620 024, Tamilnadu (India)

    2014-11-01

    The design, synthesis, characterization and application of biologically synthesized nanomaterials have become a vital branch of nanotechnology. There is a budding need to develop a method for environmentally benign metal nanoparticle synthesis, that do not use toxic chemicals in the synthesis protocols to avoid adverse effects in medical applications. Here, it is a report on an eco-friendly process for rapid synthesis of copper oxide nanoparticles using Ficus religiosa leaf extract as reducing and protecting agent. The synthesized copper oxide nanoparticles were confirmed by UV–vis spectrophotometer, absorbance peaks at 285 nm. The copper oxide nanoparticles were analyzed with field emission-scanning electron microscope (FE-SEM), Fourier transform infrared (FT-IR) spectroscopy, dynamic light scattering (DLS) and X-ray diffraction (XRD) spectrum. The FE-SEM and DLS analyses exposed that copper oxide nanoparticles are spherical in shape with an average particle size of 577 nm. FT-IR spectral analysis elucidates the occurrence of biomolecules required for the reduction of copper oxide ions. Zeta potential studies showed that the surface charge of the formed nanoparticles was highly negative. The XRD pattern revealed that synthesized nanoparticles are crystalline in nature. Further, biological activities of the synthesized nanoparticles were confirmed based on its stable anti-cancer effects. The apoptotic effect of copper oxide nanoparticles is mediated by the generation of reactive oxygen species (ROS) involving the disruption of mitochondrial membrane potential (Δψm) in A549 cells. The observed characteristics and results obtained in our in vitro assays suggest that the copper nanoparticles might be a potential anticancer agent. - Highlights: • Biogenic synthesis of copper oxide nanoparticles by leaf extract of Ficus religiosa • Characterized via UV–vis, FT-IR, DLS, FE-SEM with EDAX and XRD • Protein may act as an encapsulating, reducing and stabilizing

  5. Comparative proteomic analysis of the molecular responses of mouse macrophages to titanium dioxide and copper oxide nanoparticles unravels some toxic mechanisms for copper oxide nanoparticles in macrophages.

    Directory of Open Access Journals (Sweden)

    Sarah Triboulet

    Full Text Available Titanium dioxide and copper oxide nanoparticles are more and more widely used because of their catalytic properties, of their light absorbing properties (titanium dioxide or of their biocidal properties (copper oxide, increasing the risk of adverse health effects. In this frame, the responses of mouse macrophages were studied. Both proteomic and targeted analyses were performed to investigate several parameters, such as phagocytic capacity, cytokine release, copper release, and response at sub toxic doses. Besides titanium dioxide and copper oxide nanoparticles, copper ions were used as controls. We also showed that the overall copper release in the cell does not explain per se the toxicity observed with copper oxide nanoparticles. In addition, both copper ion and copper oxide nanoparticles, but not titanium oxide, induced DNA strands breaks in macrophages. As to functional responses, the phagocytic capacity was not hampered by any of the treatments at non-toxic doses, while copper ion decreased the lipopolysaccharide-induced cytokine and nitric oxide productions. The proteomic analyses highlighted very few changes induced by titanium dioxide nanoparticles, but an induction of heme oxygenase, an increase of glutathione synthesis and a decrease of tetrahydrobiopterin in response to copper oxide nanoparticles. Subsequent targeted analyses demonstrated that the increase in glutathione biosynthesis and the induction of heme oxygenase (e.g. by lovastatin/monacolin K are critical for macrophages to survive a copper challenge, and that the intermediates of the catecholamine pathway induce a strong cross toxicity with copper oxide nanoparticles and copper ions.

  6. Comparative proteomic analysis of the molecular responses of mouse macrophages to titanium dioxide and copper oxide nanoparticles unravels some toxic mechanisms for copper oxide nanoparticles in macrophages.

    Science.gov (United States)

    Triboulet, Sarah; Aude-Garcia, Catherine; Armand, Lucie; Collin-Faure, Véronique; Chevallet, Mireille; Diemer, Hélène; Gerdil, Adèle; Proamer, Fabienne; Strub, Jean-Marc; Habert, Aurélie; Herlin, Nathalie; Van Dorsselaer, Alain; Carrière, Marie; Rabilloud, Thierry

    2015-01-01

    Titanium dioxide and copper oxide nanoparticles are more and more widely used because of their catalytic properties, of their light absorbing properties (titanium dioxide) or of their biocidal properties (copper oxide), increasing the risk of adverse health effects. In this frame, the responses of mouse macrophages were studied. Both proteomic and targeted analyses were performed to investigate several parameters, such as phagocytic capacity, cytokine release, copper release, and response at sub toxic doses. Besides titanium dioxide and copper oxide nanoparticles, copper ions were used as controls. We also showed that the overall copper release in the cell does not explain per se the toxicity observed with copper oxide nanoparticles. In addition, both copper ion and copper oxide nanoparticles, but not titanium oxide, induced DNA strands breaks in macrophages. As to functional responses, the phagocytic capacity was not hampered by any of the treatments at non-toxic doses, while copper ion decreased the lipopolysaccharide-induced cytokine and nitric oxide productions. The proteomic analyses highlighted very few changes induced by titanium dioxide nanoparticles, but an induction of heme oxygenase, an increase of glutathione synthesis and a decrease of tetrahydrobiopterin in response to copper oxide nanoparticles. Subsequent targeted analyses demonstrated that the increase in glutathione biosynthesis and the induction of heme oxygenase (e.g. by lovastatin/monacolin K) are critical for macrophages to survive a copper challenge, and that the intermediates of the catecholamine pathway induce a strong cross toxicity with copper oxide nanoparticles and copper ions.

  7. Comparative Proteomic Analysis of the Molecular Responses of Mouse Macrophages to Titanium Dioxide and Copper Oxide Nanoparticles Unravels Some Toxic Mechanisms for Copper Oxide Nanoparticles in Macrophages

    Science.gov (United States)

    Triboulet, Sarah; Aude-Garcia, Catherine; Armand, Lucie; Collin-Faure, Véronique; Chevallet, Mireille; Diemer, Hélène; Gerdil, Adèle; Proamer, Fabienne; Strub, Jean-Marc; Habert, Aurélie; Herlin, Nathalie; Van Dorsselaer, Alain; Carrière, Marie; Rabilloud, Thierry

    2015-01-01

    Titanium dioxide and copper oxide nanoparticles are more and more widely used because of their catalytic properties, of their light absorbing properties (titanium dioxide) or of their biocidal properties (copper oxide), increasing the risk of adverse health effects. In this frame, the responses of mouse macrophages were studied. Both proteomic and targeted analyses were performed to investigate several parameters, such as phagocytic capacity, cytokine release, copper release, and response at sub toxic doses. Besides titanium dioxide and copper oxide nanoparticles, copper ions were used as controls. We also showed that the overall copper release in the cell does not explain per se the toxicity observed with copper oxide nanoparticles. In addition, both copper ion and copper oxide nanoparticles, but not titanium oxide, induced DNA strands breaks in macrophages. As to functional responses, the phagocytic capacity was not hampered by any of the treatments at non-toxic doses, while copper ion decreased the lipopolysaccharide-induced cytokine and nitric oxide productions. The proteomic analyses highlighted very few changes induced by titanium dioxide nanoparticles, but an induction of heme oxygenase, an increase of glutathione synthesis and a decrease of tetrahydrobiopterin in response to copper oxide nanoparticles. Subsequent targeted analyses demonstrated that the increase in glutathione biosynthesis and the induction of heme oxygenase (e.g. by lovastatin/monacolin K) are critical for macrophages to survive a copper challenge, and that the intermediates of the catecholamine pathway induce a strong cross toxicity with copper oxide nanoparticles and copper ions. PMID:25902355

  8. Oxidative homocoupling of alkynes using supported ionic liquid phase (SILP) catalysts--systematic investigation of the support influence.

    Science.gov (United States)

    Szesni, Normen; Kaiser, Melanie; Putzien, Sophie; Fischer, Richard W

    2012-02-01

    Supported Ionic Liquid Phase (SILP) catalysts have been prepared by effective immobilization of [Cu(TMEDA)(OH)]Cl in a nano-metric film of an ionic liquid on various oxidic support materials. The catalysts were tested for the oxidative homocoupling of 1-alkynes to the corresponding diynes in in a combined high throughput and conventional batch reaction approach. Among the screened support materials silica based materials performed best. The results indicate that for the specific reaction the thickness of the ionic liquids layer and therefore the mobility of the homogeneous copper complex within the ionic liquid layer as deduced from solid state nmr measurements have major impact on the catalytic performance. The optimized catalysts could be recycled up to four times without any loss of activity.

  9. Bioinspired copper catalyst effective for both reduction and evolution of oxygen

    Science.gov (United States)

    Wang, Jiong; Wang, Kang; Wang, Feng-Bin; Xia, Xing-Hua

    2014-10-01

    In many green electrochemical energy devices, the conversion between oxygen and water suffers from high potential loss due to the difficulty in decreasing activation energy. Overcoming this issue requires full understanding of global reactions and development of strategies in efficient catalyst design. Here we report an active copper nanocomposite, inspired by natural coordination environments of catalytic sites in an enzyme, which catalyzes oxygen reduction/evolution at potentials closely approaching standard potential. Such performances are related to the imperfect coordination configuration of the copper(II) active site whose electron density is tuned by neighbouring copper(0) and nitrogen ligands incorporated in graphene. The electron transfer number of oxygen reduction is estimated by monitoring the redox of hydrogen peroxide, which is determined by the overpotential and electrolyte pH. An in situ fluorescence spectroelectrochemistry reveals that hydroxyl radical is the common intermediate for the electrochemical conversion between oxygen and water.

  10. Removal of ammonia from aqueous solutions by catalytic oxidation with copper-based rare earth composite metal materials: catalytic performance, characterization, and cytotoxicity evaluation

    Institute of Scientific and Technical Information of China (English)

    Chang-Mao Hung

    2011-01-01

    Ammonia (NH3) has an important use in the chemical industry and is widely found in industrial wastewater.For this investigation of copper-based rare earth composite metal materials,aqueous solutions containing 400 mg/L of ammonia were oxidized in a batch-bed reactor with a catalyst prepared by the co-precipitation of copper nitrate,lanthanum nitrate and cerium nitrate.Barely any of the dissolved ammonia was removed by wet oxidation without a catalyst,but about 88% of the ammonia was reduced during wet oxidation over the catalysts at 423 K with an oxygen partial pressure of 4.0 MPa.The catalytic redox behavior was determined by cyclic voltammetry (CV).Furthermore,the catalysts were characterized using thermogravimetric analyzer (TGA) and scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDX),which showed that the catalytic behavior was related to the metal oxide properties of the catalyst.In addition,the copper-lanthanum-cerium composite-induced cytotoxicity in the human lung MRC-5 cell line was tested,and the percentage cell survival was determined by 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetra-zolium (MTS) analysis in vitro.No apparent cytotoxicity was observed when the human lung cells were exposed to the copper-lanthanum-cerium composite.

  11. Certain aspects of the formation and identification of nanosized oxide components in heterogeneous catalysts prepared by different methods

    Science.gov (United States)

    Ellert, Ol'ga G.; Tsodikov, Mark V.; Novotortsev, Vladimir M.

    2010-10-01

    The results of studies into the relationship 'methods and synthesis conditions of a catalyst→catalyst structure→catalytic properties' in highly efficient crystallo-graphically amorphous copper- and iron-containing heterogeneous systems obtained by different chemical methods are generalized. Polymorphism of active phases and catalytic properties of nanostructured copper-containing zinc, zirconium, manganese and cerium oxides are discussed. Unusual transformations of nanosized Pt- and Pd-containing components on the γ-Al2O3 surface in nanostructured catalysts of ethanol steam reforming into synthesis gas and reductive dehydration of ethanol to alkanes are considered. The results of comparative studies on the crystallographically amorphous mixed iron oxide catalysts synthesized by either the alkoxy method or the deposition on various supports obtained by the Mössbauer and XAFS spectroscopy and magnetic susceptibility measurements are presented. These materials are shown to be efficient catalysts of important processes such as liquid-phase oxidation of hydrocarbons, synthesis of alkenes and alkylaromatic hydrocarbons from CO and H2, hydrogenative transformation of brown coal organic mass to hydrocarbons.

  12. Enhanced electrochemical methanation of carbon dioxide with a dispersible nanoscale copper catalyst.

    Science.gov (United States)

    Manthiram, Karthish; Beberwyck, Brandon J; Alivisatos, A Paul

    2014-09-24

    Although the vast majority of hydrocarbon fuels and products are presently derived from petroleum, there is much interest in the development of routes for synthesizing these same products by hydrogenating CO2. The simplest hydrocarbon target is methane, which can utilize existing infrastructure for natural gas storage, distribution, and consumption. Electrochemical methods for methanizing CO2 currently suffer from a combination of low activities and poor selectivities. We demonstrate that copper nanoparticles supported on glassy carbon (n-Cu/C) achieve up to 4 times greater methanation current densities compared to high-purity copper foil electrodes. The n-Cu/C electrocatalyst also exhibits an average Faradaic efficiency for methanation of 80% during extended electrolysis, the highest Faradaic efficiency for room-temperature methanation reported to date. We find that the level of copper catalyst loading on the glassy carbon support has an enormous impact on the morphology of the copper under catalytic conditions and the resulting Faradaic efficiency for methane. The improved activity and Faradaic efficiency for methanation involves a mechanism that is distinct from what is generally thought to occur on copper foils. Electrochemical data indicate that the early steps of methanation on n-Cu/C involve a pre-equilibrium one-electron transfer to CO2 to form an adsorbed radical, followed by a rate-limiting non-electrochemical step in which the adsorbed CO2 radical reacts with a second CO2 molecule from solution. These nanoscale copper electrocatalysts represent a first step toward the preparation of practical methanation catalysts that can be incorporated into membrane-electrode assemblies in electrolyzers.

  13. An FT-IR study of NO adsorption over Cu-exchanged MFI catalysts. Effect of Si/Al ratio, copper loading and catalyst pre-treatment

    Energy Technology Data Exchange (ETDEWEB)

    Henriques, C.; Ribeiro, M.F.; Abreu, C. [Grupo de Zeolitos, Departamento de Engenharia Quimica, Instituto Superior Tecnico, Lisbon (Portugal); Murphy, D.M. [Department of Chemistry, University of Wales Cardiff, Cardiff (United Kingdom); Poignant, F.; Saussey, J.; Lavalley, J.C. [Laboratoire de Catalyse et Spectrochimie - ISMRA, Universite de Caen, URA 414, Caen (France)

    1998-03-06

    NO adsorption, at room temperature, has been studied by infrared spectroscopy on copper MFI catalysts with different Si/Al ratios and copper loadings. The relative amount of the overall Cu{sup 2+}-NO and Cu{sup +}-NO complexes has been evaluated for each catalyst, as well as that of the different Cu{sup 2+}-NO components. ESR spectra have also been recorded in order to check the different Cu{sup 2+} coordinations. It clearly appears that square planar copper sites predominate for high Cu/Al catalysts. A comparison with reactivity data, relative to SCR of NO by propene, under an excess of oxygen, strongly suggests that these sites are involved in the considered reaction

  14. Copper-catalyzed aerobic oxidative C-C bond cleavage of unstrained ketones with air and amines.

    Science.gov (United States)

    Zhou, Wang; Fan, Wenyou; Jiang, Qijian; Liang, Yu-Feng; Jiao, Ning

    2015-05-15

    A unique copper-catalyzed aerobic oxidative C-C bond cleavage of simple unstrained ketones with air and amines has been developed. In this chemistry, amides and oxo amides are easily synthesized through the selective C-C bond cleavage of simple ketones or unstrained cycloketones. The broad substrate scopes and use of an inexpensive copper catalyst and green molecular oxygen as an oxidant as well as an O-source make this protocol very attractive for potential synthetic applications. The control experiments reveal that the present copper-catalyzed oxidative C-C bond cleavage of simple ketones proceeds in a novel catalytic pathway rather than through the cleavage of a dioxetane intermediate.

  15. Bio-inspired Iron Catalysts for Hydrocarbon Oxidations

    Energy Technology Data Exchange (ETDEWEB)

    Que, Jr., Lawrence [Univ. of Minnesota, Minneapolis, MN (United States)

    2016-03-22

    Stereoselective oxidation of C–H and C=C bonds are catalyzed by nonheme iron enzymes. Inspired by these bioinorganic systems, our group has been exploring the use of nonheme iron complexes as catalysts for the oxidation of hydrocarbons using H2O2 as an environmentally friendly and atom-efficient oxidant in order to gain mechanistic insights into these novel transformations. In particular, we have focused on clarifying the nature of the high-valent iron oxidants likely to be involved in these transformations.

  16. Cyano- and polycyanometalloporphyrins as catalysts for alkane oxidation

    Science.gov (United States)

    Ellis, Jr., Paul E.; Lyons, James E.

    1992-01-01

    Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been substituted with one or more cyano groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

  17. Progress on the mechanistic understanding of SO2 oxidation catalysts

    DEFF Research Database (Denmark)

    Lapina, Olga B.; Bal'zhinimaev, B.S.; Boghosian, Soghomon

    1999-01-01

    For almost a century vanadium oxide based catalysts have been the dominant materials in industrial processes for sulfuric acid production. A vast body of information leading to fundamental knowledge on the catalytic process was obtained by Academician [G.K. Boreskov, Catalysis in Sulphuric Acid...

  18. Ti-STT: a new zeotype shape selective oxidation catalyst.

    Science.gov (United States)

    Eilertsen, Einar André; Giordanino, Filippo; Lamberti, Carlo; Bordiga, Silvia; Damin, Alessandro; Bonino, Francesca; Olsbye, Unni; Lillerud, Karl Petter

    2011-11-21

    A new zeotype titanium silicate oxidation catalyst with the STT topology has been synthesized from direct synthesis. Ti-STT has a microporous structure with small pore openings, allowing shape selective oxidation catalysis. The isomorphous substitution of Si by Ti in the framework has been confirmed by Raman, FT-IR, UV-VIS and XANES spectroscopies. This journal is © The Royal Society of Chemistry 2011

  19. The direct transformation of ethanol to ethyl acetate over Cu/SiO2 catalysts that contain copper phyllosilicate

    Indian Academy of Sciences (India)

    Xue Yu; Shubo Zhai; Wanchun Zhu; Shuang Gao; Jianbiao Yan; Hongjing Yuan; Lili Chen; Jiahuan Luo; Wenxiang Zhang; Zhenlu Wang

    2014-07-01

    Cu/SiO2 catalysts that contain copper phyllosilicate, were successfully prepared using the ammonia-evaporation method. The catalysts were characterized via XRD, ICP, BET, FTIR, TPR, XPS, NH3-TPD and FTIR of Pyridine Adsorption techniques. The results demonstrated that the formation of the copper phyllosilicate species significantly affected the structural properties and caused the CuO nanoparticles to become highly dispersed, and the copper phyllosilicate would provide access to the Lewis acidic Cu+ species. It was found that the catalyst with a 23.7 wt% copper loading exhibited the best ethanol conversion and ethyl acetate selectivity. When compared to a catalyst with the same copper loading which was prepared with the impregnation method, the higher activity and selectivity of catalysts might be ascribed to the homogenous distribution of copper nanoparticles, which was the active site for the dehydrogenation, and the amount of Lewis acidic Cu+ sites active for esterification. The synergetic effect between the Cu0 and Lewis acidic sites was the key factor to achieve direct transformation of ethanol to ethyl acetate.

  20. Method for improving catalyst function in auto-thermal and partial oxidation reformer-based processors

    Science.gov (United States)

    Ahmed, Shabbir; Papadias, Dionissios D.; Lee, Sheldon H.D.; Ahluwalia, Rajesh K.

    2014-08-26

    The invention provides a method for reforming fuel, the method comprising contacting the fuel to an oxidation catalyst so as to partially oxidize the fuel and generate heat; warming incoming fuel with the heat while simultaneously warming a reforming catalyst with the heat; and reacting the partially oxidized fuel with steam using the reforming catalyst.

  1. Sol-gel based oxidation catalyst and coating system using same

    Science.gov (United States)

    Watkins, Anthony N. (Inventor); Leighty, Bradley D. (Inventor); Oglesby, Donald M. (Inventor); Patry, JoAnne L. (Inventor); Schryer, Jacqueline L. (Inventor)

    2010-01-01

    An oxidation catalyst system is formed by particles of an oxidation catalyst dispersed in a porous sol-gel binder. The oxidation catalyst system can be applied by brush or spray painting while the sol-gel binder is in its sol state.

  2. Oxidative dehydrogenation of ethylbenzene using nitrous oxide over vanadia-magnesia catalysts

    NARCIS (Netherlands)

    Shiju, N.R.; Anilkumar, M.; Gokhale, S.P.; Rao, B.S.; Satyanarayana, C.V.V.

    2011-01-01

    A series of V-Mg-O catalysts with different loadings of vanadia were prepared by the wet impregnation method and the effect of the local structure of these catalysts on the oxidative dehydrogenation of ethylbenzene with N2O was investigated. High styrene selectivity (97%) was obtained at 773 K. The

  3. Redox Equilibria in SO2 Oxidation Catalysts

    DEFF Research Database (Denmark)

    Rasmussen, Søren Birk; Eriksen, Kim Michael; Boghosian, Soghomon

    1999-01-01

    been carried out regarding the complex and compound formation of V(V) and the formation of V(IV) and V(III) compounds with low solubility causing catalyst deactivation. However, the redox chemistry of vanadium and the complex formation of V(IV) is much less investigated and further information...... on these subjects in pyrosulfate melts is needed to obtain a deeper understanding of the reaction mechanism. The present paper describes our efforts so far to study the V(IV) chemistry using especially spectroscopic and electrochemical methods....

  4. Denitrifying kinetics and nitrous oxide emission under different copper concentrations.

    Science.gov (United States)

    Wu, Guangxue; Zhai, Xiaofeng; Jiang, Chengai; Guan, Yuntao

    2014-01-01

    Denitrifying activities and nitrous oxide (N2O) emission during denitrification can be affected by copper concentrations. Different denitrifiers were acclimated in sequencing batch reactors with acetate or methanol as the electron donor and nitrate as the electron acceptor. The effect of copper concentrations on the denitrifying activity and N2O emission for the acclimated denitrifiers was examined in batch experiments. Denitrifying activities of the acclimated denitrifiers declined with increasing copper concentrations, and the copper concentration exhibited a higher effect on denitrifiers acclimated with acetate than those acclimated with methanol. Compared with the control without the addition of copper, at the copper concentration of 1 mg/L, the acetate utilization rate reduced by 89% for acetate-acclimated denitrifiers, while the methanol utilization rate only reduced by 15% for methanol-acclimated denitrifiers. Copper also had different effects on N2O emission during denitrification carried out by various types of denitrifiers. For the acetate-acclimated denitrifiers, N2O emission initially increased and then decreased with increasing copper concentrations, while for the methanol-acclimated denitrifiers, N2O emission decreased with increasing copper concentrations.

  5. Hydroformylation of 1-Hexene over Rh/Nano-Oxide Catalysts

    Directory of Open Access Journals (Sweden)

    Sari Suvanto

    2013-03-01

    Full Text Available The effect of nanostructured supports on the activity of Rh catalysts was studied by comparing the catalytic performance of nano- and bulk-oxide supported Rh/ZnO, Rh/SiO2 and Rh/TiO2 systems in 1-hexene hydroformylation. The highest activity with 100% total conversion and 96% yield of aldehydes was obtained with the Rh/nano-ZnO catalyst. The Rh/nano-ZnO catalyst was found to be more stable and active than the corresponding rhodium catalyst supported on bulk ZnO. The favorable morphology of Rh/nano-ZnO particles led to an increased metal content and an increased number of weak acid sites compared to the bulk ZnO supported catalysts. Both these factors favored the improved catalytic performance. Improvements of catalytic properties were obtained also with the nano-SiO2 and nano-TiO2 supports in comparison with the bulk supports. All of the catalysts were characterized by scanning electron microscope (SEM, inductively coupled plasma mass spectrometry (ICP-MS, BET, powder X-ray diffraction (PXRD and NH3- temperature-programmed desorption (TPD.

  6. Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Eraenen, K.; Kumar, N.; Lindfors, L.E. [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry

    1996-12-31

    Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

  7. Selective liquid phase oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide over γ-Al2O3 supported copper and gold nanoparticles

    Science.gov (United States)

    Ndolomingo, Matumuene Joe; Meijboom, Reinout

    2017-03-01

    Benzyl alcohol oxidation to benzaldehyde was performed by tert-butyl hydroperoxide (TBHP) in the absence of any solvent using γ-Al2O3 supported copper and gold nanoparticles. Li2O and ionic liquids were used as additive and stabilizers for the synthesis of the catalysts. The physico-chemical properties of the catalysts were characterized by atomic absorption spectroscopy (AAS), X-ray diffraction spectroscopy (XRD), N2 absorption/desorption (BET), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and temperature programmed reduction (TPR), whereas, the oxidation reaction was followed by gas chromatography with a flame ionization detector (GC-FID). The as prepared catalysts exhibited good catalytic performance in terms of conversion and selectivity towards benzaldehyde. The performance of the Au-based catalysts is significantly higher than that of the Cu-based catalysts. For both Cu and Au catalysts, the conversion of benzyl alcohol increased as the reaction proceeds, while the selectivity for benzaldehyde decreased. Moreover, the catalysts can be easily recycled and reused with neither significant loss of activity nor selectivity. A kinetic study for the Cu and Au-catalyzed oxidation of benzyl alcohol to benzyldehyde is reported. The rate at which the oxidation of benzyl alcohol is occurring as a function of catalyst and oxidant amounts was investigated, with the apparent rate constant, kapp being proportional to the amount of nano catalyst and oxygen present in the system.

  8. Copper oxide as a high temperature battery cathode material

    Science.gov (United States)

    Ritchie, A. G.; Mullins, A. P.

    1994-10-01

    Copper oxide has been tested as a cathode material for high temperature primary reserve thermal batteries in single cells at 530 to 600 C and at current densities of 0.1 to 0.25 A cm(exp -2) using lithium-aluminium alloy anodes and lithium fluoride-lithium chloride-lithium bromide molten salt electrolytes. Initial on-load voltages were around 2.3 V, falling to 1.5 V after about 0.5 F mol(exp -1) had been withdrawn. Lithium copper oxide, LiCu2O2, and cuprous oxide, Cu2O, were identified as discharge products.

  9. Vibronic dispersion in the copper oxide superconductors

    Science.gov (United States)

    Goodenough, J. B.; Zhou, J.-S.

    1994-02-01

    Attempts to describe the normal-state electronic behavior of the copper oxide superconductors have been unable to reconcile the following observations: (i) a well-defined Fermi surface with a locus predicted by band theory, but having charge carriers of a sign predicted for a Mott-Hubbard splitting of the band; (ii) a change in sign of the carriers to that predicted by band theory, but without a significant change in the locus of the Fermi surface, on overdoping beyond the narrow superconductive compositional range; (iii) a remarkable stability of the narrow range of superconductive charge-carrier concentrations in the CuO2 sheets even in the presence of charge transfer from nonsuperconductive intergrowth layers; (iv) a dramatic sensitivity of the Néel temperature of the parent compound to oxidation of the CuO2 sheets, but the persistence of antiferromagnetic spin fluctuations into the superconductive compositions; and (v) unusual transport properties that cannot be treated within the Migdal approximation and are insensitive to high magnetic fields. To address this impasse, we propose a phenomenological polaron model based on the observation that the system must accommodate to the coexistence of ``ionic'' and ``covalent'' Cu-O bonding having different equilibrium Cu-O bond lengths. We designate this entity a correlation polaron. Covalent Cu-O bonding with molecular-orbital formation occurs within the polaron, which moves in a background of ionic Cu-O bonding. Vibronic coupling at the ``avoided crossover'' from ionic to covalent bonding allows diffusional motion of uncoupled polarons without any motional enthalpy in the mobility. At temperatures T>Tl>~300 K the polarons are uncoupled and move randomly; in the narrow superconductive compositional range they condense below Tl to form a distinguishable thermodynamic phase consisting of extended vibronic states. In this ``polaron liquid,'' a distinction between bonding and antibonding states within the polarons opens a

  10. Preparation and characterization of copper-doped cobalt oxide electrodes.

    Science.gov (United States)

    Rosa-Toro, A La; Berenguer, R; Quijada, C; Montilla, F; Morallón, E; Vazquez, J L

    2006-11-30

    Cobalt oxide (Co3O4) and copper-doped cobalt oxide (CuxCo(3-x)O4) films have been prepared onto titanium support by the thermal decomposition method. The electrodes have been characterized by different techniques such as cyclic voltammetry, scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). The effect on the electrochemical and crystallographic properties and surface morphology of the amount of copper in the oxide layer has been analyzed. The XPS spectra correspond to a characteristic monophasic Cu-Co spinel oxides when x is below 1. However, when the copper content exceeds that for the stoichiometric CuCo2O4 spinel, a new CuO phase segregates at the surface. The analysis of the surface cation distribution indicates that Cu(II) has preference for octahedral sites.

  11. MECHANISM OF THE OXIDATION OF HEMOGLOBIN BY COPPER (II COMPLXES

    Directory of Open Access Journals (Sweden)

    M. BAYATI

    1994-07-01

    Full Text Available An outer sphere electron transfer mechanism by which human hemoglobin reduces the complexes of copper(II and, in turn, is oxidized to methemoglobin has been characterized. We have found that the rate of oxidation of hemoglobin is a function of pH, temperature, concentration of copper(II, and the environment of the hemoglobin. Prior to oxidation, copper(II complex binds to specific sites on the surface of the protein by losing one or more of its ligands, forming a ternary complex. This process is followed by electron transfer between the Cu(II and Fe(H with the Cu(II-deoxyhemoglobin being the active intermediate. The dominant factors which govern the rate of oxidation of hemoglobin by coppcr(I I complexes seem to be the stability constant of the Cu(II complexes and the overall redox potential of the ternary complex.

  12. Perovskite-type Mixed Oxides Catalyst for Complete Oxidation of Acetone

    Institute of Scientific and Technical Information of China (English)

    DUAN; ZhiYing

    2001-01-01

    The catalytic oxidation of VOCs (volatile organic compounds) is an attractive subject in the field of environmental protection now. Furthermore, most countries have made out regulations m controlling the maximum content of VOCs in some places. Presently, the leading way of domestic and foreign means to eliminate VOCs is to completely oxidize VOCs into carbon dioxide and water in presence of noble metal catalyst. But noble metal is expensive for lack of resource[2]. So it is insistent to research a low-cost catalyst for removal of VOCs. In this work, we have used some base metals (such as La, Sr, Ce, Ni, Cu) to synthesize mixed oxides catalyst supported on γ-A12O3. We have investigated the catalytic properties in the complete oxidation of acetone over the catalyst prepared and achieved an exciting result.……

  13. Perovskite-type Mixed Oxides Catalyst for Complete Oxidation of Acetone

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ The catalytic oxidation of VOCs (volatile organic compounds) is an attractive subject in the field of environmental protection now. Furthermore, most countries have made out regulations m controlling the maximum content of VOCs in some places. Presently, the leading way of domestic and foreign means to eliminate VOCs is to completely oxidize VOCs into carbon dioxide and water in presence of noble metal catalyst. But noble metal is expensive for lack of resource[2]. So it is insistent to research a low-cost catalyst for removal of VOCs. In this work, we have used some base metals (such as La, Sr, Ce, Ni, Cu) to synthesize mixed oxides catalyst supported on γ-A12O3. We have investigated the catalytic properties in the complete oxidation of acetone over the catalyst prepared and achieved an exciting result.

  14. Catalytic Oxidative Properties and Characterization of CuO/CeO2 Catalysts

    Institute of Scientific and Technical Information of China (English)

    蒋晓原; 周仁贤; 袁骏; 吕光烈; 郑小明

    2003-01-01

    The oxidative properties and characterization of CuO, CeO2 and CuO/CeO2 catalysts were examined by means of a CO micro-reactor GC system, TPR, XPS and X-ray diffraction Rietveld methods. The results show that either CuO or CeO2 activity is quite low for CO oxidation. However, when CuO and CeO2 are mixed, the oxidative activity of the catalyst increases significantly, probably owing to the valency status of copper species (Cu2+ and Cu+) on the CeO2 surface, the dispersion and reducibility. XPS surface analysis shows that CuO loading is very important in forming of either Cu2+ or Cu+. Rietveld analysis shows that some CuO, which has smaller ion radius than Ce4+, enters the CeO2 lattice after CuO and CeO2 are mixed. When the CuO loading reaches 5.0%, the size of CuO crystals is a minimum (6.1 nm) and the micro-strain value is a maximum (2.86×10-3), resulting in high surface energy and the best activity for CO oxidation.

  15. Chemical nature of catalysts of oxide nanoparticles in environment prevailing during growth of carbon nanostructures by CCVD

    Indian Academy of Sciences (India)

    M JANA; A SIL; S RAY

    2016-12-01

    Carbon nanostructures (CNS) are often grown using oxide nanoparticles as catalyst in chemical vapour deposition and these oxides are not expected to survive as such during growth. In the present study, the catalysts of cobalt- and nickel oxide-based nanoparticles of sizes varying over a range have been reduced at 575$^{\\circ}$C under environment resulting from the introduction of C$_2$H$_2$ $+$ NH$_3$ during growth of CNS as well as under introductionof C$_2$H$_2$ and NH$_3$ separately. The structure of the reduced nanoparticles is often different from the equilibrium structure of the bulk. Nanoparticles of cobalt oxide with and without doping by copper oxide are reduced to cobalt alloy or cobalt nanoparticles having fcc structure, but the rate of reduction is relatively less in NH$_3$ environment. However, reduced nickel oxide nanoparticles with and without doping shows a mix of fcc and hcp phases. The presence of hydrogen and nitrogen in the environment appears to discourage the formation of hcp nickel as inferred from the results in NH$_3$ environment. Cobalt carbide forms when the 10 wt.% or less doped cobalt oxide is reduced in C$_2$H$_2$ $+$ NH$_3$ environment. At higher level of doping of 20 wt.%, separate metallic phase of copper appears andcarbide formation gets suppressed.

  16. Anticancer activity of Ficus religiosa engineered copper oxide nanoparticles.

    Science.gov (United States)

    Sankar, Renu; Maheswari, Ramasamy; Karthik, Selvaraju; Shivashangari, Kanchi Subramanian; Ravikumar, Vilwanathan

    2014-11-01

    The design, synthesis, characterization and application of biologically synthesized nanomaterials have become a vital branch of nanotechnology. There is a budding need to develop a method for environmentally benign metal nanoparticle synthesis, that do not use toxic chemicals in the synthesis protocols to avoid adverse effects in medical applications. Here, it is a report on an eco-friendly process for rapid synthesis of copper oxide nanoparticles using Ficus religiosa leaf extract as reducing and protecting agent. The synthesized copper oxide nanoparticles were confirmed by UV-vis spectrophotometer, absorbance peaks at 285 nm. The copper oxide nanoparticles were analyzed with field emission-scanning electron microscope (FE-SEM), Fourier transform infrared (FT-IR) spectroscopy, dynamic light scattering (DLS) and X-ray diffraction (XRD) spectrum. The FE-SEM and DLS analyses exposed that copper oxide nanoparticles are spherical in shape with an average particle size of 577 nm. FT-IR spectral analysis elucidates the occurrence of biomolecules required for the reduction of copper oxide ions. Zeta potential studies showed that the surface charge of the formed nanoparticles was highly negative. The XRD pattern revealed that synthesized nanoparticles are crystalline in nature. Further, biological activities of the synthesized nanoparticles were confirmed based on its stable anti-cancer effects. The apoptotic effect of copper oxide nanoparticles is mediated by the generation of reactive oxygen species (ROS) involving the disruption of mitochondrial membrane potential (Δψm) in A549 cells. The observed characteristics and results obtained in our in vitro assays suggest that the copper nanoparticles might be a potential anticancer agent.

  17. Pilot-Scale Oxidation Catalysts Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Catalytic oxidation of contaminants in air and water remains a key unit operation available to NASA. Its advantages include production of high-quality effluents,...

  18. Comparative effects of dissolved copper and copper oxide nanoparticle exposure to the sea anemone, Exaiptasia pallida

    Energy Technology Data Exchange (ETDEWEB)

    Siddiqui, Samreen; Goddard, Russell H.; Bielmyer-Fraser, Gretchen K., E-mail: gkbielmyer@valdosta.edu

    2015-03-15

    Highlights: • Differences between CuO NP and CuCl{sub 2} exposure were characterized. • Copper accumulation in E. pallida was concentration-dependent. • E. pallida exposed to CuCl{sub 2} accumulated higher copper tissue burdens. • The oxidative stress response was greater in E. pallida exposed to CuO NP. • Both forms of copper inhibited CA activity in E. pallida. - Abstract: Increasing use of metal oxide nanoparticles (NP) by various industries has resulted in substantial output of these NP into aquatic systems. At elevated concentrations, NP may interact with and potentially affect aquatic organisms. Environmental implications of increased NP use are largely unknown, particularly in marine systems. This research investigated and compared the effects of copper oxide (CuO) NP and dissolved copper, as copper chloride (CuCl{sub 2}), on the sea anemone, Exaiptasia pallida. Sea anemones were collected over 21 days and tissue copper accumulation and activities of the enzymes: catalase, glutathione peroxidase, glutathione reductase, and carbonic anhydrase were quantified. The size and shape of CuO NP were observed using a ecanning electron microscope (SEM) and the presence of copper was confirmed by using Oxford energy dispersive spectroscopy systems (EDS/EDX). E. pallida accumulated copper in their tissues in a concentration- and time-dependent manner, with the animals exposed to CuCl{sub 2} accumulating higher tissue copper burdens than those exposed to CuO NP. As a consequence of increased copper exposure, as CuO NP or CuCl{sub 2}, anemones increased activities of all of the antioxidant enzymes measured to some degree, and decreased the activity of carbonic anhydrase. Anemones exposed to CuO NP generally had higher anti-oxidant enzyme activities than those exposed to the same concentrations of CuCl{sub 2}. This study is useful in discerning differences between CuO NP and dissolved copper exposure and the findings have implications for exposure of aquatic

  19. Copper nanoparticles supported onto montmorillonite clays as efficient catalyst for methylene blue dye degradation

    Directory of Open Access Journals (Sweden)

    M.A. Mekewi

    2016-06-01

    Full Text Available The paper describes the production of copper nanoparticles through the reduction of copper chloride (CuCl2·2H2O by hydrazine in the aqueous cetyle trimethyl ammonium bromide (CTAB solution. The copper nanoparticles were then supported on chemically activated Montmorillonite clay (MMT. The native and modified clays as well as synthesized Cu-nanoparticle-clay were structurally and texturally characterized by XRD, FTIR, BET, SEM and TEM in addition to the estimation of exchange capacity parameters. BET surface characterization revealed a decrease in surface area of the clay support after the incorporation of Cu nanoparticles. Cu/clay was then utilized as a catalyst for the degradation of aqueous solutions containing methylene blue (MB over a wide pH range. Diverse kinetics models were employed to examine the degradation process revealing a better fit with pseudo-first-order model. The present study offers a novel modified clay based catalysts for the degradation of methylene blue dye contaminant from wastewater.

  20. Quantum Magnetic Excitations from Stripes in Copper-Oxide Superconductors

    OpenAIRE

    Tranquada, J. M.; Woo, H.; Perring, T. G.; Goka, H; Gu, G. D.; Xu, G; Fujita, M.; Yamada, K.

    2004-01-01

    In the copper-oxide parent compounds of the high-transition-temperature superconductors, the valence electrons are localized, one per copper site, due to strong intraatomic Coulomb repulsion. A symptom of the localization is antiferromagnetism, where the spins of localized electrons alternate between up and down. The superconductivity appears when mobile 'holes' are doped into this insulating state, and it coexists with antiferromagnetic fluctuations. In one approach to the coexistence, the h...

  1. A Bioinspired Molecular Polyoxometalate Catalyst with Two Cobalt(II) Oxide Cores for Photocatalytic Water Oxidation.

    Science.gov (United States)

    Wei, Jie; Feng, Yingying; Zhou, Panpan; Liu, Yan; Xu, Jingyin; Xiang, Rui; Ding, Yong; Zhao, Chongchao; Fan, Linyuan; Hu, Changwen

    2015-08-24

    To overcome the bottleneck of water splitting, the exploration of efficient, selective, and stable water oxidation catalysts (WOCs) is crucial. We report an all-inorganic, oxidatively and hydrolytically stable WOC based on a polyoxometalate [(A-α-SiW9 O34)2Co8(OH)6(H2O)2(CO3)3](16-) (Co8 POM). As a cobalt(II)-based cubane water oxidation catalyst, Co8POM embeds double Co(II)4O3 cores. The self-assembled catalyst is similar to the oxygen evolving complex (OEC) of photosystem II (PS II). Using [Ru(bpy)3](2+) as a photosensitizer and persulfate as a sacrificial electron acceptor, Co8POM exhibits excellent water oxidation activity with a turnover number (TON) of 1436, currently the highest among bioinspired catalysts with a cubical core, and a high initial turnover frequency (TOF). Investigation by several spectroscopy, spectrometry, and other techniques confirm that Co8POM is a stable and efficient catalyst for visible light-driven water oxidation. The results offer a useful insight into the design of water oxidation catalysts.

  2. Catalytic wet air oxidation of chlorophenols over supported ruthenium catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Li Ning [Institut de recherches sur la catalyse et l' environnement de Lyon (IRCELYON), UMR 5256, CNRS/Universite Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France); Descorme, Claude [Institut de recherches sur la catalyse et l' environnement de Lyon (IRCELYON), UMR 5256, CNRS/Universite Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France)]. E-mail: claude.descorme@catalyse.cnrs.fr; Besson, Michele [Institut de recherches sur la catalyse et l' environnement de Lyon (IRCELYON), UMR 5256, CNRS/Universite Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France)

    2007-07-31

    A series of noble metal (Pt, Pd, Ru) loaded zirconia catalysts were evaluated in the catalytic wet air oxidation (CWAO) of mono-chlorophenols (2-CP, 3-CP, 4-CP) under relatively mild reaction conditions. Among the investigated noble metals, Ru appeared to be the best to promote the CWAO of CPs as far as incipient-wetness impregnation was used to prepare all the catalysts. The position of the chlorine substitution on the aromatic ring was also shown to have a significant effect on the CP reactivity in the CWAO over 3 wt.% Ru/ZrO{sub 2}. 2-CP was relatively easier to degradate compared to 3-CP and 4-CP. One reason could be the higher adsorption of 2-CP on the catalyst surface. Further investigations suggested that 3 wt.% Ru/ZrO{sub 2} is a very efficient catalyst in the CWAO of 2-CP as far as high 2-CP conversion and TOC abatement could still be reached at even lower temperature (393 K) and lower total pressure (3 MPa). Additionally, the conversion of 2-CP was demonstrated to increase with the initial pH of the 2-CP solution. The dechlorination reaction is promoted at higher pH. In all cases, the adsorption of the reactants and the reaction intermediates was shown to play a major role. All parameters that would control the molecule speciation in solution or the catalyst surface properties would have a key effect.

  3. Calcium oxide based catalysts for biodiesel production: A review

    Directory of Open Access Journals (Sweden)

    Kesić Željka

    2016-01-01

    Full Text Available Vegetable oils are mainly esters of fatty acids and glycerol, which can be converted to fatty acid methyl esters (FAME, also known as biodiesel, by the transesterification reaction with methanol. In order to attain environmental benignity, a large attention has been focused in the last decades on utilizing heterogeneous catalysts for biodiesel production instead the homogenously catalyzed transesterification of vegetable oil. The pure CaO or CaO mixed with some other metal oxide due to its low solubility in methanol, FAME and glycerol, low cost and availability is one of the most promising among the proposed heterogeneous catalysts. Solid catalysts which contain CaO usually fulfill a number of important requirements, such as high activity at mild temperature, marginal leaching of Ca cations, long life activity, reusability in transesterification of vegetable oil and easy recovery from the final products of transesterification (FAME and glycerol. This review is focused to the recent application of pure CaO or CaO in complex catalyst structure and their use as heterogeneous base catalysts for biodiesel synthesis and suitability for industrial application. [Projekat Ministarstva nauke Republike Srbije, br. 45001

  4. Catalytic wet air oxidation of chlorophenols over supported ruthenium catalysts.

    Science.gov (United States)

    Li, Ning; Descorme, Claude; Besson, Michèle

    2007-07-31

    A series of noble metal (Pt, Pd, Ru) loaded zirconia catalysts were evaluated in the catalytic wet air oxidation (CWAO) of mono-chlorophenols (2-CP, 3-CP, 4-CP) under relatively mild reaction conditions. Among the investigated noble metals, Ru appeared to be the best to promote the CWAO of CPs as far as incipient-wetness impregnation was used to prepare all the catalysts. The position of the chlorine substitution on the aromatic ring was also shown to have a significant effect on the CP reactivity in the CWAO over 3wt.% Ru/ZrO(2). 2-CP was relatively easier to degradate compared to 3-CP and 4-CP. One reason could be the higher adsorption of 2-CP on the catalyst surface. Further investigations suggested that 3wt.% Ru/ZrO(2) is a very efficient catalyst in the CWAO of 2-CP as far as high 2-CP conversion and TOC abatement could still be reached at even lower temperature (393K) and lower total pressure (3MPa). Additionally, the conversion of 2-CP was demonstrated to increase with the initial pH of the 2-CP solution. The dechlorination reaction is promoted at higher pH. In all cases, the adsorption of the reactants and the reaction intermediates was shown to play a major role. All parameters that would control the molecule speciation in solution or the catalyst surface properties would have a key effect.

  5. Natural manganese oxides as catalysts for oxidative coupling of methane: a structural and degradation study

    Energy Technology Data Exchange (ETDEWEB)

    Ioffe, L.M.; Bosch, P.; Viveros, T.; Sanchez, H.; Borodko, Y.G. [Universidad Autonoma Metropolitana-Iztapalapa, Mexico (Mexico). Dept. of Chem.

    1997-12-01

    Natural manganese oxides were evaluated as oxidative coupling catalysts to convert methane into C{sub 2}-hydrocarbons. Reactions were done in a cyclic redox mode in which the oxidized catalyst was reacted with methane at 850 C in the absence of oxygen. The bulk and surface analyses (XRD, XPS, FT-IR) indicate that the catalyst deactivation in the methane atmosphere is related to reduction of manganese ions, oxygen depletion of the catalyst surface and formation of manganese carbide species. It is proposed that the XPS line of O1s electrons, Eb=528.6 eV should be assigned to the surface oxygen bound to the reduced Mn{sup 2+} cation with close oxygen vacancies, and lines ofMn2p{sub 3/2} electrons, Eb=641 eV and C1s at 282.5 eV may be assigned to the surface manganese carbide. (orig.) 27 refs.

  6. Tunable and selective conversion of 5-HMF to 2,5-furandimethanol and 2,5-dimethylfuran over copper-doped porous metal oxides

    NARCIS (Netherlands)

    Kumalaputri, Angela J; Bottari, Giovanni; Erne, Petra M; Heeres, Hero J; Barta, Katalin

    Tunable and selective hydrogenation of the platform chemical 5-hydroxymethylfurfural into valuable C-6 building blocks and liquid fuel additives is achieved with copper-doped porous metal oxides in ethanol. A new catalyst composition with improved hydrogenation/hydrogenolysis activity is obtained by

  7. Tunable and selective conversion of 5-HMF to 2,5-furandimethanol and 2,5-dimethylfuran over copper-doped porous metal oxides

    NARCIS (Netherlands)

    Kumalaputri, Angela J; Bottari, Giovanni; Erne, Petra M; Heeres, Hero J; Barta, Katalin

    2014-01-01

    Tunable and selective hydrogenation of the platform chemical 5-hydroxymethylfurfural into valuable C-6 building blocks and liquid fuel additives is achieved with copper-doped porous metal oxides in ethanol. A new catalyst composition with improved hydrogenation/hydrogenolysis activity is obtained by

  8. Water Oxidation Mechanisms of Metal Oxide Catalysts by Vibrational Spectroscopy of Transient Intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Miao [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States); Frei, Heinz [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division; Univ. of California, Berkeley, CA (United States)

    2017-02-22

    Water oxidation is an essential reaction of an artificial photosystem for solar fuel generation because it provides electrons needed to reduce carbon dioxide or protons to a fuel. Earth-abundant metal oxides are among the most attractive catalytic materials for this reaction because of their robustness and scalability, but their efficiency poses a challenge. Knowledge of catalytic surface intermediates gained by vibrational spectroscopy under reaction conditions plays a key role in uncovering kinetic bottlenecks and provides a basis for catalyst design improvements. Recent dynamic infrared and Raman studies reveal the molecular identity of transient surface intermediates of water oxidation on metal oxides. In conclusion, combined with ultrafast infrared observations of how charges are delivered to active sites of the metal oxide catalyst and drive the multielectron reaction, spectroscopic advances are poised to play a key role in accelerating progress toward improved catalysts for artificial photosynthesis.

  9. Electrocatalytic water oxidation with a copper(II) polypeptide complex.

    Science.gov (United States)

    Zhang, Ming-Tian; Chen, Zuofeng; Kang, Peng; Meyer, Thomas J

    2013-02-13

    A self-assembly-formed triglycylglycine macrocyclic ligand (TGG(4-)) complex of Cu(II), [(TGG(4-))Cu(II)-OH(2)](2-), efficiently catalyzes water oxidation in a phosphate buffer at pH 11 at room temperature by a well-defined mechanism. In the mechanism, initial oxidation to Cu(III) is followed by further oxidation to a formal "Cu(IV)" with formation of a peroxide intermediate, which undergoes further oxidation to release oxygen and close the catalytic cycle. The catalyst exhibits high stability and activity toward water oxidation under these conditions with a high turnover frequency of 33 s(-1).

  10. Ethanol dehydrogenation on copper catalysts with ytterbium stabilized tetragonal ZrO2 support

    Science.gov (United States)

    Chuklina, S. G.; Pylinina, A. I.; Podzorova, L. I.; Mikhailina, N. A.; Mikhalenko, I. I.

    2016-12-01

    The physicochemical and catalytic properties of Cu-containing crystalline zirconia, obtained via sol-gel synthesis in the presence of Yb3+ ions and polyvinylpyrrolidone, are studied. DTG/DSC, TEM, XRD and BET methods are used to analyze the crystallization, texture, phase uniformity, surface and porosity of ZrO2 nanopowders. It is shown that increasing the copper content (1, 3, and 5 wt % from ZrO2) raises the dehydrogenation activity in the temperature range of 100-400°C and lowers the activation energy of acetaldehyde formation. It is found that the activity of all Cu/ t-ZrO2 catalysts grows under the effects of the reaction medium, due to the migration and redispersion of copper.

  11. Facile synthesis of flower like copper oxide and their application to hydrogen peroxide and nitrite sensing

    Directory of Open Access Journals (Sweden)

    Zhang Li

    2011-12-01

    Full Text Available Abstract Background The detection of hydrogen peroxide (H2O2 and nitrite ion (NO2- is of great important in various fields including clinic, food, pharmaceutical and environmental analyses. Compared with many methods that have been developed for the determination of them, the electrochemical detection method has attracted much attention. In recent years, with the development of nanotechnology, many kinds of micro/nano-scale materials have been used in the construction of electrochemical biosensors because of their unique and particular properties. Among these catalysts, copper oxide (CuO, as a well known p-type semiconductor, has gained increasing attention not only for its unique properties but also for its applications in many fields such as gas sensors, photocatalyst and electrochemistry sensors. Continuing our previous investigations on transition-metal oxide including cuprous oxide and α-Fe2O3 modified electrode, in the present paper we examine the electrochemical and electrocatalytical behavior of flower like copper oxide modified glass carbon electrodes (CuO/GCE. Results Flower like copper oxide (CuO composed of many nanoflake was synthesized by a simple hydrothermal reaction and characterized using field-emission scanning electron microscopy (FE-SEM and X-ray diffraction (XRD. CuO modified glass carbon electrode (CuO/GCE was fabricated and characterized electrochemically. A highly sensitive method for the rapid amperometric detection of hydrogen peroxide (H2O2 and nitrite (NO2- was reported. Conclusions Due to the large specific surface area and inner characteristic of the flower like CuO, the resulting electrode show excellent electrocatalytic reduction for H2O2 and oxidation of NO2-. Its sensitivity, low detection limit, fast response time and simplicity are satisfactory. Furthermore, this synthetic approach can also be applied for the synthesis of other inorganic oxides with improved performances and they can also be extended to

  12. Catalysts Promoted with Niobium Oxide for Air Pollution Abatement

    Directory of Open Access Journals (Sweden)

    Wendi Xiang

    2017-05-01

    Full Text Available Pt-containing catalysts are currently used commercially to catalyze the conversion of carbon monoxide (CO and hydrocarbon (HC pollutants from stationary chemical and petroleum plants. It is well known that Pt-containing catalysts are expensive and have limited availability. The goal of this research is to find alternative and less expensive catalysts to replace Pt for these applications. This study found that niobium oxide (Nb2O5, as a carrier or support for certain transition metal oxides, promotes oxidation activity while maintaining stability, making them candidates as alternatives to Pt. The present work reports that the orthorhombic structure of niobium oxide (formed at 800 °C in air promotes Co3O4 toward the oxidation of both CO and propane, which are common pollutants in volatile organic compound (VOC applications. This was a surprising result since this structure of Nb2O5 has a very low surface area (about 2 m2/g relative to the more traditional Al2O3 support, with a surface area of 150 m2/g. The results reported demonstrate that 1% Co3O4/Nb2O5 has comparable fresh and aged catalytic activity to 1% Pt/γ-Al2O3 and 1% Pt/Nb2O5. Furthermore, 6% Co3O4/Nb2O5 outperforms 1% Pt/Al2O3 in both catalytic activity and thermal stability. These results suggest a strong interaction between niobium oxide and the active component—cobalt oxide—likely by inducing an oxygen defect structure with oxygen vacancies leading to enhanced activity toward the oxidation of CO and propane.

  13. Carbon monoxide oxidation using Zn-Cu-Ti hydrotalcite-derived catalysts

    Indian Academy of Sciences (India)

    O Saber; T Zaki

    2014-07-01

    Multioxide catalysts of zinc, copper and titanium with different ratios obtained from layered double hydroxide (LDH) precursors were used in the oxidation of carbon monoxide. The catalysts were characterized by energy-dispersive X-ray spectrometry, X-ray diffraction, thermal analyses (TG, DTG and DTA) and scanning electron microscopy. X-ray diffraction showed different phases of double hydroxide structures. On increasing the percentage of zinc, hydrotalcite structure became the main phase in these samples. SEM images confirmed the presence of layered double hydroxide as plate-like structure. Experimental results indicated a sharp increase in the catalytic activities of the calcined samples towards the oxidation of carbon monoxide at temperatures in the range of 225-275°C. High conversion of carbon monoxide (90 ∼ 95%) was achieved at reaction temperature of 275°C by samples having ZnTiO3 as a main phase. These results suggested that hydrotalcite structure of Zn-Ti has a positive catalytic effect towards carbon monoxide oxidation.

  14. Reduction and Oxidation of Copper Oxide Thin Films and Thermal Stability Issues in Copper-Based Metallization.

    Science.gov (United States)

    Li, Jian

    This thesis investigates the oxidation and reduction of Cu-oxides and thermal induced reactions of Cu with metals. The combination of ^{16}O( alpha,alpha)^{16}O oxygen resonance and transmission electron microscopy (TEM) provides an effective method of studying the oxidation and reduction of copper oxide thin films. A discontinuous morphology of grain growth of Cu_2O in found in the CuO matrix during reduction. The migration of the Cu_2O-CuO phase boundary is induced by oxygen diffusion along the moving boundary. Grain growth is the dominant process in the transformation from CuO to Cu_2O; nucleation is the dominant process in the reverse transformation, i.e. from Cu_2O to CuO. The reduction and oxidation of copper oxides are asymmetrical; the latter is significantly faster. The metastable phase Cu _4O_3 was formed by ion milling CuO. Carbon and refractory metals such as Ti or Zr can enhance the reduction rate of CuO. Three topics relating to thermal stability issues in Cu-based metallization were investigated: (1) texturing in electroless copper films on epitaxial copper seed layers; (2) predicting first phase formation in Cu/metal bilayer structures; and (3) encapsulation of Cu fine line structures with TiN. (100)- and (111)-textured copper layers were deposited by electroless plating on copper seed layers grown epitaxially on Si (100) and Si (111) substrates, respectively. (111) -textured copper films are more oxidation-resistant. Rutherford backscattering spectrometry (RBS) and in situ transmission electron microscopy (TEM) were used to determine phase formation in Cu-M (M = Ti, Zr, Mg, Sb, Pd and Pt) bilayer systems. An effective heat of formation rule was employed to predict first phase formation in these systems. A TiN-encapsulated copper structure was made by annealing a Cu-10at%Ti alloy film evaporated on a SiO _2/Si(100) substrate at 550^ circC in an NH_3 ambient. Fast heating rates (70^circC/min.) to 550^circC can effectively suppress the formation of Cu

  15. Copper oxide resistive switching memory for e-textile

    Directory of Open Access Journals (Sweden)

    Jin-Woo Han

    2011-09-01

    Full Text Available A resistive switching memory suitable for integration into textiles is demonstrated on a copper wire network. Starting from copper wires, a Cu/CuxO/Pt sandwich structure is fabricated. The active oxide film is produced by simple thermal oxidation of Cu in atmospheric ambient. The devices display a resistance switching ratio of 102 between the high and low resistance states. The memory states are reversible and retained over 107 seconds, with the states remaining nondestructive after multiple read operations. The presented device on the wire network can potentially offer a memory for integration into smart textile.

  16. Copper oxide resistive switching memory for e-textile

    Science.gov (United States)

    Han, Jin-Woo; Meyyappan, M.

    2011-09-01

    A resistive switching memory suitable for integration into textiles is demonstrated on a copper wire network. Starting from copper wires, a Cu/CuxO/Pt sandwich structure is fabricated. The active oxide film is produced by simple thermal oxidation of Cu in atmospheric ambient. The devices display a resistance switching ratio of 102 between the high and low resistance states. The memory states are reversible and retained over 107 seconds, with the states remaining nondestructive after multiple read operations. The presented device on the wire network can potentially offer a memory for integration into smart textile.

  17. Experimental Viscosity Measurements for Copper Oxide Nanoparticle Suspensions

    Institute of Scientific and Technical Information of China (English)

    李俊明; 李泽梁; 王补宣

    2002-01-01

    The viscosity of water with copper oxide nanoparticle suspensions was measured using capillary viscometers. The mass fractions of copper oxide nanoparticles in the experiment, w, varied between 0.02 and 0.10, and the temperature range was 30℃ to 80℃. The experimental results show that the temperature was the major factor affecting the viscosity of the nanoparticle suspensions, while the effect of the mass fraction on the viscosity was not so obvious as that of the temperature for the mass fractions chosen in the experiment. The effect of the capillary tube size on the viscosity was also found to be relatively important at higher mass fractions.

  18. Copper Recovery from Yulong Complex Copper Oxide Ore by Flotation and Magnetic Separation

    Science.gov (United States)

    Han, Junwei; Xiao, Jun; Qin, Wenqing; Chen, Daixiong; Liu, Wei

    2017-09-01

    A combined process of flotation and high-gradient magnetic separation was proposed to utilize Yulong complex copper oxide ore. The effects of particle size, activators, Na2S dosage, LA (a mixture of ammonium sulfate and ethylenediamine) dosage, activating time, collectors, COC (a combination collector of modified hydroxyl oxime acid and xanthate) dosage, and magnetic intensity on the copper recovery were investigated. The results showed that 74.08% Cu was recovered by flotation, while the average grade of the copper concentrates was 21.68%. Another 17.34% Cu was further recovered from the flotation tailing by magnetic separation at 0.8 T. The cumulative recovery of copper reached 91.42%. The modifier LA played a positive role in facilitating the sulfidation of copper oxide with Na2S, and the combined collector COC was better than other collectors for the copper flotation. This technology has been successfully applied to industrial production, and the results are consistent with the laboratory data.

  19. Metal-Organic Frameworks as Catalysts for Oxidation Reactions.

    Science.gov (United States)

    Dhakshinamoorthy, Amarajothi; Asiri, Abdullah M; Garcia, Hermenegildo

    2016-06-01

    This Concept is aimed at describing the current state of the art in metal-organic frameworks (MOFs) as heterogeneous catalysts for liquid-phase oxidations, focusing on three important substrates, namely, alkenes, alkanes and alcohols. Emphases are on the nature of active sites that have been incorporated within MOFs and on future targets to be set in this area. Thus, selective alkene epoxidation with peroxides or oxygen catalyzed by constitutional metal nodes of MOFs as active sites are still to be developed. Moreover, no noble metal-free MOF has been reported to date that can act as a general catalyst for the aerobic oxidation of primary and secondary aliphatic alcohols. In contrast, in the case of alkanes, a target should be to tune the polarity of MOF internal pores to control the outcome of the autooxidation process, resulting in the selective formation of alcohol/ketone mixtures at high conversion.

  20. Aerobic oxidation assisted by ligand-free palladium catalysts

    Institute of Scientific and Technical Information of China (English)

    Jia Rui Wang; Chu Ting Yang; Lei Liu; Qing Xiang Guo

    2007-01-01

    Aerobic oxidation of electron-rich benzylic and phenyl allylic alcohols was achieved with high yields with only 0.1 mol.% ofPd(OAc)2 catalyst in the absence of any ligand. This procedure was expected to be valuable for realistic industrial-scale applications from both economic as well as environmental points of view.(C) 2006 Qing Xiang Guo. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

  1. Catalytic reduction of nitric oxide with carbon monoxide on copper-cobalt oxides supported on nano-titanium dioxide.

    Science.gov (United States)

    Chen, Xia; Zhang, Junfeng; Huang, Yan; Tong, Zhiquan; Huang, Ming

    2009-01-01

    A series of copper-cobalt oxides supported on nano-titanium dioxide were prepared for the reduction of nitric oxide with carbon monoxide and characterized using techniques such as XRD, BET and TPR. Catalyst CuCoOx/TiO2 with Cu/Co molar ratio of 1/2, Cu-Co total loading of 30% at the calcination temperature of 350 degrees C formed CuCo2O4 spinel and had the highest activity. NO conversion reached 98.9% at 200 degrees C. Mechanism of the reduction was also investigated, N2O was mainly yielded below 100 degrees C, while N2 was produced instead at higher temperature. O2 was supposed to accelerate the reaction between NOx and CO for its oxidation of NO to give more easily reduced NO2, but the oxidation of CO by O2 to CO2 decreased the speed of the reaction greatly. Either SO2 or H2O had no adverse impact on the activity of NO reduction; however, in the presence of both SO2 and H2O, the catalyst deactivated quickly.

  2. CO and Soot Oxidation over Ce-Zr-Pr Oxide Catalysts.

    Science.gov (United States)

    Andana, Tahrizi; Piumetti, Marco; Bensaid, Samir; Russo, Nunzio; Fino, Debora; Pirone, Raffaele

    2016-12-01

    A set of ceria, ceria-zirconia (Ce 80 at.%, Zr 20 at.%), ceria-praseodymia (Ce 80 at.%, Pr 20 at.%) and ceria-zirconia-praseodymia (Ce 80 at.%, Zr 10 at.% and Pr 10 at.%) catalysts has been prepared by the solution combustion synthesis (SCS). The effects of Zr and Pr as dopants on ceria have been studied in CO and soot oxidation reactions. All the prepared catalysts have been characterized by complementary techniques, including XRD, FESEM, N2 physisorption at -196 °C, H2-temperature-programmed reduction, and X-ray photoelectron spectroscopy to investigate the relationships between the structure and composition of materials and their catalytic performance. Better results for CO oxidation have been obtained with mixed oxides (performance scale, Ce80Zr10Pr10 > Ce80Zr20 > Ce80Pr20) rather than pure ceria, thus confirming the beneficial role of multicomponent catalysts for this prototypical reaction. Since CO oxidation occurs via a Mars-van Krevelen (MvK)-type mechanism over ceria-based catalysts, it appears that the presence of both Zr and Pr species into the ceria framework improves the oxidation activity, via collective properties, such as electrical conductivity and surface or bulk oxygen anion mobility. On the other hand, this positive effect becomes less prominent in soot oxidation, since the effect of catalyst morphology prevails.

  3. Nickel-containing catalysts for methane oxidation to synthesis gas

    Directory of Open Access Journals (Sweden)

    Kusman Dossumov

    2014-12-01

    Full Text Available The partial oxidation of methane to synthesis gas was studied on oxides of metals of variable valence (Mn, La, Cr and Ni, supported on a carrier – ɣ-Al2O3. Among the catalysts studied, the sample of 3% Ni/ɣ-Al2O3 showed the best characteristics by yields of hydrogen and carbon monoxide in the reaction of partial oxidation of methane. The optimal conditions of the process (the reaction temperature of 850 °C, the volume rate of 4500 h-1, and the ratio CH4: O2 = 2:1 cause the increase the concentration of hydrogen and carbon monoxide to 72.2 and 75.3%, respectively. The effect of the heat-treatment temperature and textural characteristics of the Ni/ ɣ-Al2O3 catalyst on its catalytic activity was studied. The NiCe/Al2O3 catalyst developed showed a high stability during 30 hours.

  4. Study of propane partial oxidation on vanadium-containing catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Komashko, G.A.; Khalamejda, S.V.; Zazhigalov, V.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

    1998-12-31

    The present results indicate that maximum selectivity to acrylic acid can be reached over V-P-Zr-O catalysts. When the hydrocarbon concentration is 5.1 vol.% the selectivity is about 30% at quite high paraffin conversion. Conclusively, some explanations to the observed facts can be given. The V-P-O catalyst promotion with lanthanum by means of mechanochemical treatment is distinguished by the additive uniform spreading all over the matrix surface. Such twophase system is highly active in propane conversion (lanthanum oxide) and further oxidation of the desired products. The similar properties are attributed to V-P-Bi-La-O catalyst. Bismuth, tellurium and zirconium additives having clearly defined acidic properties provoke the surface acidity strengthening and make easier desorption of the acidic product (acrylic acid) from the surface lowering its further oxidation. Additionally, since bismuth and zirconium are able to form phosphates and, according to, to create space limitations for the paraffin molecule movement out of the active group boundaries, this can be one more support in favour of the selectivity increase. With this point of view very interesting results were obtained. It has been shown that the more limited the size of the vanadium unit, the higher the selectivity is. Monoclinic phase AV{sub 2}P{sub 2}O{sub 10} which consists in clusters of four vanadium atoms is sensibly more reactive than the orthorhombic phase consists in V{sub {infinity}} infinite chains. (orig.)

  5. Formation and characterization of infrared absorbing copper oxide surfaces

    Science.gov (United States)

    Arslan, Burcu; Demirci, Gökhan; Erdoğan, Metehan; Karakaya, İshak

    2017-04-01

    Copper oxide formation has been investigated to combine the advantages of producing different size and shapes of coatings that possess good light absorbing properties. An aqueous blackening solution was investigated and optimum composition was found as 2.5 M NaOH and 0.225 M NaClO to form velvet copper oxide films. A two-step oxidation mechanism was proposed for the blackening process by carefully examining the experimental results. Formation of Cu2O was observed until the entire copper surface was covered at first. In the second step, Cu2O surface was further oxidized to CuO until the whole Cu2O surface was covered by CuO. Therefore, blackened copper surfaces consisted of Cu2O/CuO duplex oxides. Characterization of the coatings were performed in terms of microstructure, phase analysis, chemical state, infrared specular and total reflectivity by SEM, XRD, XPS, FTIR and UV-vis spectrophotometry, respectively.

  6. The Manipulation of Hydrophobicity in Catalyst Design for Applications of Aerobic Alcohols Oxidation and Electrocatalytic Water Oxidation

    KAUST Repository

    Chen, Batian

    2016-05-17

    Hydrophobicity is the generalized characteristic of non-polar substances that brings about their exclusion from aqueous phases. This property, entropic in its nature, drives key self-assembly and phase separation processes in water. Protein folding, the formation of DNA double helix, the existence of lipid bilayers and the wetting properties of leaf surfaces are all due to hydrophobic interactions. Inspired by Nature, we aimed to use hydrophobicity for creating novel and improved catalytic systems. (I) A number of fluorous amphiphilic star block-copolymers containing a tris(benzyltriazolylmethyl)amine motif have been prepared. These polymers assembled into well-defined nanostructures in water, and their mode of assembly could be controlled by changing the composition of the polymer. The polymers were used for enzyme-inspired catalysis of alcohol oxidation. (II) An enzyme-inspired catalytic system based on a rationally designed multifunctional surfactant was developed. The resulting micelles feature metal-binding sites and stable free radical moieties as well as fluorous pockets that attract and preconcentrate molecular oxygen. In the presence of copper ions, the micelles effect chemoselective aerobic alcohol oxidation under ambient conditions in water, a transformation that is challenging to achieve nonenzymatically. (III) Development of a facile means of photo/electrocatalytic water splitting is one of the main barriers to establishing of a solar hydrogen economy. Of the two half-reactions involved in splitting water into O2 and H2, water oxidation presents the most challenge due to its mechanistic complexity. A practical water oxidation catalyst must be highly active, yet inexpensive and indefinitely stable under harsh oxidative conditions. Here, I shall describe the synthesis of a library of molecular water oxidation catalysts based on the Co complex of tris(2-benzimidazolylmethyl)amine, (BimH)3. A wide range of catalysts differing in their electronic properties

  7. Copper oxide transistor on copper wire for e-textile

    Science.gov (United States)

    Han, Jin-Woo; Meyyappan, M.

    2011-05-01

    A Cu2O-based field effect transistor was fabricated on Cu wire. Thermal oxidation of Cu forms Cu-Cu2O core-shell structure, where the metal-semiconductor Schottky junction was used as a gate barrier with Pt Ohmic contacts for source and drain. The device was coated with polydimethylsiloxane (PDMS) to protect from contamination and demonstrated as a humidity sensor. The cylindrical structure of the Cu wire and the transistor function enable embedding of simple circuits into textile which can potentially offer smart textile for wearable computing, environmental sensing, and monitoring of human vital signs.

  8. Hydroxylation of benzene to phenol over magnetic recyclable nanostructured CuFe mixed-oxide catalyst

    CSIR Research Space (South Africa)

    Makgwane, PR

    2015-03-01

    Full Text Available A highly active and magnetically recyclable nanostructured copper–iron oxide (CuFe) catalyst has been synthesized for hydroxylation of benzene to phenol under mild reaction conditions. The obtained catalytic results were correlated with the catalyst...

  9. High-efficiency palladium catalysts supported on ppy-modified C60 for formic acid oxidation.

    Science.gov (United States)

    Bai, Zhengyu; Yang, Lin; Guo, Yuming; Zheng, Zhi; Hu, Chuangang; Xu, Pengle

    2011-02-14

    A facile preparation of polypyrrole-modified fullerene supported Pd nanoparticles catalyst is introduced; electrochemical measurements demonstrate that the obtained Pd/ppy-C(60) catalyst shows a good electrocatalytic activity and stability for the oxidation of formic acid.

  10. Nanostructured manganese oxide on silica aerogel: a new catalyst toward water oxidation.

    Science.gov (United States)

    Najafpour, Mohammad Mahdi; Salimi, Saeideh; Madadkhani, Sepideh; Hołyńska, Małgorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

    2016-12-01

    Herein we report on the synthesis and characterization of nano-sized Mn oxide/silica aerogel with low density as a good catalyst toward water oxidation. The composite was synthesized by a simple and low-cost hydrothermal procedure. In the next step, we studied the composite in the presence of cerium(IV) ammonium nitrate and photo-produced Ru(bpy) 3(3+) as a water-oxidizing catalyst. The low-density composite is a good Mn-based catalyst with turnover frequencies of ~0.3 and 0.5 (mmol O2/(mol Mn·s)) in the presence of Ru(bpy) 3(3+) and cerium(IV) ammonium nitrate, respectively. In addition to the water-oxidizing activities of the composite under different conditions, its self-healing reaction in the presence of cerium(IV) ammonium nitrate was also studied.

  11. A hybrid water-splitting cycle using copper sulfate and mixed copper oxides

    Science.gov (United States)

    Schreiber, J. D.; Remick, R. J.; Foh, S. E.; Mazumder, M. M.

    1980-01-01

    The Institute of Gas Technology has derived and developed a hybrid thermochemical water-splitting cycle based on mixed copper oxides and copper sulfate. Similar to other metal oxide-metal sulfate cycles that use a metal oxide to 'concentrate' electrolytically produced sulfuric acid, this cycle offers the advantage of producing oxygen (to be vented) and sulfur dioxide (to be recycled) in separate steps, thereby eliminating the need of another step to separate these gases. The conceptual process flow-sheet efficiency of the cycle promises to exceed 50%. It has been completely demonstrated in the laboratory with recycled materials. Research in the electrochemical oxidation of sulfur dioxide to produce sulfuric acid and hydrogen performed at IGT indicates that the cell performance goals of 200 mA/sq cm at 0.5 V will be attainable using relatively inexpensive electrode materials.

  12. Moessbauer spectra of ferrite catalysts used in oxidative dehydrogenation

    Science.gov (United States)

    Cares, W. R.; Hightower, J. W.

    1971-01-01

    Room temperature Mossbauer spectroscopy was used to examine bulk changes which occur in low surface area CoFe2O4 and CuFe2O4 catalysts as a result of contact with various mixtures of trans-2-butene and O2 during oxidative dehydrogenation reactions at about 420 C. So long as there was at least some O2 in the gas phase, the CoFe2O4 spectrum was essentially unchanged. However, the spectrum changed from a random spinel in the oxidized state to an inverse spinel as it was reduced by oxide ion removal. The steady state catalyst lies very near the fully oxidized state. More dramatic solid state changes occurred as the CuFe2O4 underwent reduction. Under severe reduction, the ferrite was transformed into Cu and Fe3O4, but it could be reversibly recovered by oxidation. An intense doublet located near zero velocity persisted in all spectra of CuFe2O4 regardless of the state of reduction.

  13. High performance CuO-CeO_2 catalysts for selective oxidation of CO in excess hydrogen: Effect of hydrothermal preparation conditions

    Institute of Scientific and Technical Information of China (English)

    Pengfei Zhu; Jing Li; Qinqin Huang; Siming Yan; Mei Liu; Renxian Zhou

    2009-01-01

    High performance CuO-CeO_2 catalysts for selective oxidation of CO in excess hydrogen were prepared by a hydrothermal method under different preparation conditions and evaluated for catalytic activities and selectivities. By changing the nCTAB/nCe ratio and hydrothermal aging time,the catalytic activity of the CuO-CeO_2 catalysts increased and the operating temperature window,in which the CO conversion was higher than 99%,was widened. XRD results showed no peaks of CuOx species and Cu-Ce-O solid solution were observed. On the other hand,Cu+ species in the CuO-CeO_2 catalysts,which was associated with a strong interaction between copper oxide clusters and cerium oxide and could be favorable for improving the selective oxidation performance of CO in excess H2,were detected by H2-TPR and XPS techniques.

  14. Influence of promoters and oxidants on propane dehydrogenation over chromium-oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Agafonov, Yu.A.; Shaporeva, N.Yu.; Trushin, D.V.; Gaidai, N.A.; Nekrasov, N.V. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry

    2010-12-30

    Possibilities for increasing the efficiency of supported on SiO{sub 2} chromium-oxide catalysts in propane oxidative dehydrogenation in CO{sub 2} presence are investigated: the introduction of Li, Na, K, Ca in catalysts and the addition of O{sub 2} in the reaction mixture. It was been found that the positive role of K - the increase of the selectivity to propene and stability of catalysts at long-duration tests - appeared at the relation of Cr:K=20. It was shown that the presence of little amount of O{sub 2} (2%) in the reaction mixtures of propane and carbon dioxide resulted in the increase of propene yield and catalyst stability. (orig.)

  15. Metal oxides modified NiO catalysts for oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo

    2014-06-01

    The sol-gel method was applied to the synthesis of Zr, Ti, Mo, W, and V modified NiO based catalysts for the ethane oxidative dehydrogenation reaction. The synthesized catalysts were characterized by XRD, N2 adsorption, SEM and TPR techniques. The results showed that the doping metals could be highly dispersed into NiO domains without the formation of large amount of other bulk metal oxide. The modified NiO materials have small particle size, larger surface area, and higher reduction temperature in contrast to pure NiO. The introduction of group IV, V and VI transition metals into NiO decreases the catalytic activity in ethane ODH. However, the ethylene selectivity is enhanced with the highest level for the Ni-W-O and Ni-Ti-O catalysts. As a result, these two catalysts show improved efficiency of ethylene production in the ethane ODH reaction. © 2014 Elsevier B.V. All rights reserved.

  16. Silver-Copper Nanoalloy Catalyst Layer for Bifunctional Air Electrodes in Alkaline Media.

    Science.gov (United States)

    Wu, Xiaoqiang; Chen, Fuyi; Jin, Yachao; Zhang, Nan; Johnston, Roy L

    2015-08-19

    A carbon-free and binder-free catalyst layer composed of a Ag-Cu nanoalloy on Ni foam was used as the air cathode in a zinc-air battery for the first time. The Ag-Cu catalyst was prepared using pulsed laser deposition. The structures of the catalysts were found to consist of crystalline Ag-Cu nanoalloy particles with an average size of 2.58 nm embedded in amorphous Cu films. As observed in the X-ray photoelectron spectra, the Ag 3d core levels shifted to higher binding energies, whereas the Cu 2p core levels shifted to lower binding energies, indicating alloying of the silver and copper. Rotating disk electrode measurements indicated that the oxygen reduction reaction (ORR) proceeded through a four-electron pathway on the Ag50Cu50 and Ag90Cu10 nanoalloy catalysts in alkaline solution. Moreover, the catalytic activity of Ag50Cu50 in the ORR is more efficient than that of Ag90Cu10. By performing charge and discharge cycling measurements, the Ag50Cu50 catalyst layer was confirmed to have a maximum power density of approximately 86.3 mW cm(-2) and an acceptable cell voltage at 0.863 V for current densities up to 100 mA cm(-2) in primary zinc-air batteries. In addition, a round-trip efficiency of approximately 50% at a current density of 20 mA cm(-2) was also obtained in the test.

  17. Biodynamics of copper oxide nanoparticles and copper ions in an oligochaete, Part I

    DEFF Research Database (Denmark)

    Ramskov, Tina; Thit, Amalie; Croteau, Marie-Noelle

    2015-01-01

    Copper oxide (CuO) nanoparticles (NPs) are widely used, and likely released into the aquatic environment. Both aqueous (i.e., dissolved Cu) and particulate Cu can be taken up by organisms. However, how exposure routes influence the bioavailability and subsequent toxicity of Cu remains largely...

  18. Molecularly imprinted Ru complex catalysts integrated on oxide surfaces.

    Science.gov (United States)

    Muratsugu, Satoshi; Tada, Mizuki

    2013-02-19

    Selective catalysis is critical for the development of green chemical processes, and natural enzymes that possess specialized three-dimensional reaction pockets with catalytically active sites represent the most sophisticated systems for selective catalysis. A reaction space in an enzyme consists of an active metal center, functional groups for molecular recognition (such as amino acids), and a surrounding protein matrix to prepare the reaction pocket. The artificial design of such an integrated catalytic unit in a non-enzymatic system remains challenging. Molecular imprinting of a supported metal complex provides a promising approach for shape-selective catalysis. In this process, an imprinted cavity with a shape matched to a template molecule is created in a polymer matrix with a catalytically active metal site. In this Account, we review our studies on molecularly imprinted metal complex catalysts, focusing on Ru complexes, on oxide surfaces for shape-selective catalysis. Oxide surface-attached transition metal complex catalysts not only improve thermal stability and catalyst dispersion but also provide unique catalytic performance not observed in homogeneous precursors. We designed molecularly imprinted Ru complexes by using surface-attached Ru complexes with template ligands and inorganic/organic surface matrix overlayers to control the chemical environment around the active metal complex catalysts on oxide surfaces. We prepared the designed, molecularly imprinted Ru complexes on SiO(2) surfaces in a step-by-step manner and characterized them with solid-state (SS) NMR, diffuse-reflectance (DR) UV-vis, X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller isotherm (BET), X-ray fluorescence (XRF), and Ru K-edge extended X-ray absorption fine structure (EXAFS). The catalytic performances of these Ru complexes suggest that this process of molecular imprinting facilitates the artificial integration of catalytic functions at surfaces. Further advances such

  19. Comparison of direct and indirect plasma oxidation of NO combined with oxidation by catalyst

    DEFF Research Database (Denmark)

    Jogi, Indrek; Stamate, Eugen; Irimiea, Cornelia

    2015-01-01

    Direct and indirect plasma oxidation of NOx was tested in a medium-scale test-bench at gas flows of 50 slm (3 m(3)/h). For direct plasma oxidation the synthetic flue gas was directed through a stacked DBD reactor. For indirect plasma oxidation, a DBD reactor was used to generate ozone from pure O-2...... of the DBD reactor decreased the long-term efficiency of direct plasma oxidation. At the same time, the efficiency of indirect oxidation increased at elevated reactor temperatures. Additional experiments were carried out to investigate the improvement of indirect oxidation by the introduction of catalyst...

  20. Oxidative alkoxylation of phosphine in alcohol solutions of copper halides

    Science.gov (United States)

    Polimbetova, G. S.; Borangazieva, A. K.; Ibraimova, Zh. U.; Bugubaeva, G. O.; Keynbay, S.

    2016-08-01

    The phosphine oxidation reaction with oxygen in alcohol solutions of copper (I, II) halides is studied. Kinetic parameters, intermediates, and by-products are studied by means of NMR 31P-, IR-, UV-, and ESR- spectroscopy; and by magnetic susceptibility, redox potentiometry, gas chromatography, and elemental analysis. A reaction mechanism is proposed, and the optimum conditions are found for the reaction of oxidative alkoxylation phosphine.

  1. CuO/CeO{sub 2} catalysts prepared with different cerium supports for CO oxidation at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Chi-Yuan [School of Public Health, Chung Shan Medical University, Taichung 402, Taiwan, ROC (China); Department of Occupational Medicine, Chung Shan Medical University Hospital, Taichung 402, Taiwan, ROC (China); Chang, Wen-Chi [Department of Environmental Engineering, National Chung Hsing University, Taichung 402, Taiwan, ROC (China); Wey, Ming-Yen, E-mail: mywey@dragon.nchu.edu.tw [Department of Environmental Engineering, National Chung Hsing University, Taichung 402, Taiwan, ROC (China)

    2013-08-15

    The activity of a catalyst depends on the nature of its support, its active site, and its preparation method. This study aimed to employ various types of CeO{sub 2} supports such as commercial CeO{sub 2} and self-prepared CeO{sub 2} for the preparation of copper catalysts. The CuO/CeO{sub 2} catalysts were prepared using the polyol process and impregnation method. The catalysts were characterized using Brunauer–Emmett–Teller analysis, scanning electron microscopy, and X-ray analysis, and their catalytic activity for CO removal was evaluated in a microcatalytic reactor. The experimental results showed that the catalytic activity of the CuO/CeO{sub 2} catalysts with different calcination temperatures decreased in the following order: 500 °C > 300 °C > 700 °C. Compared to the impregnation method, the polyol process generated well-dispersed metal particles over the support and showed higher CO removal efficiency with low activation energy. Compared to CuO/CeO{sub 2} catalysts with commercial CeO{sub 2}, those with CeO{sub 2} that was self-prepared by pyrolysis had a large pore volume and good crystal structure of CeO{sub 2} and showed good performance. The catalytic activity for CO removal was in the following order: CuO/CeO{sub 2}-P (pyrolysis) > CuO/CeO{sub 2}-C (commercial) > CuO/CeO{sub 2}-D (deposition precipitation). CuO/CeO{sub 2}-P catalysts showed good activity even at low temperature. The CuO/CeO{sub 2}-P(300)-P-120 min catalyst was found to possess the good CO removal rate when the oxygen content was 6%, CO concentration was 500 ppm, catalyst weighed 1.0 g, pollutant gas velocity was 500 mL min{sup −1}, SV was 3.7 × 10{sup 4} h{sup −1}, and reaction temperature was 150 °C. - Highlights: • CuO/CeO{sub 2} catalysts were prepared using polyol and impregnation methods. • The supports of catalyst were self-prepared cerium oxide and commercial cerium oxide. • Pyrolysis and deposition precipitation methods were used for cerium preparation.

  2. Hydrogen purification for fuel cell by copper promoted gold catalysts; Purificacao de hidrogenio para pilha a combustivel utilizando catalisadores de ouro promovidos com cobre

    Energy Technology Data Exchange (ETDEWEB)

    Mozer, Thiago S.; Vieira, Carlos T.P.; Passos, Fabio B. [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil); Dziuba, Dominika A. [Hochschule Mannheim (Germany)

    2008-07-01

    Copper promoted gold catalysts were studied for hydrogen purification through selective CO oxidation. The Cu acted as a selectivity promoter favoring the CO conversion and decreasing the H{sub 2} consumption. The deposition-precipitation method, used to prepare the samples generated small and well dispersed gold particles, as the UV-vis DRS spectra did not show the 'plasmon' band, which indicates that the samples are active for SELOX. The activity tests showed high CO conversion, the bimetallic 2,5%Au-0,5%Cu/Al{sub 2}O{sub 3} catalyst showed the best behavior in the tested condition, 95% of CO conversion and 75% of selectivity at 50 deg C. Increasing the O{sub 2} content in the feedstream the CO conversion also increased, although the selectivity decreased. (author)

  3. Copper Nanoparticles for Printed Electronics: Routes Towards Achieving Oxidation Stability.

    Science.gov (United States)

    Magdassi, Shlomo; Grouchko, Michael; Kamyshny, Alexander

    2010-09-08

    In the past few years, the synthesis of Cu nanoparticles has attracted much attention because of its huge potential for replacing expensive nano silver inks utilized in conductive printing. A major problem in utilizing these copper nanoparticles is their inherent tendency to oxidize in ambient conditions. Recently, there have been several reports presenting various approaches which demonstrate that copper nanoparticles can resist oxidation under ambient conditions, if they are coated by a proper protective layer. This layer may consist of an organic polymer, alkene chains, amorphous carbon or graphenes, or inorganic materials such as silica, or an inert metal. Such coated copper nanoparticles enable achieving high conductivities by direct printing of conductive patterns. These approaches open new possibilities in printed electronics, for example by using copper based inkjet inks to form various devices such as solar cells, Radio Frequency Identification (RFID) tags, and electroluminescence devices. This paper provides a review on the synthesis of copper nanoparticles, mainly by wet chemistry routes, and their utilization in printed electronics.

  4. Copper Nanoparticles for Printed Electronics: Routes Towards Achieving Oxidation Stability

    Directory of Open Access Journals (Sweden)

    Shlomo Magdassi

    2010-09-01

    Full Text Available In the past few years, the synthesis of Cu nanoparticles has attracted much attention because of its huge potential for replacing expensive nano silver inks utilized in conductive printing. A major problem in utilizing these copper nanoparticles is their inherent tendency to oxidize in ambient conditions. Recently, there have been several reports presenting various approaches which demonstrate that copper nanoparticles can resist oxidation under ambient conditions, if they are coated by a proper protective layer. This layer may consist of an organic polymer, alkene chains, amorphous carbon or graphenes, or inorganic materials such as silica, or an inert metal. Such coated copper nanoparticles enable achieving high conductivities by direct printing of conductive patterns. These approaches open new possibilities in printed electronics, for example by using copper based inkjet inks to form various devices such as solar cells, Radio Frequency Identification (RFID tags, and electroluminescence devices. This paper provides a review on the synthesis of copper nanoparticles, mainly by wet chemistry routes, and their utilization in printed electronics.

  5. Self-Supported Copper Oxide Electrocatalyst for Water Oxidation at Low Overpotential and Confirmation of Its Robustness by Cu K-edge X-ray Absorption Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xiang; Cui, Shengsheng; Sun, Zijun; Ren, Yang; Zhang, Xiaoyi; Du, Pingwu

    2016-01-21

    Developing efficient water oxidation catalysts made of earth-abundant elements is a demanding challenge that should be met to fulfill the promise of water splitting for clean energy. Herein we report an annealing approach to synthesize binder-free, self-supported heterogeneous copper oxide (CuO) on conductive electrodes for oxygen evolution reaction (OER), producing electrodes with excellent electrocatalytic properties such as high efficiency, low overpotential, and good stability. The catalysts were grown in situ on fluorine-doped tin oxide (FTO) by electrodeposition from a simple Cu(II) salt solution, followed by annealing at a high temperature. Under optimal conditions, the CuO-based OER catalyst shows an onset potential of <0.58 V (vs Ag/AgCl) in 1.0 M KOH at pH 13.6. From the Tafel plot, the required overpotentials for current densities of 0.1 and 1.0 mA/cm2 are only 360 and 430 mV, respectively. The structure and the presence of a CuO motif in the catalyst have been identified by high-energy X-ray diffraction (HE-XRD), Cu K-edge X-ray absorption (XAS) spectra including X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS). To the best of our knowledge, this represents the best catalytic activity for CuO-based OER catalysts to date.

  6. Graphyne-supported single Fe atom catalysts for CO oxidation.

    Science.gov (United States)

    Wu, Ping; Du, Pan; Zhang, Hui; Cai, Chenxin

    2015-01-14

    Single atom catalysts (SACs) are highly desirable for the effort to maximize the efficiency of metal atom use. However, the synthesis of SACs is a major challenge that largely depends on finding an appropriate supporting substrate to achieve a well-defined and highly dispersed single atom. This work demonstrates that, based on the density functional theory (DFT) calculation, graphyne is a good substrate for single Fe atom catalysts. The Fe atom can be tightly embedded in a graphyne sheet with a high binding energy of ∼4.99 eV and a high diffusion energy barrier of ∼1.0 eV. The graphyne-supported Fe (Fe-graphyne) SAC shows high catalytic activity towards CO oxidation, which is often regarded as a prototype reaction for designing atomic-scale catalysts. We studied the adsorption characteristics of CO and O2 on Fe-graphyne SACs, and simulated the reaction mechanism of CO oxidation involving Fe-graphyne. The simulation results indicate that O2 binding on Fe-graphyne is much stronger than that of CO, and the adsorbed O2 prior to occupy the Fe atoms as the co-existence of O2 and CO. The reaction of CO oxidation by adsorbed O2 on Fe-graphyne SACs favors to proceed via the Eley-Rideal (ER) mechanism with the energy barrier of as low as ∼0.21 eV in the rate-limiting step. Calculation of the electronic density of states (DOS) of each reaction step demonstrates that the strong interaction of the O2 and Fe adatom promotes the CO oxidation on Fe-graphyne SACs. The results presented here suggest that graphyne could provide a unique platform to synthesize SACs, and the Fe-graphyne SACs could find potential use in solving the growing environmental problems caused by CO emission from automobiles and industrial processes, in removing CO contamination from vehicle exhaust and in fuel cells.

  7. Catalyst and method for reduction of nitrogen oxides

    Science.gov (United States)

    Ott, Kevin C.

    2008-05-27

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  8. Kinetics of carbon monoxide oxidation over modified supported CuO catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Loc, Luu Cam; Tri, Nguyen; Cuong, Hoang Tien; Thoang, Ho Si [Vietnam Academy of Science and Technology (VAST), Ho Chi Minh City (Viet Nam). Inst. of Chemical Technology; Agafonov, Yu.A.; Gaidai, N.A.; Lapidus, A.L. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Institute of Organic Chemistry

    2013-11-01

    The following supported on {gamma}-Al{sub 2}O{sub 3} catalysts: 10(wt.)%CuO (CuAl), 10%CuO+10%Cr{sub 2}O{sub 3} (CuCrAl) and 10%CuO+20%CeO{sub 2} (CuCeAl) were under the investigation. Physico-chemical characteristics of the catalysts were determined by the methods of BET, X-ray Diffraction (XRD), and Temperature-Programmed Reduction (TPR). A strong interaction of copper with support in CuAl resulted in the formation of low active copper aluminates. The bi-oxide CuCrAl was more active than CuAl owing to the formation of high catalytically active spinel CuCr{sub 2}O{sub 4}. The fact of very high activity of the sample CuCeAl can be explained by the presence of the catalytically active form of CuO-CeO{sub 2}-Al{sub 2}O{sub 3}. The kinetics of CO total oxidation was studied in a gradientless flow-circulating system at the temperature range between 200 C and 270 C. The values of initial partial pressures of carbon monoxide (P{sup o}{sub CO}), oxygen (P{sup o}{sub O2}), and specially added carbon dioxide (P{sup o}{sub CO{sub 2}}) were varied in ranges (hPa): 10 / 45; 33 / 100, and 0 / 30, respectively. (orig.)

  9. Mechanism-Based Design of Green Oxidation Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rybak-Akimova, Elena [Tufts Univ., Medford, MA (United States)

    2015-03-16

    In modern era of scarce resources, developing chemical processes that can eventually generate useful materials and fuels from readily available, simple, cheap, renewable starting materials is of paramount importance. Small molecules, such as dioxygen, dinitrogen, water, or carbon dioxide, can be viewed as ideal sources of oxygen, nitrogen, or carbon atoms in synthetic applications. Living organisms perfected the art of utilizing small molecules in biosynthesis and in generating energy; photosynthesis, which couples carbohydrate synthesis from carbon dioxide with photocatalytic water splitting, is but one impressive example of possible catalytic processes. Small molecule activation in synthetic systems remains challenging, and current efforts are focused on developing catalytic reactions that can convert small molecules into useful building blocks for generating more complicated organic molecules, including fuels. Modeling nature is attractive in many respects, including the possibility to use non-toxic, earth-abundant metals in catalysis. Specific systems investigated in our work include biomimetic catalytic oxidations with dioxygen, hydrogen peroxide, and related oxygen atom donors. More recently, a new direction was been also pursued in the group, fixation of carbon dioxide with transition metal complexes. Mechanistic understanding of biomimetic metal-catalyzed oxidations is critical for the design of functional models of metalloenzymes, and ultimately for the rational synthesis of useful, selective and efficient oxidation catalysts utilizing dioxygen and hydrogen peroxide as terminal oxidants. All iron oxidases and oxygenases (both mononuclear and dinuclear) utilize metal-centered intermediates as reactive species in selective substrate oxidation. In contrast, free radical pathways (Fenton chemistry) are common for traditional inorganic iron compounds, producing hydroxyl radicals as very active, non-selective oxidants. Recent developments, however, changed this

  10. Mechanism-Based Design of Green Oxidation Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rybak-Akimova, Elena [Tufts Univ., Medford, MA (United States)

    2015-03-16

    In modern era of scarce resources, developing chemical processes that can eventually generate useful materials and fuels from readily available, simple, cheap, renewable starting materials is of paramount importance. Small molecules, such as dioxygen, dinitrogen, water, or carbon dioxide, can be viewed as ideal sources of oxygen, nitrogen, or carbon atoms in synthetic applications. Living organisms perfected the art of utilizing small molecules in biosynthesis and in generating energy; photosynthesis, which couples carbohydrate synthesis from carbon dioxide with photocatalytic water splitting, is but one impressive example of possible catalytic processes. Small molecule activation in synthetic systems remains challenging, and current efforts are focused on developing catalytic reactions that can convert small molecules into useful building blocks for generating more complicated organic molecules, including fuels. Modeling nature is attractive in many respects, including the possibility to use non-toxic, earth-abundant metals in catalysis. Specific systems investigated in our work include biomimetic catalytic oxidations with dioxygen, hydrogen peroxide, and related oxygen atom donors. More recently, a new direction was been also pursued in the group, fixation of carbon dioxide with transition metal complexes. Mechanistic understanding of biomimetic metal-catalyzed oxidations is critical for the design of functional models of metalloenzymes, and ultimately for the rational synthesis of useful, selective and efficient oxidation catalysts utilizing dioxygen and hydrogen peroxide as terminal oxidants. All iron oxidases and oxygenases (both mononuclear and dinuclear) utilize metal-centered intermediates as reactive species in selective substrate oxidation. In contrast, free radical pathways (Fenton chemistry) are common for traditional inorganic iron compounds, producing hydroxyl radicals as very active, non-selective oxidants. Recent developments, however, changed this

  11. Gold-Iron Oxide Catalyst for CO Oxidation: Effect of Support Structure

    Directory of Open Access Journals (Sweden)

    Hui-Zhen Cui

    2016-03-01

    Full Text Available Gold-iron oxide (Au/FeOx is one of the highly active catalysts for CO oxidation, and is also a typical system for the study of the chemistry of gold catalysis. In this work, two different types of iron oxide supports, i.e., hydroxylated (Fe_OH and dehydrated iron oxide (Fe_O, have been used for the deposition of gold via a deposition-precipitation (DP method. The structure of iron oxide has been tuned by either selecting precipitated pH of 6.7–11.2 for Fe_OH or changing calcination temperature of from 200 to 600 °C for Fe_O. Then, 1 wt. % Au catalysts on these iron oxide supports were measured for low-temperature CO oxidation reaction. Both fresh and used samples have been characterized by multiple techniques including transmission electron microscopy (TEM and high-resolution TEM (HRTEM, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, X-ray absorption near edge structure (XANES and temperature-programmed reduction by hydrogen (H2-TPR. It has been demonstrated that the surface properties of the iron oxide support, as well as the metal-support interaction, plays crucial roles on the performance of Au/FeOx catalysts in CO oxidation.

  12. Electrical conduction in composites containing copper core-copper oxide shell nanostructure in silica gel

    Indian Academy of Sciences (India)

    D Das; T K Kundu; M K Dey; S Chakraborty; D Chakravorty

    2003-10-01

    Composites of nanometre-sized copper core-copper oxide shell with diameters in the range 6.1 to 7.3 nm dispersed in a silica gel were synthesised by a technique comprising reduction followed by oxidation of a suitably chosen precursor gel. The hot pressed gel powders mixed with nanometre-sized copper particles dispersed in silica gel showed electrical resistivities several orders of magnitude lower than that of the precursor gel. Electrical resistivities of the different specimens were measured over the temperature range 30 to 300°C. Activation energies for the coreshell nanostructured composites were found to be a fraction of that of the precursor gel. Such dramatic changes are ascribed to the presence of an interfacial amorphous phase. The resistivity variation as a function of temperature was analysed on the basis of Mott’s small polaron hopping conduction model. The effective dielectric constant of the interfacial phase as extracted from the data analysis was found to be much higher than that of the precursor glass. This has been explained as arising from the generation of very high pressure at the interface due to the oxidation step to which the copper nanoparticles are subjected.

  13. Ceria doped mixed metal oxide nanoparticles as oxidation catalysts: Synthesis and their characterization

    Directory of Open Access Journals (Sweden)

    S.S.P. Sultana

    2015-11-01

    Full Text Available Mixed metal nanoparticles (NPs have attracted significant attention as catalysts for various organic transformations. In this study, we have demonstrated the preparation of nickel–manganese mixed metal oxide NPs doped with X% nano cerium oxide (X = 1, 3, 5 mol% by a facile co-precipitation technique using surfactant and surfactant free methodologies. The as-synthesized materials were calcined at different temperatures (300 °C, 400 °C, and 500 °C, and were characterized using various spectroscopic techniques, including, FTIR and XRD. SEM analysis, TEM analysis and TGA were employed to evaluate the structural properties of the as-prepared catalyst. These were evaluated for their catalytic behaviour towards the conversion of benzyl alcohol to benzaldehyde, which was used as a model reaction with molecular oxygen as oxidant. Furthermore, the effect of the variation of the percentage of nano ceria doping and the calcination temperature on the performance of as-prepared mixed metal catalysts was also evaluated. The kinetic studies of the reactions performed employing gas chromatographic technique have revealed that the mixed metal oxide catalyst doped with 5% nano ceria displayed excellent catalytc activity, among various catalysts synthesized.

  14. Oxidative dehydrogenation of ethane on rare-earth oxide-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Buyevskaya, O.; Baerns, M. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany)

    1998-12-31

    Results on the oxidative dehydrogenation of ethane on rare-earth oxide (REO) based catalysts (Na-P-Sm-O, Sm-Sr(Ca)-O, La-Sr-O and Nd-Sr-O) are described. Oxygen adsorption was found to be a key factor which determines the activity of this type of catalysts. Continuous flow experiments in the presence of catalysts which reveal strong oxygen adsorption showed that the reaction mixture is ignited resulting in an enhanced heat generation at the reactor inlet. The heat produced by the oxidative reactions was sufficient under the conditions chosen for the endothermic thermal pyrolysis which takes place preferentially in the gas phase. Ignition of the reaction mixture is an important catalyst function. Contrary to non-catalytic oxidative dehydrogenation, reaction temperatures above 700 C could be achieved without significant external heat input. Ethylene yields of up to 34-45% (S=66-73%) were obtained on REO-based catalysts under non-isothermal conditions (T{sub max}=810-865 C) at contact times in the order of 30 to 40 ms. (orig.)

  15. Wet oxidation of phenol on Ce{sub 1{minus}x}Cu{sub x}O{sub 2{minus}{delta}} catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Hocevar, S.; Batista, J. [National Inst. of Chemistry, Ljubljana (Slovenia). Lab. of Catalysis and Chemical Reaction Engineering; Levec, J. [National Inst. of Chemistry, Ljubljana (Slovenia). Lab. of Catalysis and Chemical Reaction Engineering]|[Univ. of Ljubljana (Slovenia). Dept. of Chemical Engineering

    1999-05-15

    Ce{sub 1{minus}x}Cu{sub x}O{sub 2{minus}{delta}} catalysts with 0.05 < x < 0.20 for catalytic wet oxidation of phenol in aqueous solutions have been synthesized using the coprecipitation method. The three most important synthesis parameters, the concentration of the mixed metal salt solution, the rate of coprecipitant addition and the stirrer speed during coprecipitation, were optimized with central composite design using the catalytic activity as a response function. The catalytic activity strongly depends on stirrer speed during coprecipitation. A high mutual dispersion of copper oxide and ceria, having the average crystallite size of about 9 nm, enhances solid solution formation. The unit cell parameter of ceria decreases when the overall concentration of copper in the catalyst increases, most probably obeying Vegard`s law. The catalysts proved to be very stable in hydrothermal reaction conditions at low pH values. After 5 h of reaction in the semibatch CST reactor less than 100 ppm of Cu was leached out of catalyst samples that were calcined in a flow of air for 2 h above 1033 K, and only a very low quantity of carbonaceous deposits were formed on the surface of the catalysts (0.6 wt%). The kinetics of phenol degradation could be interpreted by an equation valid for homogeneous autocatalytic reactions, in which the rate constant depends linearly on the heterogeneous catalyst (Cu) concentrations. This demonstrates that the reaction proceeds through a heterogeneous-homogeneous radical-branched chain mechanism.

  16. 含铋复合氧化物催化剂的研究进展%Research progress in bismuth-containing complex oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    王鹏; 陈晓晖; 魏可镁

    2011-01-01

    Bismuth-containing complex oxides is an research hotspot of selective oxidation and photocatalysis at present. Bismuth oxide can combine with titanium oxide, vanadium oxide, iron oxide, copper oxide,molybdenum oxide ,silicon oxide and tungsten oxide to form bismuth-containing complex oxide catalysts.The research advance on bismuth-containing complex oxide catalysts was reviewed. The research aspects of bismuth-containing complex oxide catalysts in the future were outlined.%含铋复合金属氧化物是当前选择性氧化和光催化方面的研究热点.主要介绍了近年来氧化铋与氧化钛、氧化钒、氧化铁、氧化铜、氧化钼、氧化硅和氧化钨等的复合氧化物催化剂的研究进展,并指出了含铋复合氧化物今后的研究方向.

  17. Copper Oxide Nanoparticles Impact Several Toxicological Endpoints and Cause Neurodegeneration in Caenorhabditis elegans

    OpenAIRE

    Mashock, Michael J.; Zanon, Tyler; Kappell, Anthony D.; Petrella, Lisa N.; Andersen, Erik C.; Hristova, Krassimira R.

    2016-01-01

    Engineered nanoparticles are becoming increasingly incorporated into technology and consumer products. In 2014, over 300 tons of copper oxide nanoparticles were manufactured in the United States. The increased production of nanoparticles raises concerns regarding the potential introduction into the environment or human exposure. Copper oxide nanoparticles commonly release copper ions into solutions, which contribute to their toxicity. We quantified the inhibitory effects of both copper oxide ...

  18. Bioleaching of copper oxide ore by Pseudomonas aeruginosa

    Science.gov (United States)

    Shabani, M. A.; Irannajad, M.; Azadmehr, A. R.; Meshkini, M.

    2013-12-01

    Bioleaching is an environmentally friendly method for extraction of metal from ores. In this study, bioleaching of copper oxide ore by Pseudomonas aeruginosa was investigated. Pseudomonas aeruginosa is a heterotrophic bacterium that can produce various organic acids in an appropriate culture medium, and these acids can operate as leaching agents. The parameters, such as particle size, glucose percentage in the culture medium, bioleaching time, and solid/liquid ratio were optimized. Optimum bioleaching conditions were found as follows: particle size of 150-177 μm, glucose percentage of 6%, bioleaching time of 8 d, and solid/liquid ratio of 1:80. Under these conditions, 53% of copper was extracted.

  19. Bioleaching of copper oxide ore by P seudomonas aeruginosa

    Institute of Scientific and Technical Information of China (English)

    MA Shabani; M Irannajad; AR Azadmehr; M Meshkini

    2013-01-01

    Bioleaching is an environmentally friendly method for extraction of metal from ores. In this study, bioleaching of copper oxide ore by Pseudomonas aeruginosa was investigated. Pseudomonas aeruginosa is a heterotrophic bacterium that can produce various organic acids in an appropriate culture medium, and these acids can operate as leaching agents. The parameters, such as particle size, glucose percentage in the culture medium, bioleaching time, and solid/liquid ratio were optimized. Optimum bioleaching conditions were found as follows: particle size of 150-177 μm, glucose percentage of 6%, bioleaching time of 8 d, and solid/liquid ratio of 1:80. Under these conditions, 53%of copper was extracted.

  20. Oxidative desulfurization of synthetic diesel using supported catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Caero, Luis Cedeno; Hernandez, Emiliano [UNICAT, Departamento de Ingenieria Quimica, Facultad de Quimica, UNAM. Cd. Universitaria, 04510 Mexico D.F. (Mexico); Pedraza, Francisco; Murrieta, Florentino [Programa de Tratamiento en Crudo Maya, Instituto Mexicano del Petroleo, Eje Central 152, 07730 Mexico D.F. (Mexico)

    2005-10-30

    In this work, an experimental study was carried out to obtain the reactivity of different organic sulfur compounds and to examine the effect of various parameters, such as temperature, solvent and the amount of oxidant reagent in oxidative desulfurization (ODS) reaction. The oxidation was performed through a vanadium based catalyst in the presence of hydrogen peroxide under mild reaction conditions, atmospheric pressure and temperature range of 303-343K. The sulfur compounds studied were: 2-methylthiophene (2-MT), 2,5-dimethylthiophene (2,5-DMT), benzothiophene (BT), dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT). All of them are typical thiophenic sulfur compounds present in diesel fuels. A synthetic diesel was prepared with these compounds in hexadecane. The experimental results showed that oxidation reactivities decreased according to the following order: DBT>BT>4-MDBT>2-MT>2,5-DMT>4,6-DMDBT. A fraction of the S compounds removed from the diesel phase, was not transformed to its corresponding sulfone, under these experimental conditions. It is only removed as sulfur compound by extraction, without ODS reaction. The surplus amount of oxidant promoted the equilibrium reaction, but the thermal decomposition of oxidant and oxidation reactions produces water, which inhibits the ODS reactions. Therefore, the controlled addition of H{sub 2}O{sub 2} improves ODS reactivity of sulfur compounds.

  1. Structural and surface changes of copper modified manganese oxides

    Energy Technology Data Exchange (ETDEWEB)

    Gac, Wojciech, E-mail: wojciech.gac@umcs.lublin.pl; Słowik, Grzegorz; Zawadzki, Witold

    2016-05-01

    Highlights: • Formation of MnO with regular rippled-like surface patterns. • Synthesis of copper nanorods supported on MnO nanoparticles. • Hydrogen production in steam methanol reforming over supported copper nanorods. - Abstract: The structural and surface properties of manganese and copper–manganese oxides were investigated. The oxides were prepared by the redox-precipitation method. X-ray diffraction and electron microscopy studies evidenced transformation of cryptomelane-type nanoparticles with 1-D channel structure into the large MnO crystallites with regular rippled-like surface patterns under reduction conditions. The development of Cu/CuO nanorods from strongly dispersed species was evidenced. Coper-modified manganese oxides showed good catalytic performance in methanol steam reforming reaction for hydrogen production. Low selectivity to CO was observed in the wide range of temperatures.

  2. Microstructure and Mechanical Properties of Graphene Oxide/Copper Composites

    Directory of Open Access Journals (Sweden)

    HONG Qi-hu

    2016-09-01

    Full Text Available Graphene oxide/copper (GO/Cu composites were successfully synthesized through the ball milling and vacuum hot press sintering process. The morphologies of the mixture powders, and the microstructure and mechanical properties of GO/Cu composites were investigated by OM, SEM, XRD, hardness tester and electronic universal testing machine, respectively. The results show that the GO/Cu composites are compact. Graphene oxide with flake morphology is uniformly dispersed and well consolidated with copper matrix. When the mass fraction of graphene oxide is 0.5%, the microhardness and compress strength at RT reach up to 63HV and 276MPa, increased by 8.6% and 28%, respectively. The strengthening mechanism is load transfer effect, dislocation strengthening and fine crystal reinforcing.

  3. A novel, green 1-glycyl-3-methyl imidazolium chloride-copper(Ⅱ)complex catalyzed C-H oxidation of alkyl benzene and cyclohexane

    Institute of Scientific and Technical Information of China (English)

    Parasuraman Karthikeyan; Pundlik Rambhau Bhagat; S. Senthil Kumar

    2012-01-01

    A variety of alkyl-arenes and cyclohexane were converted to the corresponding ketones with NaClO as the oxidant in the presence of 1-glycyl-3-methyl imidazolium chloride-copper(Ⅱ) complex.This method contains simplified product isolation and catalyst recycling,affording benzylic C-H oxidation of alkyl-arenes imparting high yield of ketones.Furthermore,complex could be reused seven times without a significant loss of its catayfic activity.

  4. A porphyrin-stabilized iridium oxide water oxidation catalyst

    National Research Council Canada - National Science Library

    Pillai, Smitha; Gust, Devens; Moore, Ana L; Kodis, Gerdenis; Mallouk, Thomas E; Moore, Thomas A; Bergkamp, Jesse; Sherman, Benjamin D

    2011-01-01

    Colloidal solutions of iridium oxide hydrate (IrO 2 ·nH 2 O) were formed using porphyrin stabilizers bearing malonate-like functional groups at each of the four meso positions of the porphyrin ring...

  5. CO oxidation activity of Cu-CeO2 nano-composite catalysts prepared by laser vaporization and controlled condensation

    Science.gov (United States)

    Sundar, Rangaraj S.; Deevi, Sarojini

    2006-08-01

    Ceria supported copper catalysts were synthesized by laser vaporization and controlled condensation method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDAX) and temperature programmed reduction (TPR). The catalytic activity of the nanopowders for CO oxidation reaction was tested in a fixed bed flow tube reactor in Ar-20%O2-4%CO mixture. Irrespective of the copper content, the catalytic activity of the nanopowders is similar in the initial CO test, and the catalytic activity improves (i.e. the light-off temperature decreases) during a subsequent run. The lowest light-off temperature during the second run is recorded in the material with 20% copper. TEM studies on 20%Cu-CeO2 sample in the as-prepared condition and after CO test exhibit two types of ceria particles namely, polygonal particles 3-5 nm in size and spherical particles of 15-20 nm in size. Rapid cooling of the nanoparticles formed during the laser ablation results in incorporation of a large amount of copper within the ceria as solid solution. Presence of solid solution of copper is confirmed by EDAX and electron diffraction analyses. In addition, copper-rich surface layer of Cu2O is found over the spherical particles. The cerium oxide components are essentially identical before and after CO test, except that the polygonal CeO2 particles contain newly formed fine crystals of CuO. TPR results reveal two reduction peaks, which further supports, the presence of two different copper species in the material. The shift in light-off temperature during the second run is attributed to the synergistic interaction between newly formed CuO crystals with the CeO2 matrix.

  6. Selective Oxidation of Isobutane to Methacrylic Acid over Supported V-Mo-P Based Composite Oxide Catalysts

    Institute of Scientific and Technical Information of China (English)

    Feifei Sun; Yunfeng Geng; Shunhe Zhong

    2002-01-01

    Heteropolyacid, the most popular catalyst for the direct oxidation of isobutane, exhibits high catalytic activity, poor thermal stability and a short lifetime. Therefore, the catalyst requires further research to improve its performance. Catalysts composed of mixed oxides (V2O5, P2O5, or MoO3) supported on silica were prepared by the sol-gel method to catalyze the reaction. Results of XRD, IR, and BET corroborated that the mixed oxides were dispersed homogeneously on the surface of support. The activity of lattice oxygen in the catalysts was studied by TPR, and the chemisorption property of isobutane on the surface of the catalysts was investigated by the TPD method. H2-TPR of the catalysts revealed that the lattice oxygen of the vanadium-based catalysts is more active than that of the molybdenum-based catalysts. The rcdox property of V or Mo species is slightly affected by other compositions of the series catalysts. The TPD curves illustrate that there are two kinds of adsorptive species of isobutane on the surface of the V and Mo based catalysts. The adsorbing species on the VMoP/SiO2 catalyst are identical to the main adsorbing species on VP/SiO2 and MoP/SiO2. The catalyst VMoP/SiO2 is more active than others in the selective oxidation of isobutane.

  7. Formation of copper oxychloride and reactive oxygen species as causes of uterine injury during copper oxidation of Cu-IUD.

    Science.gov (United States)

    Beltran-Garcia, M J; Espinosa, A; Herrera, N; Perez-Zapata, A J; Beltran-Garcia, C; Ogura, T

    2000-02-01

    The lining of the uterus and cervix might be injured by a variety of oxidation products of Cu in a Cu-IUD, including cuprous ions, dissolved and precipitated cupric ions, and reactive oxygen species such as superoxide radicals, hydrogen peroxide, and hydroxyl radicals. In this study, the human amnious WISH cell line was employed as a model of uterine cells in the presence of copper. The cell viability was decreased by elemental copper, which was alleviated up to 70% by the addition of catalase. The addition of copper oxychloride caused cell death in a dose-dependent manner. Hydroxyl radicals in the presence of copper were determined by the formation of malondialdehyde. Soluble cuprous chloride complexes are formed in the uterus by slowly entering oxygen. The complexes are partly oxidized to insoluble copper oxychloride. which damages the endometrium. Unoxidized cuprous ions migrate to the oxygen-rich cervix and are oxidized to copper oxychloride, causing cervix damage.

  8. Preparation of rare-earth metal complex oxide catalysts for catalytic wet air oxidation

    Institute of Scientific and Technical Information of China (English)

    LI Ning; LI Guangming; YAO Zhenya; ZHAO Jianfu

    2007-01-01

    Catalytic wet air oxidation(CWAO)is one of the most promising technologies for pollution abatement.Developing catalysts with high activity and stability is crucial for the application of the CWAO process.The Mn/Ce complex oxide catalyrsts for CWAO of high concentration phenol containing wastewater were prepared by coprecipitation.The catalyst preparation conditions were optimized by using an orthogonal layout method and single-factor experimental analysis.The Mn/Ce serial catalysts were characterized by Brunauer-Emmett-Teller(BET)analysis and the metal cation leaching was measured by inductively coupled plasma torch-atomic emission spectrometry(ICP-AES).The results show that the catalysts have high catalytic activities even at a low temperature(80℃)and low oxygen partial pressure(0.5 MPa)in a batch reactor.The metallic ion leaching is comparatively low(Mn<6.577 mg/L and Ce<0.6910 mg/L,respectively)in the CWAO process.The phenol,CODCD and TOC removal efficiencies in the solution exceed 98.5% using the optimal catalyst(named CSP).The new catalyst would have a promising application in CWAO treatment of high concentration organic wastewater.

  9. Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts

    Science.gov (United States)

    Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor)

    2011-01-01

    The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

  10. Dry air effects on the copper oxides sensitive layers formation for ethanol vapor detection

    Energy Technology Data Exchange (ETDEWEB)

    Labidi, A., E-mail: Ahmed_laabidi@yahoo.fr [URPSC (UR 99/13-18) Unite de Recherche de Physique des Semiconducteurs et Capteurs, IPEST, Universite de Carthage, BP 51, La Marsa 2070, Tunis (Tunisia); Bejaoui, A.; Ouali, H. [URPSC (UR 99/13-18) Unite de Recherche de Physique des Semiconducteurs et Capteurs, IPEST, Universite de Carthage, BP 51, La Marsa 2070, Tunis (Tunisia); Akkari, F. Chaffar [Laboratoire de Photovoltaique et Materiaux Semi-conducteurs, ENIT, Universite de Tunis el Manar, BP 37, Le belvedere 1002, Tunis (Tunisia); Hajjaji, A.; Gaidi, M. [Laboratoire de Photovoltaique, Centre de Recherches et de technologies de l' energie, Technopole de Borj-Cedria, BP 95, 2050 Hammam-Lif (Tunisia); Kanzari, M. [Laboratoire de Photovoltaique et Materiaux Semi-conducteurs, ENIT, Universite de Tunis el Manar, BP 37, Le belvedere 1002, Tunis (Tunisia); Bessais, B. [Laboratoire de Photovoltaique, Centre de Recherches et de technologies de l' energie, Technopole de Borj-Cedria, BP 95, 2050 Hammam-Lif (Tunisia); Maaref, M. [URPSC (UR 99/13-18) Unite de Recherche de Physique des Semiconducteurs et Capteurs, IPEST, Universite de Carthage, BP 51, La Marsa 2070, Tunis (Tunisia)

    2011-09-15

    The copper oxide films have been deposited by thermal evaporation and annealed under ambient air and dry air respectively, at different temperatures. The structural characteristics of the films were investigated by X-ray diffraction. They showed the presences of two hydroxy-carbonate minerals of copper for annealing temperatures below 250 deg. C. Above this temperature the conductivity measurements during the annealing process, show a transition phase from metallic copper to copper oxides. The copper oxides sensitivity toward ethanol were performed using conductivity measurements at the working temperature of 200 deg. C. A decrease of conductivity was observed under ethanol vapor, showing the p-type semi-conducting characters of obtained copper oxide films. It was found that the sensing properties of copper oxide toward ethanol depend mainly on the annealing conditions. The best responses were obtained with copper layers annealed under dry air.

  11. Selective oxidation of propane to acrylic acid over mixed metal oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    Wei Zheng; Zhenxing Yu; Ping Zhang; Yuhang Zhang; Hongying Fu; Xiaoli Zhang; Qiquan Sun; Xinguo Hu

    2008-01-01

    The effects of metal atomic ratio, water content, oxygen content, and calcination temperature on the catalytic perfor-mances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of propane to acrylic acid have been investigated and discussed. Among the catalysts studied, it was found that the MoVTeNbO catalyst calcined at a temperature of 600 ℃ showed the best performance in terms of propane conversion and selectivity for acrylic acid under an atmosphere of nitrogen. An effective MoVTeNbO oxide catalyst for propane selective oxidation to acrylic acid was obtained with a combination of a preferred metal atomic ratio (Mo1 V0.31Te0.23Nb0.12). The optimum reaction condition for the selective oxidation of propane was the molar ratio of C3H81 :O2 : H2O : N1 = 4.4 : 12.8 : 15.3 : 36.9. Under such conditions, the conversion of propane and the maximum yield of acrylic acid reached about 50% and 21%, respectively.

  12. SO2 oxidation catalyst model systems characterized by thermal methods

    DEFF Research Database (Denmark)

    Hatem, G; Eriksen, Kim Michael; Gaune-Escard, M;

    2002-01-01

    The molten salts M2S2O7 and MHSO4, the binary molten salt Systems M2S2O7-MHSO4 and the molten salt-gas systems M2S2O7 V2O5 and M2S2O7-M2SO4 V2O5 (M = Na, K, Rb, Cs) in O-2, SO2 and At atmospheres have been investigated by thermal methods like calorimetry, Differential Enthalpic Analysis (DEA) and...... to the mechanism Of SO2 oxidation by V2O5 based industrial catalysts....

  13. Study on emissions reduction of DMCC engine with oxidation catalyst

    Institute of Scientific and Technical Information of China (English)

    YAO Chunde; LIU Xibo; WANG Hongfu; LIU Xiaoping; CHENG Chuanhui; WANG Yinshan

    2007-01-01

    A new combustion model diesel/methanol compound combustion (DMCC) is presented,in which methanol is injected into manifold and ignited by certain amount of diesel fuel.The results showed that DMCC remarkably decreased the emission of NOx and the smoke,but increased the emission of HC,CO and PM.However,HC,CO and NOx were dramatically decreased with a catalytic converter,and PM was also decreased compared with that of diesel engine.The testing results illustrated that,combined with oxidation catalyst converter,DMCC could improve engine emissions.

  14. Selective oxidation of propylene to acrolein by silica-supported bismuth molybdate catalysts

    DEFF Research Database (Denmark)

    Duc, Duc Truong; Ha, Hanh Nguyen; Fehrmann, Rasmus

    2011-01-01

    Silica-supported bismuth molybdate catalysts have been prepared by impregnation, structurally characterized and examined as improved catalysts for the selective oxidation of propylene to acrolein. Catalysts with a wide range of loadings (from 10 to 90 wt%) of beta bismuth molybdate (β-Bi2Mo2O9...

  15. A Green Recyclable Poly(4-vinylpyridine)-Supported Copper Iodide Nanoparticles Catalyst for the Multicomponent Synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones

    Energy Technology Data Exchange (ETDEWEB)

    Albadi, Jalal [Behbahan Khatam Alanbia Univ. of Technology, Behbahan (Iran, Islamic Republic of); Mansournezhad, Azam; Baghernehad, Mojtba; Frozan, Nasrin [Islamic Azad Univ., Gachsaran (Iran, Islamic Republic of)

    2013-04-15

    Dihydropyrimidone derivatives are important class of compounds that received significant attention from many pharmaceutical and organic chemists because of the broad spectrum of their biological and pharmaceutical properties such as antibacterial, anti-inflammatory, and antivirial properties. The initial synthesis of dihydropyrimidone was reported by Biginelli involving a one pot condensation of an aldehydes, β-ketoester and urea under acidic conditions. However, this reaction suffers from the harsh conditions, long reaction times and low yields of the products. In order to improve the efficiency of this reaction, several modified procedures have been reported. Recently, the application of CuI as the catalyst for the Bignielli reaction have been reported. However, in spite of its application potentials, CuI have some limitations such as thermodynamic instability, long reaction times, non-recyclable, toxicity and difficulty in separation of the product from the reaction medium. Such drawbacks could be obviated by using the supported catalyst. Nitrogen-based polymer have been shown to protect the metal center from oxidation and disproportionation, while enhancing its catalytic activity. To improve the recovery and reuse, copper species have been immobilized on the various supports such as carbon, amine-functionalized polymers, zeolites, amine-functionalized silica and aluminum oxyhydroxide fiber. Poly(4-vinylpyridine)-supported reagents are active for various organic reactions including oxidations, reductions and halogenations. Simple recovery from reaction mixtures, their reusability, compatibility with a wide range of solvents, physical stability, and their toleration of a great number of reaction conditions bodes well for the future of P{sub 4}VPy-supported reagents in which their properties can be finetuned for specific chemical transformations. In recent years, nano-catalysts has emerged as a sustainable and competitive alternative to conventional catalysits

  16. EFFECTS OF CONFORMATION OF POLYMER LIGANDS IN COPPER(Ⅱ) COMPLEXES ON CATALYLIC ACTIVITIES AND MECHANISM OF OXIDATIVE COUPLING OF β-NAPHTHOL

    Institute of Scientific and Technical Information of China (English)

    BIAN Kejian; LUO Chunqiao; CAO Mengjun

    1987-01-01

    Copper(Ⅱ) complexes of sericin, chitosan, 6-and 2-aminodeoxystarch were used as catalysts in oxidative coupling of β-naphthol, the effects of conformation of the polymer ligands in these complexes on activities of the catalysts and mechanisms of the reaction were studied. It was found that if the catalysts react with the substrate by mechanism similar to the enzymic catalysis they must be composed of polymer ligands with highly coiled, especially with densely helicoidal,conformations. While catalysts composed of loosely coiled or helicoidal ligands react with the substrate through molecular collision and have relatively lower activities only. Under nitrogen,catalysts from sericin and chitosam reacting with β-naphthol give optically active β-binaphthol,rotating polarized light to right, but the stereoselectivities are rather low.

  17. Oxidation Behavior of GRCop-84 Copper Alloy Assessed

    Science.gov (United States)

    Thomas-Ogbuji, Linus U.

    2002-01-01

    NASA's goal of safe, affordable space transportation calls for increased reliability and lifetimes of launch vehicles, and significant reductions of launch costs. The areas targeted for enhanced performance in the next generation of reusable launch vehicles include combustion chambers and nozzle ramps; therefore, the search is on for suitable liner materials for these components. GRCop-84 (Cu-8Cr-4Nb), an advanced copper alloy developed at the NASA Glenn Research Center in conjunction with Case Western Reserve University, is a candidate. The current liner of the Space Shuttle Main Engine is another copper alloy, NARloy-Z (Cu-3Ag-0.1Zr). It provides a benchmark against which to compare the properties of candidate successors. The thermomechanical properties of GRCop-84 have been shown to be superior, and its physical properties comparable, to those of NARloy-Z. However, environmental durability issues control longevity in this application: because copper oxide scales are not highly protective, most copper alloys are quickly consumed in oxygen environments at elevated temperatures. In consequence, NARloy-Z and most other copper alloys are prone to blanching, a degradation process that occurs through cycles of oxidation-reduction as the oxide is repeatedly formed and removed because of microscale fluctuations in the oxygen-hydrogen fuel systems of rocket engines. The Space Shuttle Main Engine lining typically degraded by blanching-induced hot spots that lead to surface roughening, pore formation, and coolant leakage. Therefore, resistance to oxidation and blanching are key requirements for second-generation reusable launch vehicle liners. The rocket engine ambient includes H2 (fuel) and H2O (combustion product) and is, hence, under reduced oxygen partial pressures. Accordingly, our studies were expanded to include oxygen partial pressures as low as 322 parts per million (ppm) at the temperatures likely to be experienced in service. A comparison of 10-hr weight gains of

  18. Comparison and distribution of copper oxide nanoparticles and copper ions in activated sludge reactors.

    Science.gov (United States)

    Zhang, Dongqing; Trzcinski, Antoine P; Oh, Hyun-Suk; Chew, Evelyn; Tan, Soon Keat; Ng, Wun Jern; Liu, Yu

    2017-05-12

    Copper oxide nanoparticles (CuO NPs) are being increasingly applied in the industry which results inevitably in the release of these materials into the hydrosphere. In this study, simulated waste-activated sludge experiments were conducted to investigate the effects of Copper Oxide NPs at concentrations of 0.1, 1, 10 and 50 mg/L and to compare it with its ionic counterpart (CuSO4). It was found that 0.1 mg/L of CuO NPs had negligible effects on Chemical Oxygen Demand (COD) and ammonia removal. However, the presence of 1, 10 and 50 mg/L of CuO NPs decreased COD removal from 78.7% to 77%, 52.1% and 39.2%, respectively (P copper ions were more toxic towards microorganisms compared to CuO NPs. CuO NPs were removed effectively (72-93.2%) from wastewater due to a greater biosorption capacity of CuO NPs onto activated sludge, compared to the copper ions (55.1-83.4%). The SEM images clearly showed the accumulation and adsorption of CuO NPs onto activated sludge. The decrease in Live/dead ratio after 5 h of exposure of CuO NPs and Cu(2+) indicated the loss of cell viability in sludge flocs.

  19. Characterization and Catalytic Activity for the Oxidation of Ethane and Propane on Platinum and Copper Supported on CeO2/Al2O3

    Directory of Open Access Journals (Sweden)

    Cataluña R.

    1998-01-01

    Full Text Available Ethane and propane oxidation on platinum and copper supported on Al2O3 and CeO2/Al2O3 catalysts were studied comparatively by examining reaction rates as a function of temperature. Results show that the addition of cerium oxide shifts the catalytic activity to higher temperatures. This negative influence is less pronounced in the case of supported copper samples, which on the basis of EPR and FTIR of adsorbed CO results is attributed to the low relative amount of this metal is in contact with ceria. The decrease in activity the presence of ceria might be due to changes in metal particle size or to the stabilization of the oxidized states of the metals, induced by their interactions with cerium oxide. The higher activity of platinum, in comparison with copper, is attributed to its higher reducibility along with an easier hydrocarbon activation on that metal.

  20. Nano-sized Mn oxide/agglomerated silsesquioxane composite as a good catalyst for water oxidation.

    Science.gov (United States)

    Najafpour, Mohammad Mahdi; Madadkhani, Sepideh

    2016-12-01

    Water splitting to hydrogen and oxygen is an important reaction to store sustainable energies, and water oxidation is identified as the bottleneck for water splitting because it requires the high activation energy to perform. Herein a nano-sized Mn oxide/agglomerated silsesquioxane composite was used to synthesize an efficient catalyst for water oxidation. The composite was synthesized by a straightforward and simple procedure and characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, dynamic light scattering, X-ray diffraction spectrometry, and electrochemical methods. Silsesquioxane causes good dispersion of Mn in the composite. The water-oxidizing activity of this composite was studied in the presence of cerium(IV) ammonium nitrate. The composite at the best calcination temperature (300 °C) shows a turnover frequency 0.3 (mmol O2/mol Mn.s). Regarding the low-cost, environmentally friendly precursors, simple synthesis, and efficiency for water oxidation, the composite is a promising catalyst that can be used in artificial photosynthetic systems for water splitting. We used Agglomerated silsesquioxane as a support for nano-sized Mn oxide to synthesize a good water-oxidizing catalyst.

  1. Efficient oxidation of benzyl alcohol with heteropolytungstate as reaction-controlled phase-transfer catalyst

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A series of heteropolytungstates has been synthesized and utilized as catalysts to catalyze oxidation of benzyl alcohol with aqueous hydrogen peroxide. The results indicated that three of these catalysts showed the properties of reaction-controlled phasetransfer catalysis, and they had excellent catalytic ability to the oxidation of benzyl alcohol. No other by-products were detected by gas chromatography. Once the hydrogen peroxide was consumed completely, the catalyst precipitated from solvent, and the results of the catalyst recycle showed that the catalyst had high stability.

  2. Dinuclear thiazolylidene copper complex as highly active catalyst for azid–alkyne cycloadditions

    Science.gov (United States)

    Schöffler, Anne L; Makarem, Ata; Rominger, Frank

    2016-01-01

    Summary A dinuclear N-heterocyclic carbene (NHC) copper complex efficiently catalyzes azide–alkyne cycloaddition (CuAAC) “click” reactions. The ancillary ligand comprises two 4,5-dimethyl-1,3-thiazol-2-ylidene units and an ethylene linker. The three-step preparation of the complex from commercially available starting compounds is more straightforward and cost-efficient than that of the previously described 1,2,4-triazol-5-ylidene derivatives. Kinetic experiments revealed its high catalytic CuAAC activity in organic solvents at room temperature. The activity increases upon addition of acetic acid, particularly for more acidic alkyne substrates. The modular catalyst design renders possible the exchange of N-heterocyclic carbene, linker, sacrificial ligand, and counter ion. PMID:27559407

  3. Dinuclear thiazolylidene copper complex as highly active catalyst for azid–alkyne cycloadditions

    Directory of Open Access Journals (Sweden)

    Anne L. Schöffler

    2016-07-01

    Full Text Available A dinuclear N-heterocyclic carbene (NHC copper complex efficiently catalyzes azide–alkyne cycloaddition (CuAAC “click” reactions. The ancillary ligand comprises two 4,5-dimethyl-1,3-thiazol-2-ylidene units and an ethylene linker. The three-step preparation of the complex from commercially available starting compounds is more straightforward and cost-efficient than that of the previously described 1,2,4-triazol-5-ylidene derivatives. Kinetic experiments revealed its high catalytic CuAAC activity in organic solvents at room temperature. The activity increases upon addition of acetic acid, particularly for more acidic alkyne substrates. The modular catalyst design renders possible the exchange of N-heterocyclic carbene, linker, sacrificial ligand, and counter ion.

  4. Copper sulfate improves pullulan production by bioconversion using whole cells of Aureobasidium pullulans as the catalyst.

    Science.gov (United States)

    Wang, Dahui; Ju, Xiaomin; Zhang, Gaochuan; Wang, Donghua; Wei, Gongyuan

    2016-10-01

    The effects of mineral salts on pullulan production by bioconversion using whole cells of Aureobasidium pullulans CCTCC M 2012259 as the catalyst were investigated. Copper sulfate (CuSO4) improved pullulan production by 36.2% and 42.3% when added at the optimum concentration of 0.2mg/L to the bioconversion broth or seed medium, respectively, as compared with controls without CuSO4 addition. Pullulan production was further enhanced when CuSO4 was added to both seed medium and bioconversion broth simultaneously. In order to probe the mechanism of CuSO4 improvement, cell viability, membrane integrity, intracellular adenosine triphosphate (ATP) levels and the activities of key enzymes involved in pullulan biosynthesis were determined. As a result, CuSO4 increased the activities of key biosynthetic enzymes, maintained intracellular ATP at a higher level, and accelerated the rate of pullulan secretion, all of which contributed to improved pullulan production by bioconversion.

  5. Dynamic Kinetics of Methanol Synthesis over a Commercial Copper-Based Catalyst

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Adsorption, surface reaction and process dynamics on the surface of a commercial copper-based cata lyst for methanol synthesis from CO/CO2/H2 were systematically studied by means of temperature programmed desorption (TPD), tsmperature programmed surface reaction (TPSR), in-situ Fourier transform-inferred spec troscopy(FTIR) and stimulua-response techniques. As a part of results, an elementary step sequence was suggested and a group of ordinary differential equations (ODEs) for describing transient conversations relevant to all species on the catalyst surface and in the gas phase in a micro-fixed-bed reactor was derived. The values of the parameters referred to dynamic kinetics were estimated by fitting the solution of the ODEs with the transient response data obtained by the stimulus-response technique with a FTIR analyzer as an on-line detector.

  6. Computationally Probing the Performance of Hybrid, Heterogeneous, and Homogeneous Iridium-Based Catalysts for Water Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    García-Melchor, Max [SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford CA (United States); Vilella, Laia [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST),Tarragona (Spain); Departament de Quimica, Universitat Autonoma de Barcelona, Barcelona (Spain); López, Núria [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Tarragona (Spain); Vojvodic, Aleksandra [SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park CA (United States)

    2016-04-29

    An attractive strategy to improve the performance of water oxidation catalysts would be to anchor a homogeneous molecular catalyst on a heterogeneous solid surface to create a hybrid catalyst. The idea of this combined system is to take advantage of the individual properties of each of the two catalyst components. We use Density Functional Theory to determine the stability and activity of a model hybrid water oxidation catalyst consisting of a dimeric Ir complex attached on the IrO2(110) surface through two oxygen atoms. We find that homogeneous catalysts can be bound to its matrix oxide without losing significant activity. Hence, designing hybrid systems that benefit from both the high tunability of activity of homogeneous catalysts and the stability of heterogeneous systems seems feasible.

  7. Platinum nanoparticles–manganese oxide nanorods as novel binary catalysts for formic acid oxidation

    Directory of Open Access Journals (Sweden)

    Mohamed S. El-Deab

    2012-01-01

    Full Text Available The current study proposes a novel binary catalyst system (composed of metal/metal oxide nanoparticles as a promising electrocatalyst in formic acid oxidation. The electro-catalytic oxidation of formic acid is carried out with binary catalysts of Pt nanoparticles (nano-Pt and manganese oxide nanorods (nano-MnOx electrodeposited onto glassy carbon (GC electrodes. Cyclic voltammetric (CV measurements showed that unmodified GC and nano-MnOx/GC electrodes have no catalytic activity. While two oxidation peaks were observed at nano-Pt/GC electrode at ca. 0.2 and 0.55 V (corresponding to the direct oxidation of formic acid and the oxidation of the poisoning CO intermediate, respectively. The combined use of nano-MnOx and nano-Pt results in superb enhancement of the direct oxidation pathway. Nano-MnOx is shown to facilitate the oxidation of CO (to CO2 by providing oxygen at low over-potential. This leads to retrieval of Pt active sites necessary for the direct oxidation of formic acid. The higher catalytic activity of nano-MnOx/nano-Pt/GC electrode (with Pt firstly deposited compared to its mirror image electrode (i.e., with MnOx firstly deposited, nano-Pt/nano-MnOx/GC reveals that the order of the electrodeposition is an essential parameter.

  8. Investigation of PCDD/F emissions from mobile source diesel engines: impact of copper zeolite SCR catalysts and exhaust aftertreatment configurations.

    Science.gov (United States)

    Liu, Z Gerald; Wall, John C; Barge, Patrick; Dettmann, Melissa E; Ottinger, Nathan A

    2011-04-01

    This study investigated the impact of copper zeolite selective catalytic reduction (SCR) catalysts and exhaust aftertreatment configurations on the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from mobile source diesel engines. Emissions of PCDD/Fs, reported as the weighted sum of 17 congeners called the toxic equivalency quotient (TEQ), were measured using a modified EPA Method 0023A in the absence and presence of exhaust aftertreatment. Engine-out emissions were measured as a reference, while aftertreatment configurations included various combinations of diesel oxidation catalyst (DOC), diesel particulate filter (DPF), Cu-zeolite SCR, Fe-zeolite SCR, ammonia oxidation catalyst (AMOX), and aqueous urea dosing. In addition, different chlorine concentrations were evaluated. Results showed that all aftertreatment configurations reduced PCDD/F emissions in comparison to the engine-out reference, consistent with reduction mechanisms such as thermal decomposition or combined trapping and hydrogenolysis reported in the literature. Similarly low PCDD/F emissions from the DOC-DPF and the DOC-DPF-SCR configurations indicated that PCDD/F reduction primarily occurred in the DOC-DPF with no noticeable contribution from either the Cu- or Fe-zeolite SCR systems. Furthermore, experiments performed with high chlorine concentration provided no evidence that chlorine content has an impact on the catalytic synthesis of PCDD/Fs for the chlorine levels investigated in this study.

  9. Model studies with gold: a versatile oxidation and hydrogenation catalyst.

    Science.gov (United States)

    Pan, Ming; Gong, Jinlong; Dong, Guangbin; Mullins, C Buddie

    2014-03-18

    Historically, scientists have considered gold an inert catalyst constituent. However, in recent decades, chemists have discovered that nanoscale gold shows exceptional activity for many chemical reactions. They have investigated model gold surfaces in order to obtain fundamental understanding of catalytic properties. In this Account, we present our current understanding of oxidation and hydrogenation reactions on the Au(111) single crystal as a planar representative of gold catalysts, revealing the interesting surface chemistry of gold. We begin by comparing two inverse reactions, alcohol oxidation and aldehyde hydrogenation, on a Au(111) surface. Beyond the expected different chemistry, we observe intriguing similarities since the same surface is employed. First, both molecular oxygen and hydrogen have high barriers to dissociation on Au(111), and frequently chemists study reactions here by using atomic O and H to populate the surfaces. Recombinative desorption features of oxygen and hydrogen are apparent at ∼500 and ∼110 K, lower than other transition metals. These results indicate that oxygen and hydrogen have low desorption activation energies and weakly chemisorb on the surface, likely leading to selective reactions. On the oxygen-precovered Au(111) surface, alcohols are selectively oxidized to aldehydes. Similarly, weakly bound hydrogen atoms on Au(111) also show chemoselective reactivity for hydrogenation of propionaldehyde and acetone. The second similarity is that the gold surface activates self-coupling of alcohol or aldehyde with oxygen or hydrogen, resulting in the formation of esters and ethers, respectively, in alcohol oxidation and aldehyde hydrogenation. During these two reactions, both alkoxy groups and alcohol-like species show up as intermediates, which likely play a key role in the formation of coupling products. In addition, the cross coupling reaction between alcohol and aldehyde occurs on both O- and H-modified surfaces, yielding the

  10. Selective oxidation of methane to ethane and ethylene over various oxide catalysts

    NARCIS (Netherlands)

    Roos, J.A.; Bakker, A.G.; Bosch, H.; van Ommen, J.G.; Ross, J.R.H.

    1987-01-01

    Preliminary results are reported for the oxidative coupling of methane to give ethane/ethylene mixtures over a series of different catalyst formulations; the temperature range studied is 650–850°C. A comparison is made of the behaviour of lead/alumina and lithium/magnesia materials. It is found that

  11. Use of Graphite Oxide and Graphene Oxide as Catalysts in the Synthesis of Dipyrromethane and Calix[4]pyrrole

    Directory of Open Access Journals (Sweden)

    Sweta Mishra

    2011-08-01

    Full Text Available Graphite oxide and graphene oxides have been used as solid catalysts for the synthesis of 5,5-dialkyldipyrromethanes and calix[4]pyrroles in organic and aqueous solutions at room temperature.

  12. Controlled Growth of Copper Oxide Nano-Wires through Direct Oxidation

    Science.gov (United States)

    Hilman, Joann; Neupane, Ravi; Yost, Andrew J.; Chien, Teyu

    Copper oxides, both Cu2O and CuO, have many applications in solar cells, sensors, and nano-electronics. The properties of the copper oxides are further influenced by the dimension of the materials, especially when made in nanoscale. In particular, the properties of the copper oxide nanowires could be tuned by their structures, lengths, and widths. While several methods have been reported to grow nanowires, direct oxidation is arguably the most economical one. This research examines the effects of oxidization duration and temperature in dry air environment on the development of copper oxide nanowires in order to achieve cost effective controllable growth. Using the direct oxidation method in dry air we have demonstrated growth of CuO nano-wires at temperatures as low as 300 °C and as short as 1hr. Furthermore we have observed that the lengths and diameters of the CuO NWs can be controlled by the duration and temperature of the oxidation process. WY NASA Space Grant Consortium.

  13. Bond-length fluctuations in the copper oxide superconductors

    CERN Document Server

    Goodenough, J B

    2003-01-01

    Superconductivity in the copper oxides occurs at a crossover from localized to itinerant electronic behaviour, a transition that is first order. A spinodal phase segregation is normally accomplished by atomic diffusion; but where it occurs at too low a temperature for atomic diffusion, it may be realized by cooperative atomic displacements. Locally cooperative, fluctuating atomic displacements may stabilize a distinguishable phase lying between a localized-electron phase and a Fermi-liquid phase; this intermediate phase exhibits quantum-critical-point behaviour with strong electron-lattice interactions making charge transport vibronic. Ordering of the bond-length fluctuations at lower temperatures would normally stabilize a charge-density wave (CDW), which suppresses superconductivity. It is argued that in the copper oxide superconductors, crossover occurs at an optimal doping concentration for the formation of ordered two-electron/two-hole bosonic bags of spin S = 0 in a matrix of localized spins; the correl...

  14. Alumina and Silica Oxides as Catalysts for the Oxidation of Benzoins to Benzils under Solvent-free Conditions

    Directory of Open Access Journals (Sweden)

    A. H. Dabbagh

    2005-11-01

    Full Text Available Alumina or silica gel are used as catalysts for a solvent-free oxidation of benzoins to the corresponding benzils. These catalysts are easily recovered after completion of the reactions, which are carried out either by heating in a sand bath or using microwave irradiation. Comparison of the results obtained with both catalysts indicates that all the reactants examined were oxidized faster on alumina than on silica under these conditions.

  15. Novel vanadium phosphate phases as catalysts for selective oxidation

    Indian Academy of Sciences (India)

    Arunabha Datta; Monika Agarwal; Soumen Dasgupta

    2002-08-01

    In our effort to induce novel modifications in the structure of some important vanadium phosphate phases used as selective oxidation catalysts, it has been observed that metal ions such as Zn2+, Ni2+, Pd2+ can be incorporated into the vanadyl hydrogen phosphate VOHPO4$\\cdot$0.5H2O phase in very different ways depending upon the medium of preparation. It has been found that the metal ions are either substituted into the lattice with retention of structure of the parent compound or intercalated between the layers of a new mixed-valent phase. These new metalincorporated phases are catalytically active and the palladium incorporated compound in particular displays shape selective catalysis for different oxidation and reduction reactions. In another approach, the preparation of VOHPO4$\\cdot$0.5H2O has been modified to give a novel crystalline phase containing mixed-valent vanadium and having NH3 species bound to the lattice. This phase could be a potential catalyst for ammoxidation reactions. In addition, novel mesostructured vanadium phosphate phases have been prepared using a long-chain amine as the templating agent involving a ligand templating mechanism of formation.

  16. Roles of zinc and copper in modulating the oxidative refolding of bovine copper, zinc superoxide dismutase.

    Science.gov (United States)

    Li, Hong-Tao; Jiao, Ming; Chen, Jie; Liang, Yi

    2010-03-15

    The structural integrity of the ubiquitous enzyme copper, zinc superoxide dismutase (SOD1) depends critically on the correct coordination of zinc and copper. We investigate here the roles of the stoichiometric zinc and copper ions in modulating the oxidative refolding of reduced, denatured bovine erythrocyte SOD1 at physiological pH and room temperature. Fluorescence experiment results showed that the oxidative refolding of the demetalated SOD1 (apo-SOD1) is biphasic, and the addition of stoichiometric Zn(2+) into the refolding buffer remarkably accelerates both the fast phase and the slow phase of the oxidative refolding, compared with without Zn(2+). Aggregation of apo-SOD1 in the presence of stoichiometric Zn(2+) is remarkably slower than that in the absence of Zn(2+). In contrast, the effects of stoichiometric Cu(2+) on both the rates of the oxidative refolding and the aggregation of apo-SOD1 are not remarkable. Experiments of resistance to proteinase K showed that apo-SOD1 forms a conformation with low-level proteinase K resistance during refolding and stoichiometric Cu(2+) has no obvious effect on the resistance to proteinase K. In contrast, when the refolding buffer contains stoichiometric zinc, SOD1 forms a compact conformation with high-level proteinase K resistance during refolding. Our data here demonstrated that stoichiometric zinc plays an important role in the oxidative refolding of low micromolar bovine SOD1 by accelerating the oxidative refolding, suppressing the aggregation during refolding, and helping the protein to form a compact conformation with high protease resistance activity.

  17. Development of Nitric Oxide Oxidation Catalysts for the Fast SCR Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mark Crocker

    2005-09-30

    This study was undertaken in order to assess the potential for oxidizing NO to NO{sub 2} in flue gas environments, with the aim of promoting the so-called fast SCR reaction. In principle this can result in improved SCR kinetics and reduced SCR catalyst volumes. Prior to commencing experimental work, a literature study was undertaken to identify candidate catalysts for screening. Selection criteria comprised (1) proven (or likely) activity for NO oxidation, (2) low activity for SO2 oxidation (where data were available), and (3) inexpensive component materials. Catalysts identified included supported base metal oxides, supported and unsupported mixed metal oxides, and metal ion exchanged ZSM-5 (Fe, Co, Cu). For comparison purposes, several low loaded Pt catalysts (0.5 wt% Pt) were also included in the study. Screening experiments were conducted using a synthetic feed gas representative of flue gas from coal-fired utility boilers: [NO] = 250 ppm, [SO{sub 2}] = 0 or 2800 ppm, [H{sub 2}O] = 7%, [CO{sub 2}] = 12%, [O{sub 2}] = 3.5%, balance = N{sub 2}; T = 275-375 C. Studies conducted in the absence of SO{sub 2} revealed a number of supported and unsupported metal oxides to be extremely active for NO oxidation to NO{sub 2}. These included known catalysts (Co{sub 3}O{sub 4}/SiO{sub 2}, FeMnO{sub 3}, Cr{sub 2}O{sub 3}/TiO{sub 2}), as well as a new one identified in this work, CrFeO{sub x}/SiO{sub 2}. However, in the presence of SO{sub 2}, all the catalysts tested were found to be severely deactivated with respect to NO oxidation. Of these, Co{sub 3}O{sub 4}/SiO{sub 2}, Pt/ZSM-5 and Pt/CeO{sub 2} showed the highest activity for NO oxidation in the presence of SO{sub 2} (based on peak NO conversions to NO{sub 2}), although in no cases did the NO conversion exceed 7%. Reactor studies indicate there are two components to SO{sub 2}-induced deactivation of Co{sub 3}O{sub 4}/SiO{sub 2}, corresponding to an irreversible deactivation due to sulfation of the surface of the Co{sub 3

  18. Copper Oxide Nanoparticles Impact Several Toxicological Endpoints and Cause Neurodegeneration in Caenorhabditis elegans.

    Science.gov (United States)

    Mashock, Michael J; Zanon, Tyler; Kappell, Anthony D; Petrella, Lisa N; Andersen, Erik C; Hristova, Krassimira R

    2016-01-01

    Engineered nanoparticles are becoming increasingly incorporated into technology and consumer products. In 2014, over 300 tons of copper oxide nanoparticles were manufactured in the United States. The increased production of nanoparticles raises concerns regarding the potential introduction into the environment or human exposure. Copper oxide nanoparticles commonly release copper ions into solutions, which contribute to their toxicity. We quantified the inhibitory effects of both copper oxide nanoparticles and copper sulfate on C. elegans toxicological endpoints to elucidate their biological effects. Several toxicological endpoints were analyzed in C. elegans, including nematode reproduction, feeding behavior, and average body length. We examined three wild C. elegans isolates together with the Bristol N2 laboratory strain to explore the influence of different genotypic backgrounds on the physiological response to copper challenge. All strains exhibited greater sensitivity to copper oxide nanoparticles compared to copper sulfate, as indicated by reduction of average body length and feeding behavior. Reproduction was significantly reduced only at the highest copper dose, though still more pronounced with copper oxide nanoparticles compared to copper sulfate treatment. Furthermore, we investigated the effects of copper oxide nanoparticles and copper sulfate on neurons, cells with known vulnerability to heavy metal toxicity. Degeneration of dopaminergic neurons was observed in up to 10% of the population after copper oxide nanoparticle exposure. Additionally, mutants in the divalent-metal transporters, smf-1 or smf-2, showed increased tolerance to copper exposure, implicating both transporters in copper-induced neurodegeneration. These results highlight the complex nature of CuO nanoparticle toxicity, in which a nanoparticle-specific effect was observed in some traits (average body length, feeding behavior) and a copper ion specific effect was observed for other traits

  19. PREPARATION OF Au/SULFONATED POLYSTYRENE CATALYSTS FOR LOW-TEMPERATURE CO OXIDATION

    Institute of Scientific and Technical Information of China (English)

    Shi-hua Wu; Xiu-cheng Zheng; Wei-ping Huang; Shou-min Zhang; Wei Wei

    2001-01-01

    Supported Au catalysts for low-temperature CO oxidation were prepared by solvated metal atom impregnation (SMAI) and conventional impregnation (CI). X-ray photoelectron spectroscopy (XPS) investigations indicated that the elemental gold in all the samples was in the metallic state. XRD measurements showed that the mean diameters of Au particles prepared by SMAI were smaller than those prepared by CI with the same gold content. Catalytic tests showed that the SMAI catalyst had higher CO oxidation activity than the CI catalyst with the same compositions. Both SMAI and CI catalysts exhibited high activity in Iow temperature CO oxidation. Full CO conversion was obtained at 323-383K.``

  20. Catalytic wet air oxidation of aniline with nanocasted Mn-Ce-oxide catalyst.

    Science.gov (United States)

    Levi, R; Milman, M; Landau, M V; Brenner, A; Herskowitz, M

    2008-07-15

    The catalytic wet air oxidation of aqueous solution containing 1000 ppm aniline was conducted in a trickle-bed reactor packed with a novel nanocasted Mn-Ce-oxide catalyst (surface area of 300 m2/g) prepared using SBA-15 silica as a hard template. A range of liquid hourly space velocities (5-20 h(-1)) and temperatures (110-140 degrees C) at 10 bar of oxygen were tested. The experiments were conducted to provide the intrinsic performance of the catalysts. Complete aniline conversion, 90% TOC conversion, and 80% nitrogen mineralization were achieved at 140 degrees C and 5 h(-1). Blank experiments yielded relatively low homogeneous aniline (<35%) and negligible TOC conversions. Fast deactivation of the catalysts was experienced due to leaching caused by complexation with aniline. Acidification of the solution with HCI (molar HCI to aniline ratio of 1.2) was necessary to avoid colloidization and leaching of the nanoparticulate catalyst components. The catalyst displayed stable performance for over 200 h on stream.

  1. Size-Controlled Synthesis of Copper Oxide Particles on Reduced Graphene Oxide for Lithium-Ion Battery Anode Applications.

    Science.gov (United States)

    Jang, Haneul; Kim, Kyungbae; Chang, Hyejung; Kim, Jae-Hun; Choi, Hyunjoo

    2015-11-01

    Copper oxide/reduced graphene oxide (rGO) hybrids have been successfully synthesized by attaching copper ions onto the functional groups of GO by means of a solution process, which causes precipitation and agglomeration of copper oxides during subsequent thermal reduction of the GO. The resulting copper oxide/rGO hybrid exhibited improved electrochemical performance compared to monolithic CuO, which is presumed to be due to rGO acting as a mechanical support that buffers the volume change in copper oxides that occurs as a result of the conversion reaction during charge/discharge cycling. Furthermore, it was found that the size of the copper oxide particles can be optimized by adjusting the annealing time, with a hybrid annealed for 30 min achieving a reversible capacity of 544 mA h g(-1) and an initial coulombic efficiency of 62.7%.

  2. Catalytic partial oxidation of methane to synthesis gas over a ruthenium catalyst: the role of the oxidation state.

    Science.gov (United States)

    Rabe, Stefan; Nachtegaal, Maarten; Vogel, Frédéric

    2007-03-28

    The catalytic partial oxidation of methane to synthesis gas over ruthenium catalysts was investigated by thermogravimetry coupled with infrared spectroscopy (TGA-FTIR) and in situ X-ray absorption spectroscopy (XAS). It was found that the oxidation state of the catalyst influences the product formation. On oxidized ruthenium sites, carbon dioxide was formed. The reduced catalyst yielded carbon monoxide as a product. The influence of the temperature was also investigated. At temperatures below the ignition point of the reaction, the catalyst was in an oxidized state. At temperatures above the ignition point, the catalyst was reduced. This was also confirmed by the in situ XAS spectroscopy. The results indicate that both a direct reaction mechanism as well as a combustion-reforming mechanism can occur. The importance of knowing the oxidation state of the surface is discussed and a method to determine it under reaction conditions is presented.

  3. Influence of phosphorous addition on Bi3Mo2Fe1 oxide catalysts for the oxidative dehydrogenation of 1-butene

    KAUST Repository

    Park, Jung-Hyun

    2016-01-22

    Bi3Mo2Fe1Px oxide catalysts were prepared by a co-precipitation method and the influence of phosphorous content on the catalytic performance in the oxidative dehydrogenation of 1-butene was investigated. The addition of phosphorous up to 0.4mole ratio to Bi3Mo2Fe1 oxide catalyst led to an increase in the catalytic performance; however, a higher phosphorous content (above P=0.4) led to a decrease of conversion. Of the tested catalysts, Bi3Mo2Fe1P0.4 oxide catalyst exhibited the highest catalytic performance. Characterization results showed that the catalytic performance was related to the quantity of a π-allylic intermediate, facile desorption behavior of adsorbed intermediates and ability for re-oxidation of catalysts. © 2015 Korean Institute of Chemical Engineers, Seoul, Korea

  4. Noble Metal Catalysts for Mercury Oxidation in Utility Flue Gas: Gold, Palladium and Platinum Formulations

    Energy Technology Data Exchange (ETDEWEB)

    Presto, A.A.; Granite, E.J

    2008-07-01

    The use of noble metals as catalysts for mercury oxidation in flue gas remains an area of active study. To date, field studies have focused on gold and palladium catalysts installed at pilot scale. In this article, we introduce bench-scale experimental results for gold, palladium and platinum catalysts tested in realistic simulated flue gas. Our initial results reveal some intriguing characteristics of catalytic mercury oxidation and provide insight for future research into this potentially important process.

  5. Chitosan-based Schiff base-metal complexes (Mn, Cu, Co) as heterogeneous, new catalysts for the -isophorone oxidation

    Indian Academy of Sciences (India)

    C S Thatte; M V Rathnam; A C Pise

    2014-05-01

    A new chitosan-based Schiff base was prepared and complexed with manganese, cobalt and copper. These Schiff base metal complexes were used as heterogeneous catalysts for the air oxidation of -isophorone to ketoisophorone. The obtained complexes were characterized by means of FT-IR, 1HNMR spectroscopy, elemental analysis, powder X-ray diffraction, field emission gun scanning electron microscopy, electron spin resonance spectroscopy, ICP-AES and solubility tests. Thermal properties were also investigated using thermal gravimetric analysis. Data obtained by thermal analysis revealed that these complexes showed good thermal stability. The conversion and selectivity of -isophorone to ketoisophorone for each prepared catalyst was studied using a batch reactor and gas chromatography for product identification and quantification. The results were compared against the homogeneous bis-salicylaldehyde ethylenedi-imine-Mn catalyst. The use of methanol, acetone, methyl isobutyl ketone and -hexane as solvent and its effect on conversion and selectivity was also investigated. Acetone was found to be a promising solvent for the -isophorone oxidation. The role of triethyl amine and acetyl acetone in the oxidation reaction has also been investigated.

  6. Unravelling the properties of supported copper oxide: can the particle size induce acidic behaviour?

    Science.gov (United States)

    Zaccheria, Federica; Scotti, Nicola; Marelli, Marcello; Psaro, Rinaldo; Ravasio, Nicoletta

    2013-02-07

    There is a renewed interest in designing solid acid catalysts particularly due to the significance of Lewis acid catalyzed processes such as Friedel-Crafts acylation and alkylation and cellulose hydrolysis for the development of sustainable chemistry. This paper reports a new focus point on the properties of supported CuO on silica, a material that up to now has been considered only as the precursor of an effective hydrogenation catalyst. Thus, it deals with a re-interpretation of some of our results with supported copper oxide aimed to unveil the root of acidic activity exhibited by this material, e.g. in alcoholysis reactions. Several techniques were used to highlight the very high dispersion of the oxide phase on the support allowing us to ascribe the acidic behavior to coordinative unsaturation of the very small CuO particles. In turn this unsaturation makes the CuO particles prone to coordinate surrounding molecules present in the reaction mixture and to exchange them according to their nucleophilicity.

  7. Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature.

    Science.gov (United States)

    Narsimhan, Karthik; Iyoki, Kenta; Dinh, Kimberly; Román-Leshkov, Yuriy

    2016-06-22

    The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C-H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483-498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions.

  8. Inorganic compounds and materials as catalysts for oxidations with aqueous hydrogen peroxide

    NARCIS (Netherlands)

    Nardello, veronique; Aubry, Jean-Marie; De Vos, Dirk E.; Neumann, Ronny; Adam, Waldemar; Zhang, Rui; ten Elshof, Johan E.; Witte, Peter T.; Alsters, Paul L.

    2006-01-01

    This paper reviews our work on oxidations with aqueous hydrogen peroxide catalyzed by inorganic catalysts devoid of organic ligands. In the first part of the review, the use of the [WZn3(ZnW9O34)2]12− “sandwich” polyoxometalate as a multi-purpose oxidation catalyst is described. Attention is paid to

  9. Inorganic compounds and materials as catalysts for oxidations with aqueous hydrogen peroxide

    NARCIS (Netherlands)

    Nardello, veronique; Aubry, Jean-Marie; Vos, De Dirk E.; Neumann, Ronny; Adam, Waldemar; Zhang, Rui; Elshof, ten Johan E.; Witte, Peter T.; Alsters, Paul L.

    2006-01-01

    This paper reviews our work on oxidations with aqueous hydrogen peroxide catalyzed by inorganic catalysts devoid of organic ligands. In the first part of the review, the use of the [WZn3(ZnW9O34)2]12− “sandwich” polyoxometalate as a multi-purpose oxidation catalyst is described. Attention is paid to

  10. Chemoselective Oxidation of Bio-Glycerol with Nano-Sized Metal Catalysts

    DEFF Research Database (Denmark)

    Li, Hu; Kotni, Ramakrishna; Zhang, Qiuyun

    2015-01-01

    to selectively oxidize glycerol and yield products with good selectivity is the use of nano-sized metal particles as heterogeneous catalysts. In this short review, recent developments in chemoselective oxidation of glycerol to specific products over nano-sized metal catalysts are described. Attention is drawn...

  11. Photocatalytic polyoxometalate compositions of tungstovanadates and uses as water oxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Hill, Craig L.; Gueletii, Iourii V.; Song, Jie; Lv, Hongjin; Musaev, Djamaladdin; Luo, Zhen

    2017-08-22

    This disclosure relates to photocatalytic polyoxometalate compositions of tungstovanadates and uses as water oxidation catalysts. In certain embodiments, the disclosure relates to compositions comprising water, a complex of a tetra-metal oxide cluster and VW.sub.9O.sub.34 ligands, and a photosensitizer. Typically, the metal oxide cluster is Co. In certain embodiments, the disclosure relates to electrodes and other devices comprising water oxidation catalysts disclosed herein and uses in generating fuels and electrical power from solar energy.

  12. Reduction and re-oxidation of Cu/Al{sub 2}O{sub 3} catalysts investigated with quick-scanning XANES and EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Stoetzel, J; Luetzenkirchen-Hecht, D; Frahm, R [Department of Physics, University of Wuppertal, Gaussstr. 20, D-42097 Wuppertal (Germany); Kimmerle, B; Baiker, A [Department of Chemistry and Applied Biosciences, ETH Zuerich, CH-8093 Zuerich (Switzerland); Nachtegaal, M [Paul Scherrer Institut, CH-5232 Villigen (Switzerland); Beier, M J; Grunwaldt, J-D, E-mail: j.stoetzel@uni-wuppertal.d, E-mail: jdg@kt.dtu.d [Department of Chemical and Biochemical Engineering, Technical University of Denmark, Building 229, DK-2800 Kgs. Lyngby (Denmark)

    2009-11-15

    In the present study the structure of copper catalysts on alumina support were investigated in situ and time resolved during reduction and re-oxidation at different temperatures with the quick-scanning EXAFS (QEXAFS) technique. Different impregnation times (2 min and 90 min) were chosen for the preparation which resulted in different copper species that show a strong variation in the reduction/re-oxidation behaviour. These dynamic changes as well as possible intermediate phases during the gas atmospheres changes were followed with up to 20 EXAFS spectra per second at the copper K-edge covering an energy range of 450 eV. The high time resolution provided new insights into the dynamics of the catalysts e.g. revealing Cu(I) as intermediate state during re-oxidation. Latest advances in the data acquisition hardware are leading to an improved data quality of spectra collected at the SuperXAS beamline. Thus, not only accurate analysis of the catalysts via XANES but also by EXAFS was possible. This is also due to the recent upgrade to monitor the Bragg angle directly with an encoder during the experiments.

  13. Stepwise mechanism of oxidative ammonolysis of propane to acrylonitrile over gallium-antimony oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Osipova, Z.G.; Sokolovskii, V.D.

    1979-03-01

    The stepwise mechanism of oxidative ammonolysis of propane to acrylonitrile over gallium-antimony oxide catalysts GaSb/sub 19/O/sub x/, GaSb/sub 3/Ni/sub 1.5/0/sub x/, and GaSb/sub 2.5/Ni/sub 1.5/PW/sub 0//sub 0.25/O/sub x/ was studied at 450/sup 0/ and 550/sup 0/C by introducing alternating pulses of 0.5Vertical Bar3< propane/0.6Vertical Bar3< ammonia/helium (to reduce the steady-state catalytic surface) and 0.5Vertical Bar3< propane/0.6Vertical Bar3< ammonia/1.86Vertical Bar3< oxygen/helium mixtures into a fluidized-bed catalytic reactor. Over all the catalysts studied, the rates of acrylonitrile formation during the two types of pulses were very similar, but carbon dioxide was formed much faster during the reducing pulses, particularly at 450/sup 0/C. These findings suggested that acrylonitrile is formed by a stepwise redox mechanism involving consecutive interaction of propane and ammonia with the surface oxygen of the catalysts and oxidation of the reduced catalyst surface by gas-phase oxygen. The formation of carbon dioxide proceeds by both stepwise and associative mechanisms, the latter being more important at higher temperatures. The results are similar to published results for ammoxidation of propylene and olefins.

  14. Graphene oxide as an effective catalyst for wet air oxidation of phenol.

    Science.gov (United States)

    Yang, Shaoxia; Cui, Yuhong; Sun, Yu; Yang, Hongwei

    2014-09-15

    The graphene oxide (GO) and chemically reduced graphene oxides, used as catalysts in absence of any metals, were investigated in the catalytic wet air oxidation (CWAO) of phenol in a batch reactor. The characterization of the materials was measured with scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman, fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The carbon materials exhibited good phenol and total organic compounds (TOC) removals in the CWAO of phenol. The GO had the highest catalytic activity, total phenol removal was achieved after 40 min, and ca. 84% TOC removal was obtained after 120 min at reaction temperature of 155°C, total pressure of 2.5 MPa and catalyst loading of 0.2 gL(-1).

  15. Catalytic oxidation of n-hexane promoted by Ce{sub 1−x}Cu{sub x}O{sub 2} catalysts prepared by one-step polymeric precursor method

    Energy Technology Data Exchange (ETDEWEB)

    Araújo, Vinícius D., E-mail: dantas@ursa.ifsc.usp.br [Instituto de Física, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Lima, Maurício M. de [Instituto de Ciencia de los Materiales, Universidad de Valencia, E-46071 Valencia (Spain); Fundación General, Universitat de Valencia, Valencia (Spain); Cantarero, Andrés [Instituto de Ciencia de los Materiales, Universidad de Valencia, E-46071 Valencia (Spain); Bernardi, Maria I.B. [Instituto de Física, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Bellido, Jorge D.A. [CAP-Engenharia Química, Universidade Federal de São João Del-Rei – UFSJ, São João Del-Rei, MG (Brazil); Assaf, Elisabete M. [Instituto de Química, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Balzer, Rosana; Probst, Luiz F.D. [Departamento de Química, Universidade Federal de Santa Catarina – UFSC, 88040-900 Florianópolis, SC (Brazil); Fajardo, Humberto V. [Departamento de Química, Universidade Federal de Ouro Preto – UFOP, 35400-000 Ouro Preto, MG (Brazil)

    2013-11-01

    Ceria-supported copper catalysts (Ce{sub 1−x}Cu{sub x}O{sub 2}, with x (mol) = 0, 0.01, 0.03, 0.05 and 0.10) were prepared in one step through the polymeric precursor method. The textural properties of the catalysts were investigated by X-ray diffraction (XRD), Rietveld refinement, N{sub 2}-physisorption (BET surface area), electron paramagnetic resonance (EPR), UV–visible diffuse reflectance and photoluminescence spectroscopies and temperature-programmed reduction (TPR). In a previous study ceria-supported copper catalysts were found to be efficient in the preferential oxidation of CO. In this study, we extended the catalytic application of Ce{sub 1−x}Cu{sub x}O{sub 2} systems to n-hexane oxidation and it was verified that the catalysts were highly efficient in the proposed reaction. The best performance (up to 95% conversion) was observed for the catalysts with low copper loads (Ce{sub 0.97}Cu{sub 0.03}O{sub 2} and Ce{sub 0.99}Cu{sub 0.01}O{sub 2}, respectively). The physicochemical characterizations revealed that these behaviors could be attributed to the copper species present in the catalysts and the interaction between CuO and CeO{sub 2}, which vary according to the copper content. - Highlights: • Synthesis of CuO/CeO2 catalysts by the one-step polymeric precursor method. • 95% n-hexane conversion on Ce0.97Cu0.03O2 catalyst. • Redox properties play a key role in the catalytic performance.

  16. The selective oxidation of ammonia over alumina supported catalysts. Experiments and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Jones, J.M.; Pourkashanian, M.; Williams, A.; Backreedy, R.I.; Darvell, L.I. [Energy and Resources Research Institute, School of Process Environmental and Materials Engineering, University of Leeds, Leeds LS29JT (United Kingdom); Simell, P.; Heiskanen, K. [VTT Processes, P.O. Box 1601, FIN-02044 VTT (Finland); Kilpinen, P. [AAbo Akademi Process Chemistry Centre, Laboratory for Industrial Chemistry, Turku (Finland)

    2005-09-01

    Hot gas-clean up will improve the efficiency of emerging gasification technologies. Selective catalytic oxidation (SCO) of ammonia is a promising approach for dealing with the main fixed nitrogen species. The work presented here comprises both laboratory scale experimental measurements of potential SCO catalysts, as well as the development of a simple four-step reaction model to describe the behaviour of one of the more promising catalysts. A range of transition metal oxides supported on {gamma}-alumina were studied for their activity in the SCO of ammonia in a simulated gasification gas mixture containing CO, H{sub 2}O, H{sub 2}, CO{sub 2}, CH{sub 4}, H{sub 2}S and toluene as model tar species. Both copper and chromium based catalysts demonstrated a window of operating temperature over which they were resistant to poisoning by H{sub 2}S; Cu/Al{sub 2}O{sub 3} was in fact promoted by this gas for the SCO reaction. The ammonia conversion over 7% Cu/Al{sub 2}O{sub 3} was studied in more detail, and this data was further used to develop a kinetic model for the reactions taking place over the temperature range 723-906K. Excellent conversion and selectivity to N{sub 2} was found in the temperature window 973-1173K and 2.6vol% O{sub 2}. However, it also catalyses a rapid H{sub 2}-O{sub 2} reaction. This reaction consumes all remaining available oxygen so that no other oxidation reactions take place (e.g. of methane or 'tar'). The four-step reaction model was developed using the PLUG application of Chemkin and Surface Chemkin software coupled with the gas-phase mechanism. Rates for the heterogeneous oxidation of ammonia and hydrogen are included as well as forward and reverse reactions of the water gas shift. Over the temperature range in question, the surface reaction rates are much faster than the gas-phase reactions. The model is applicable for the 723-906K temperature range using a gas mixture containing 0.4vol% ammonia and 0.01vol% H{sub 2}S in the presence

  17. Electro-oxidation of ethanol on ternary non-alloyed Pt-Sn-Pr/C catalysts

    Science.gov (United States)

    Corradini, Patricia G.; Antolini, Ermete; Perez, Joelma

    2015-02-01

    Ternary Pt-Sn-Pr/C (70:10:20), (70:15:15) and (45:45:10) electro-catalysts were prepared by a modified formic acid method, and their activity for the ethanol oxidation reaction (EOR) was compared with that of Pt-Pr/C catalysts prepared by the same methods and that of commercial Pt-Sn/C (75:25) and Pt/C catalysts. Among all the catalysts, the Pt-Sn-Pr/C (45:45:10) catalyst presented both the highest mass activity and the highest specific activity. The steady state electrochemical stability of ternary Pt-Sn-Pr catalysts increased with the surface Sn/Pt atomic ratio. Following repetitive potential cycling (RPC), the activity for ethanol oxidation of Pt-Sn-Pr/C catalysts with high surface Sn/Pt atomic ratio was considerably higher than that of the corresponding as-prepared catalysts, and increased with increasing the Sn/Pt ratio. The increase of the EOR mass activity following RPC was ascribed to the increase of either the specific activity (for the Pt-Sn-Pr/C (70:15:15) catalyst) or the electrochemically active surface area (for the Pt-Sn-Pr/C (45:45:10) catalyst). Dissolution of Sn and Pr oxides from Pt-Sn-Pr/C catalyst surface was observed following RPC.

  18. Oxidative dehydrogenation of ethane to ethylene using vanadia based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Qiao, Ailing; Kalevaru, V.N. [Univ. Rostock e.V., Rostock (Germany). Leibniz-Inst. fuer Katalyse; Humar, A.S.; Lingaiah, N.; Sai Prasad, P.S.; Martin, A. [Indian Institute of Chemical Technology, Hyderabad (India). Inorganic and Physical Chemistry Div.

    2011-07-01

    In this work, we describe the application of V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} catalysts for the oxidative dehydrogenation (ODH) of ethane to ethylene. A series of Nb{sub 2}O{sub 5} supported V{sub 2}O{sub 5} catalysts were prepared by impregnation technique. NH{sub 4}VO{sub 3} was used as a precursor for V{sub 2}O{sub 5}. The content of V{sub 2}O{sub 5} is varied in the range from 5 to 20 wt%. Catalytic tests were carried out in a fixed bed quartz reactor in the temperature range from 500 to 600 C. The conversion of ethane has been increased from ca. 20 to 35 % with increase in temperature from 500 to 600 C, while the yield of ethylene is increased from about 5 to 12 % only. CO and CO{sub 2} are the only major by-products of the reaction. The activity tests were performed at low O{sub 2} concentration in the feed and hence low conversions were achieved. Furthermore, the conversion of ethane is found to increase continuously with increase in V{sub 2}O{sub 5} loading while the yield of C{sub 2}H{sub 4} increased only up to 10wt% V{sub 2}O{sub 5} and then decreased. Results revealed that the catalytic activity and selectivity is found to depend on the V{sub 2}O{sub 5} loading. Among all, 10wt% V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} catalyst has displayed the superior performance. (orig.)

  19. Oxidative dehydrogenation of ethane to ethylene using vanadia based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Qiao, Ailing; Kalevaru, V.N. [Univ. Rostock e.V., Rostock (Germany). Leibniz-Inst. fuer Katalyse; Humar, A.S.; Lingaiah, N.; Sai Prasad, P.S.; Martin, A. [Indian Institute of Chemical Technology, Hyderabad (India). Inorganic and Physical Chemistry Div.

    2011-07-01

    In this work, we describe the application of V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} catalysts for the oxidative dehydrogenation (ODH) of ethane to ethylene. A series of Nb{sub 2}O{sub 5} supported V{sub 2}O{sub 5} catalysts were prepared by impregnation technique. NH{sub 4}VO{sub 3} was used as a precursor for V{sub 2}O{sub 5}. The content of V{sub 2}O{sub 5} is varied in the range from 5 to 20 wt%. Catalytic tests were carried out in a fixed bed quartz reactor in the temperature range from 500 to 600 C. The conversion of ethane has been increased from ca. 20 to 35 % with increase in temperature from 500 to 600 C, while the yield of ethylene is increased from about 5 to 12 % only. CO and CO{sub 2} are the only major by-products of the reaction. The activity tests were performed at low O{sub 2} concentration in the feed and hence low conversions were achieved. Furthermore, the conversion of ethane is found to increase continuously with increase in V{sub 2}O{sub 5} loading while the yield of C{sub 2}H{sub 4} increased only up to 10wt% V{sub 2}O{sub 5} and then decreased. Results revealed that the catalytic activity and selectivity is found to depend on the V{sub 2}O{sub 5} loading. Among all, 10wt% V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} catalyst has displayed the superior performance. (orig.)

  20. Enhancing the stability of copper chromite catalysts for the selective hydrogenation of furfural with ALD overcoating (II) – Comparison between TiO2 and Al2O3 overcoatings

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hongbo; Canlas, Christian; Kropf, A. Jeremy; Elam, Jeffrey W.; Dumesic, James A; Marshall, Christopher L.

    2015-01-01

    TiO2 atomic layer deposition (ALD) overcoatings were applied to copper chromite catalysts to increase the stability for 2-furfuraldehyde (“furfural”) hydrogenation. After overcoating, about 75% activity was preserved compared to neat copper chromite: much higher activity than an alumina ALD overcoated catalyst with a similar number of ALD cycles. The effects of ALD TiO2 on the active Cu nanoparticles were studied extensively using both in-situ TPR/isothermal-oxidation and in-situ furfural hydrogenation via Cu XAFS. The redox properties of Cu were modified only slightly by the TiO2 ALD overcoat. However, a subtle electronic interaction was observed between the TiO2 ALD layers and the Cu nanoparticles. With calcination at 500 °C the interaction between the TiO2 overcoat and the underlying catalyst is strong enough to inhibit migration and site blocking by chromite, but is sufficiently weaker than the interaction between the Al2O3 overcoat and copper chromite that it does not strongly inhibit the catalytic activity of the copper nanoparticles.

  1. Mo-V-Te-Nb oxides as catalysts for ethene production by oxidative dehydrogenation of ethane

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, D. [Technische Universitaet Muenchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center; Meiswinkel, A.; Thaller, C.; Bock, M.; Alvarado, L. [Linde AG, Pullach (Germany)

    2013-11-01

    The availability of ethane in shale gas, as well as the interest in valorising previously underutilized carbon feedstocks, makes the oxidative dehydrogenation (ODH) of ethane an attractive alternative to the industrially established processes for production of ethylene. Mo-V-Te-Nb mixed oxide has been chosen as catalyst for the ODH reaction in view of its outstanding ability to activate alkane molecules. Catalytic test results showed that this type of catalyst can selectively oxidize ethane to ethene at moderate temperatures (350-400 C) with minor production of CO{sub x}. The catalytic performance of Mo-V-Te-Nb mixed-oxide is mainly attributable to the crystalline phase 'M1'. Rietveld analysis of the X-Ray diffractograms allowed us to quantify the amount of MoVTeNb oxide that has crystallized as M1. In this way, it was possible to find a linear correlation of the reaction rate with the abundance of M1 in the solid. Therefore, it is clear that for improving the efficiency of MoVTeNb oxide in ODH, the amount of M1 in the catalyst should be maximized. With this purpose, several MoVTeNb oxides were subject to different thermal treatments prior to the catalytic test. Structural changes in the catalyst were monitored by in-situ XRD technique. Under oxidative atmosphere, it was observed a recrystallization of M2 and possibly, amorphous oxide, into M1 phase, leading to correspondingly more active and selective catalysts (selectivities above 95 % for ethane conversions up to 40 % under industrially relevant conditions). The active site of M1 involves V species, likely with redox properties enhanced by the proximity of Mo and Te species, while the function of the crystalline structure itself is to provide the spatial configuration that allows interaction between these species. However, ethene formation rate was observed to be independent of the V content of the samples. The vanadium species exposed at the surface were studied by LEIS and by IR spectroscopy of CO

  2. High performance Pd-based catalysts for oxidation of formic acid

    Science.gov (United States)

    Wang, Rongfang; Liao, Shijun; Ji, Shan

    Two novel catalysts for anode oxidation of formic acid, Pd 2Co/C and Pd 4Co 2Ir/C, were prepared by an organic colloid method with sodium citrate as a complexing agent. These two catalysts showed better performance towards the anodic oxidation of formic acid than Pd/C catalyst and commercial Pt/C catalyst. Compared with Pd/C catalyst, potentials of the anodic peak of formic acid at the Pd 2Co/C and Pd 4Co 2Ir/C catalyst electrodes shifted towards negative value by 140 and 50 mV, respectively, meanwhile showed higher current densities. At potential of 0.05 V (vs. SCE), the current density for Pd 4Co 2Ir/C catalyst is as high as up to 13.7 mA cm -2, which is twice of that for Pd/C catalyst, and six times of that for commercial Pt/C catalyst. The alloy catalysts were nanostructured with a diameter of ca. 3-5 nm and well dispersed on carbon according to X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements. The composition of alloy catalysts was analyzed by energy dispersive X-ray analysis (EDX). Pd 4Co 2Ir/C catalyst showed the highest activity and best stability making it the best potential candidate for application in a direct formic acid fuel cell (DFAFC).

  3. Evaluation of copper slag to catalyze advanced oxidation processes for the removal of phenol in water

    Energy Technology Data Exchange (ETDEWEB)

    Huanosta-Gutierrez, T. [Instituto de Ingenieria, Coordinacion de Ingenieria Ambiental, Universidad Nacional Autonoma de Mexico, Cd. Universitaria, Coyoacan 04510, Mexico, D.F. (Mexico); Dantas, Renato F., E-mail: falcao@angel.qui.ub.es [Departament d' Enginyeria Quimica, Universitat de Barcelona, Marti i Franques 1, 08028 Barcelona (Spain); Ramirez-Zamora, R.M. [Instituto de Ingenieria, Coordinacion de Ingenieria Ambiental, Universidad Nacional Autonoma de Mexico, Cd. Universitaria, Coyoacan 04510, Mexico, D.F. (Mexico); Esplugas, S. [Departament d' Enginyeria Quimica, Universitat de Barcelona, Marti i Franques 1, 08028 Barcelona (Spain)

    2012-04-30

    Highlights: Black-Right-Pointing-Pointer We evaluate the use of an industrial residue (copper slag) as catalyst in water treatment. Black-Right-Pointing-Pointer The copper slag was effective to remove organic pollutants (phenol) from water. Black-Right-Pointing-Pointer During experimentation, Cu and Fe leaching were not higher than the acceptable levels. Black-Right-Pointing-Pointer Slag/H{sub 2}O{sub 2}/UV and slag/H{sub 2}O{sub 2} treatments promoted biodegradability increment of the contaminated water. Black-Right-Pointing-Pointer The control of the reaction time would minimize the environmental impact of the produced effluents in terms of acute toxicity. - Abstract: The aim of this work was to evaluate the use of copper slag to catalyze phenol degradation in water by advanced oxidation processes (AOPs). Copper slag was tested in combination with H{sub 2}O{sub 2} (slag/H{sub 2}O{sub 2}) and H{sub 2}O{sub 2}/UV (slag/H{sub 2}O{sub 2}/UV). The studied methods promoted the complete photocatalytic degradation of phenol. Besides, they were able to reduce about 50% the TOC content in the samples. Slag/H{sub 2}O{sub 2}/UV and slag/H{sub 2}O{sub 2} treatments have favored biodegradability increment along the reaction time. Nevertheless, the irradiated method achieved higher values of the biodegradability indicator (BOD{sub 5}/TOC). The toxicity assessment indicated the formation of more toxic compounds in both treatments. However, the control of the reaction time would minimize the environmental impact of the effluents.

  4. Oxidative Coupling of Methane over Li/MgO: Catalyst and Nanocatalyst Performance

    Science.gov (United States)

    Farsi, Ali; Moradi, Ali; Ghader, Sattar; Shadravan, Vahid

    2011-02-01

    The Li/MgO catalyst and nanocatalyst were prepared by the incipient wetness impregnation and sol-gel method, respectively. The catalytic performance of the Li/MgO catalyst and nanocatalyst on oxidative coupling of methane was compared. The catalysts prepared in two ways were characterized by X-ray powder diffraction, Brunauer-Emmett-Teller surface and transmission electron microscope. The catalyst was tested at temperature of 973-1073 K with constant total pressure of 101 kPa. Experimental results showed that Li/MgO nanocatalyst in the oxidative coupling of methane would result in higher conversion of methane, higher selectivity, and higher yield of main products (ethane and ethylene) compared to ordinary catalyst. The results show the improved influence of nanoscale Li/MgO catalyst performance on oxidative coupling of methane.

  5. Quantum magnetic excitations from stripes in copper oxide superconductors.

    Science.gov (United States)

    Tranquada, J M; Woo, H; Perring, T G; Goka, H; Gu, G D; Xu, G; Fujita, M; Yamada, K

    2004-06-03

    In the copper oxide parent compounds of the high-transition-temperature superconductors the valence electrons are localized--one per copper site--by strong intra-atomic Coulomb repulsion. A symptom of this localization is antiferromagnetism, where the spins of localized electrons alternate between up and down. Superconductivity appears when mobile 'holes' are doped into this insulating state, and it coexists with antiferromagnetic fluctuations. In one approach to describing the coexistence, the holes are believed to self-organize into 'stripes' that alternate with antiferromagnetic (insulating) regions within copper oxide planes, which would necessitate an unconventional mechanism of superconductivity. There is an apparent problem with this picture, however: measurements of magnetic excitations in superconducting YBa2Cu3O6+x near optimum doping are incompatible with the naive expectations for a material with stripes. Here we report neutron scattering measurements on stripe-ordered La1.875Ba0.125CuO4. We show that the measured excitations are, surprisingly, quite similar to those in YBa2Cu3O6+x (refs 9, 10) (that is, the predicted spectrum of magnetic excitations is wrong). We find instead that the observed spectrum can be understood within a stripe model by taking account of quantum excitations. Our results support the concept that stripe correlations are essential to high-transition-temperature superconductivity.

  6. Quantum magnetic excitations from stripes in copper oxide superconductors

    Science.gov (United States)

    Tranquada, J. M.; Woo, H.; Perring, T. G.; Goka, H.; Gu, G. D.; Xu, G.; Fujita, M.; Yamada, K.

    2004-06-01

    In the copper oxide parent compounds of the high-transition-temperature superconductors the valence electrons are localized-one per copper site-by strong intra-atomic Coulomb repulsion. A symptom of this localization is antiferromagnetism, where the spins of localized electrons alternate between up and down. Superconductivity appears when mobile `holes' are doped into this insulating state, and it coexists with antiferromagnetic fluctuations. In one approach to describing the coexistence, the holes are believed to self-organize into `stripes' that alternate with antiferromagnetic (insulating) regions within copper oxide planes, which would necessitate an unconventional mechanism of superconductivity. There is an apparent problem with this picture, however: measurements of magnetic excitations in superconducting YBa2Cu3O6+x near optimum doping are incompatible with the naive expectations for a material with stripes. Here we report neutron scattering measurements on stripe-ordered La1.875Ba0.125CuO4. We show that the measured excitations are, surprisingly, quite similar to those in YBa2Cu3O6+x (refs 9, 10) (that is, the predicted spectrum of magnetic excitations is wrong). We find instead that the observed spectrum can be understood within a stripe model by taking account of quantum excitations. Our results support the concept that stripe correlations are essential to high-transition-temperature superconductivity.

  7. NANOSTRUCTURED METAL OXIDE CATALYSTS VIA BUILDING BLOCK SYNTHESES

    Energy Technology Data Exchange (ETDEWEB)

    Craig E. Barnes

    2013-03-05

    A broadly applicable methodology has been developed to prepare new single site catalysts on silica supports. This methodology requires of three critical components: a rigid building block that will be the main structural and compositional component of the support matrix; a family of linking reagents that will be used to insert active metals into the matrix as well as cross link building blocks into a three dimensional matrix; and a clean coupling reaction that will connect building blocks and linking agents together in a controlled fashion. The final piece of conceptual strategy at the center of this methodology involves dosing the building block with known amounts of linking agents so that the targeted connectivity of a linking center to surrounding building blocks is obtained. Achieving targeted connectivities around catalytically active metals in these building block matrices is a critical element of the strategy by which single site catalysts are obtained. This methodology has been demonstrated with a model system involving only silicon and then with two metal-containing systems (titanium and vanadium). The effect that connectivity has on the reactivity of atomically dispersed titanium sites in silica building block matrices has been investigated in the selective oxidation of phenols to benezoquinones. 2-connected titanium sites are found to be five times as active (i.e. initial turnover frequencies) than 4-connected titanium sites (i.e. framework titanium sites).

  8. Multiphase enantioselective Kharasch-Sosnovsky allylic oxidation based on neoteric solvents and copper complexes of ditopic ligands.

    Science.gov (United States)

    Aldea, Luis; García, José I; Mayoral, José A

    2012-07-21

    Recoverable multiphase enantioselective catalytic systems for the Kharasch-Sosnovsky oxidation of cycloalkenes with tert-butyl peroxybenzoate are described, based on the use of [BMIM][PF(6)] and a new solvent derived from glycerol as the catalyst reservoir phases, and chiral copper complexes with different ligands from the bis(oxazoline) family. The best results are obtained with the glycerol-derived solvent and a recently described azabisoxazoline-based ditopic ligand, allowing up to four uses of the catalytic phase with good results.

  9. Effective phototransformation in a heterostructure based on copper(I) oxide and cadmium tin oxide

    Science.gov (United States)

    Shelovanova, G. N.; Patrusheva, T. N.

    2017-02-01

    We present a heterostructure consisting of anodic copper oxide Cu2O on a copper substrate and a transparent Cd-Sn-O conducting film for use in solar cells. Focusing on simplicity and the availability of film fabrication techniques, we chose anodic oxidation for forming the Cu2O film and the extraction-pyrolysis technique for forming the transparent Cd-Sn-O conducting layer. We demonstrate the possibility of considerable enhancement of the phototransformation efficiency in the Cu-Cu2O/Cd-Sn-O structure over this parameter in the Cu-Cu2O structure.

  10. Properties of Copper Doped Neodymium Nickelate Oxide as Cathode Material for Solid Oxide Fuel Cells

    OpenAIRE

    Lee Kyoung-Jin; Choe Yeong-Ju; Hwang Hae-Jin

    2016-01-01

    Mixed ionic and electronic conducting K2NiF4-type oxide, Nd2Ni1-xCuxO4+δ (x=0~1) powders were synthesized by solid state reaction technique and solid oxide fuel cells consisting of a Nd2Ni1-xCuxO4+δ cathode, a Ni-YSZ anode and ScSZ as an electrolyte were fabricated. The effect of copper substitution for nickel on the electrical and electrochemical properties was examined. Small amount of copper doping (x=0.2) resulted in the increased electrical conductivity and decreased polarization resista...

  11. Extraordinary Spin-Wave Thermal Conductivity in Low-Dimensional Copper Oxides

    Science.gov (United States)

    2015-01-23

    Low-Dimensional Copper Oxides Sb. GRANT NUMBER Sc. PROGRAM ELEMENT NUMBER 611102 6. AUTHORS Sd. PROJECT NUMBER David Cahill Se. TASK NUMBER Sf...TDTR) to advance understanding of the1mal transp01i in low dimensional copper - oxides that display extraordina1y thennal transp01i by the1mal...by ANSI Std. Z39.18 ABSTRACT Final Report: Extraoridinary Spin-Wave Thermal Conductivity in Low-Dimensional Copper Oxides Report Title We applied

  12. Role of vanadium in Keggin heteropoly molybdate supported on titania catalysts for oxidation reactions

    Indian Academy of Sciences (India)

    A Srivani; K T Venkateswara Rao; P S Sai Prasad; N Lingaiah

    2014-03-01

    Vanadium-incorporated molybdophosporic acid catalysts supported on titania were prepared and characterized by FT-IR, X-ray diffraction and laser Raman spectroscopy. Characterization data reveals the incorporation of vanadium into the primary structure of Keggin ion of MPA. Catalysts activities were evaluated for oxidation of 1,2-benzenedimethanol using H2O2 and O2 as oxidants. Vanadium-containing catalysts showed high activity compared to their parent heteropoly acids. Oxidation ability depended on the number of V atoms present in Keggin heteropoly molybdate. Effect of reaction parameters on the oxidation ability was also evaluated.

  13. Partial oxidation of n- and i-pentane over promoted vanadium-phosphorus oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zazhigalov, V.A.; Mikhajluk, B.D.; Komashko, G.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

    1998-12-31

    It is known, that the cost of raw materials for catalytic oxidation processes is about 60% of the product price. Cheap initial compounds to produce variety of products and to replace olefins and aromatic hydrocarbons are paraffins. That is why catalytic systems which could be possibly rather efficient in selective oxidation of paraffin hydrocarbons are under very close investigation now. One of such processes in n-pentane oxidation. The obtained results on n-pentane oxidation over VPO catalysts were quite encouraging in respect of possible reach high selectivity and yield of phthalic anhydride. However, in our work it was shown that the main product of n-pentane oxidation in the presence of VPO catalytic system as well as VPMeO was maleic anhydride. Some later our results were confirmed in, where to grow the selectivity towards phthalic anhydride the Co-additive was introduced. On the basis of the proposal made before on the mechanism of paraffins conversion over the vanadyl pyrophosphate surface with their activation at the first and fourth carbon atoms, we assumed possible methylmaleic (citraconic) anhydride forming at n- and i-pentane oxidation. This assumption has been recently supported by both our and other researchers` experimental results. In it was also hypothized possible mechanistic features for phthalic anhydride forming from n-pentane. The present work deals with the results of n- and i-pentane oxidation over VPO catalysts promoted with Bi, Cs, Te, Zr. (orig.)

  14. Copper oxide nanoparticles and copper sulphate act as antigenotoxic agents in drosophila melanogaster.

    Science.gov (United States)

    Alaraby, Mohamed; Hernández, Alba; Marcos, Ricard

    2017-01-01

    The biological reactivity of metal and metal oxide nanomaterials is attributed to their redox properties, which would explain their pro- or anti-cancer properties depending on exposure circumstances. In this sense, copper oxide nanoparticles (CuONP) have been proposed as a potential anti-tumoral agent. The aim of this study was to assess if CuONP can exert antigenotoxic effects using Drosophila melanogaster as an in vivo model. Genotoxicity was induced by two well-known genotoxic compounds, namely potassium dichromate (PD) and ethyl methanesulfonate (EMS). The wing-spot assay and the comet assay were used as biomarkers of genotoxic effects. In addition, changes in the expression of Ogg1 and Sod genes were determined. The effects of CuONP cotreatment were compared with those induced by copper sulfate (CS), an agent releasing copper ions. Using the wing-spot assay, CuONP and CS were not able to reduce the genotoxic effects of EMS exposure, but had the ability to decrease the effects induced by PD, reducing the frequency of mutant twin-spots that arise from mitotic recombination. In addition, CuONP and CS were able to reduce the DNA damage induced by PD as determined by the comet assay. In general, similar qualitative antigenotoxic effects were obtained with both copper compounds. The antigenotoxic effects of environmentally relevant and non-toxic doses of CuONP and CS may be explained by their ability to partially restore the expression levels of the repair gene Ogg1 and the antioxidant gene Cu,ZnSod, both of which are inhibited by PD treatment. Environ. Mol. Mutagen. 58:46-55, 2017. © 2016 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  15. WATER-GAS SHIFT KINETICS OVER IRON OXIDE CATALYSTS AT MEMBRANE REACTOR CONDITIONS

    Energy Technology Data Exchange (ETDEWEB)

    Carl R.F. Lund

    2002-08-02

    The kinetics of water-gas shift were studied over ferrochrome catalysts under conditions with high carbon dioxide partial pressures, such as would be expected in a membrane reactor. The catalyst activity is inhibited by increasing carbon dioxide partial pressure. A microkinetic model of the reaction kinetics was developed. The model indicated that catalyst performance could be improved by decreasing the strength of surface oxygen bonds. Literature data indicated that adding either ceria or copper to the catalyst as a promoter might impart this desired effect. Ceria-promoted ferrochrome catalysts did not perform any better than unpromoted catalyst at the conditions tested, but copper-promoted ferrochrome catalysts did offer an improvement over the base ferrochrome material. A different class of water-gas shift catalyst, sulfided CoMo/Al{sub 2}O{sub 3} is not affected by carbon dioxide and may be a good alternative to the ferrochrome system, provided other constraints, notably the requisite sulfur level and maximum temperature, are not too limiting. A model was developed for an adiabatic, high-temperature water-gas shift membrane reactor. Simulation results indicate that an excess of steam in the feed (three moles of water per mole of CO) is beneficial even in a membrane reactor as it reduces the rate of adiabatic temperature rise. The simulations also indicate that much greater improvement can be attained by improving the catalyst as opposed to improving the membrane. Further, eliminating the inhibition by carbon dioxide will have a greater impact than will increasing the catalyst activity (assuming inhibition is still operative). Follow-up research into the use of sulfide catalysts with continued kinetic and reactor modeling is suggested.

  16. Oxidative Esterification of Methacrolein to Methyl Methacrylate over Supported Palladium Catalyst

    Institute of Scientific and Technical Information of China (English)

    Wei ZHAO; Wei Guo CHENG; Zeng Xi LI; Lei WANG; Xiang Ping ZHANG; Suo Jiang ZHANG

    2006-01-01

    Supported palladium catalysts, which were used in the oxidative esterification of methacrolein to methyl methacrylate, have been prepared with different carriers and Pd precursors.Experimental results revealed that Pd catalysts with γ-Al2O3 support and Na2PdCl4 precursor showed good performance. Pd catalyst modified with Pb and Mg indicated that Pd-Mg bimetallic catalyst exhibited considerably higher activity and Pd-Pb exhibited both higher activity and selectivity. 92.27% methacrolein conversion and 90.57% methyl methacrylate selectivity were obtained on Pd-Pb-Mg catalyst.

  17. Effect of La on Partial Oxidation of Ethanol to Hydrogen over Ni/Fe Catalysts

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The partial oxidation of ethanol to hydrogen was investigated over Ni/Fe/La catalysts prepared by the co-precipitation method. The effects of introduction of La promoter and the reaction temperature on the catalytic performance were studied. It was found that the introduction of La into Ni/Fe catalysts is helpful to increase the selectivity to hydrogen and the stability of the catalysts. The results of XRD and XPS characterization show that the structure of the catalyst was changed during the reaction. The existence of LaFeO3 species is possibly the main reason of the increase of the catalyst stability.

  18. CATALYTIC OXIDATION OF DIMETHYL SULFIDE WITH OZONE: EFFECT OF PROMOTER AND PHYSICO-CHEMICAL PROPERTIES OF METAL OXIDE CATALYSTS

    Science.gov (United States)

    This study reports improved catalytic activities and stabilities for the oxidation of dimethyl sulfide (DMS), a major pollutant of pulp and paper mills. Ozone was used as an oxidant and Cu, Mo, V, Cr and Mn metal oxides, and mixed metal oxides support on y-alumina as catalysts ov...

  19. Calcium oxide based catalysts for ethanolysis of soybean oil

    Directory of Open Access Journals (Sweden)

    Kornkanok Watcharathamrongkul

    2010-12-01

    Full Text Available Transesterification of soybean oil and ethanol catalyzed by calcium oxides prepared from the calcinations of CaO,Ca(OH2, limestone, and Ca(OH2/CaO as solid base catalysts was investigated. It was found that the catalytic activitiessignificantly depended upon their base site strengths and their structures. Increases in catalytic performance of CaO could beachieved by loading Ca(OH2 on CaO and calcinations at a high temperature. The catalytic reaction using a 9:1 molar ratio ofethanol to oil at 70 °C, using CaO loaded with 3.7 wt% Ca(OH2 exhibited the optimal results, where the conversion of soybeanoil reached 96.3% after 10 hrs of the reaction.

  20. Investigation of the oxidation of NO over platinum catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Despres, J.; Koebel, M.; Elsener, M.; Wokaun, A.

    2002-03-01

    The oxidation of NO to NO{sub 2} over Pt/SiO{sub 2} was investigated in the temperature range 150-450{sup o}C. Powdered catalysts were prepared by incipient wetness impregnation, followed by calcination and reduction. The feed gas typically contained oxygen, nitrogen monoxide, water and nitrogen. The concentration of NO in the feed was varied at constant concentration of O{sub 2} in order to study its influence on the reaction. A decrease of the conversion with increasing concentration of NO was observed. A similar study was performed with various oxygen concentrations at constant concentration of NO. Oxygen involved in the surface reaction originates from the dissociative chemisorption of O{sub 2} on the platinum surface. (author)

  1. Facile Synthesis of Copper Oxide Nanoparticles via Electrospinning

    Directory of Open Access Journals (Sweden)

    Abdullah Khalil

    2014-01-01

    Full Text Available A novel approach for synthesizing copper oxide (CuO nanoparticles (NPs through electrospinning is reported. The approach is based on producing rough and discontinuous electrospun nanofibers from a precursor based on copper acetate salt and polyvinyl alcohol (PVA polymer. Selectively removing the polymeric phase from the fibers produced highly rough CuO nanofibers, which were composed of NPs that are weakly held together in a one-dimensional (1D manner. Sonication in a suitable liquid under controlled conditions completely disintegrated the nanofibers into NPs, resulting in the formation of uniform CuO NPs suspension. Aberration corrected high resolution transmission electron microscope (HRTEM showed that the obtained NPs are highly crystalline and nearly sphere-like with a diameter of 30 to 70 nm. Thus, electrospinning, which is a low cost and industrially scalable technique, can also be employed for economic and large scale synthesis of NPs.

  2. On the Electric Field Gradient at Copper Nuclei in Oxides

    Science.gov (United States)

    Shimizu, Tadashi

    1993-02-01

    A useful interpretation is presented of the material dependence of Cu electric field gradient (EFG) in a great variety of insulating and superconducting copper oxides. The present study is concerned only with copper sites in nearly tetragonal symmetry and in stoichiometric compositions. The experimental data of Cu EFGs have been analyzed in terms of ionic picture. The analysis has revealed for the first time a systematic correlation between the observed Cu EFG and the ionic contribution to the EFG. By using the correlation, we have extracted empirical values of the Sternheimer antishielding factor γ∞ and the hyperfine constant for Cu2+ and Cu1+ ions. Those values are somewhat different from the traditional ones of the results of unrestricted Hartree-Fock (UHF) calculations for free ions.

  3. Synthesis and structural characterisation of (aryl-BIAN)copper(I) complexes and their application as catalysts for the cycloaddition of azides and alkynes.

    Science.gov (United States)

    Li, Lidong; Lopes, Patrícia S; Rosa, Vitor; Figueira, Cláudia A; Lemos, M Amélia N D A; Duarte, M Teresa; Avilés, Teresa; Gomes, Pedro T

    2012-05-07

    A series of Ar-BIAN-based copper(I) complexes (where Ar-BIAN = bis(aryl)acenaphthenequinonediimine) were synthesised and characterised by (1)H and (13)C NMR spectroscopies, FT-IR spectroscopy, MALDI-TOF-MS spectrometry, cyclic voltammetry and single crystal X-ray diffraction. The bis-chelated complexes of general formula [Cu(Ar-BIAN)(2)]BF(4) (where Ar = C(6)H(5) (1), 4-iPrC(6)H(4) (3), 2-iPrC(6)H(4) (4)) were prepared by reaction of [Cu(NCMe)(4)]BF(4) with two equivalents of the corresponding Ar-BIAN ligands, in dichloromethane, while the mono-chelated complexes of the type [Cu(Ar-BIAN)L(2)]BF(4) (where Ar = 2,6-iPr(2)C(6)H(3), L = PhCN (6); Ar = 4-iPrC(6)H(4), L = PPh(3) (7)) were readily accessible by treatment of [Cu(NCR)(4)]BF(4) (R = Me, Ph) with one equivalent of the corresponding Ar-BIAN ligands in the absence or presence of two equivalents of PPh(3), in the same solvent. The structures of complexes 3, 4, 6 and 7 were obtained by single crystal X-ray diffraction, showing distorted tetrahedral geometries around the copper centres in all cases. The electrochemical studies of these complexes and of the already reported [Cu(2,4,6-Me(3)C(6)H(2)-BIAN)(2)]BF(4) (2) and [Cu(2,6-iPr(2)C(6)H(3)-BIAN)(NCMe)(2)] (5), demonstrated that the bis-chelated complexes 1-4 undergo a reversible one-electron reduction or oxidation processes on copper, while the mono-chelated complexes 5-7 show a partially reversible oxidation and an irreversible reduction feature. Both kinds of (Ar-BIAN)copper(I) complexes are active catalysts for the copper(I)-catalysed azide-alkyne cycloaddition reaction (CuAAC). Complex 7, bearing PPh(3) ligands, exhibits the highest catalytic activity, which is comparable with that of the typical CuSO(4)-sodium ascorbate catalyst system.

  4. Autothermal and partial oxidation reformer-based fuel processor, method for improving catalyst function in autothermal and partial oxidation reformer-based processors

    Science.gov (United States)

    Ahmed, Shabbir; Papadias, Dionissios D.; Lee, Sheldon H. D.; Ahluwalia, Rajesh K.

    2013-01-08

    The invention provides a fuel processor comprising a linear flow structure having an upstream portion and a downstream portion; a first catalyst supported at the upstream portion; and a second catalyst supported at the downstream portion, wherein the first catalyst is in fluid communication with the second catalyst. Also provided is a method for reforming fuel, the method comprising contacting the fuel to an oxidation catalyst so as to partially oxidize the fuel and generate heat; warming incoming fuel with the heat while simultaneously warming a reforming catalyst with the heat; and reacting the partially oxidized fuel with steam using the reforming catalyst.

  5. Catalytic Activity and Deactivation of SO2 Oxidation Catalysts in Simulated Power Plant Flue Gases

    DEFF Research Database (Denmark)

    Masters, Stephen G.; Chrissanthopoulos, Asthanassios; Eriksen, Kim Michael

    1997-01-01

    The catalyst deactivation and the simultaneious formation of compounds in commercial SO2 oxidation catalysts have been studied by combined activity measurements and in situ EPR spectroscopy in the temperature range 350-480 C in wet and dry simulated power plant flue gas.......The catalyst deactivation and the simultaneious formation of compounds in commercial SO2 oxidation catalysts have been studied by combined activity measurements and in situ EPR spectroscopy in the temperature range 350-480 C in wet and dry simulated power plant flue gas....

  6. Vanadia-silica and vanadia-cesium-silica catalysts for oxidation of SO2

    DEFF Research Database (Denmark)

    Pârvulescu, Vasile I.; Paun, Christina; Pârvulescu, Viorica

    2004-01-01

    of the V/Cs catalysts vanadia is dissolved in a sulfate containing molten salt. The activity of these catalysts for the oxidation of SO2 was tested in a gas containing 2% SO2, 19% O-2, 79% N-2 in the temperature range 523-823 K. Similar experiments with gases containing 10% H2O in the feed or with wet......)-based industrial catalyst, where kieselghur is used as carrier material. The high dispersion of vanadium in the studied catalysts results in an increased catalytic activity for the oxidation of SO2 contained in feed gases with low SO2 content....

  7. "Catalysis in a tea bag": synthesis, catalytic performance and recycling of dendrimer-immobilised bis- and trisoxazoline copper catalysts.

    Science.gov (United States)

    Gaab, Manuela; Bellemin-Laponnaz, Stéphane; Gade, Lutz H

    2009-01-01

    Bis- and trisoxazolines (BOX and trisox), containing a linker unit in the ligand backbone that allows their covalent attachment to carbosilane dendrimers, have been employed as polyfunctional ligands for recyclable Cu(II) Lewis acid catalysts that were immobilised in a membrane bag. The oxazolines contained an alkynyl unit attached to their backbone that was deprotonated with LDA or BuLi and then reacted with the chlorosilyl termini of zeroth-, first- and second-generation carbosilane dendrimers in the presence of TlPF(6). The functionalised dendritic systems were subsequently separated from excess ligand by way of dialysis. The general catalytic potential of these systems was assessed by studying two benchmark reactions, the alpha-hydrazination of a beta-keto ester as well as the Henry reaction of 2-nitrobenzaldehyde with nitromethane. For both reactions the bisoxazoline-based catalysts displayed superior selectivity and, in particular, catalyst activity. The latter was interpreted as being due to the hindered decoordination of the third oxazoline unit, the key step in the generation of the active catalyst, in the immobilised trisox-copper complexes. Solutions of the second-generation dendrimer catalysts were placed in membrane bags, fabricated from commercially available dialysis membranes, with the purpose of catalyst recycling based on dialysis. Overall, the supported BOX catalyst gave good and highly reproducible results throughout the study, whereas the performance of the trisox dendrimer system decreased monotonically. The reason for the different behaviour is the markedly lower activity of trisox-based catalysts relative to those based on the BOX ligand. This necessitated an increased reaction time for each cycle of the trisox derivatives, resulting in higher levels of catalyst leaching, which was attributed to a modification of the structure of the membrane by its exposure to the solvent trifluoroethanol at 40 degrees C.

  8. A basic approach to evaluate methane partial oxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Parmaliana, A. (Universita degli Studi di Messina (Italy)); Frusteri, F.; Mezzapica, A.; Micelli, D.; Giordano, N. (Instituto CNR-TAE, Messina (Italy)); Scurrell, M.S. (CSIR, Pretoria (South Africa))

    1993-09-01

    The partial oxidation of methane to formaldehyde by molecular oxygen on silica and silica-supported oxide catalysts has been investigated at a pressure of 1.7 bar in the temperature range 520-650[degrees]C by using a batch reactor with external recycle. The effects of reactor diameter, recycle flow rate, catalyst weight, and methane-to-oxygen ratio on the catalyst activity have been outlined. By performing several blank tests with an empty and a quartz-filled reactor, it has been demonstrated that the gas-phase reaction does not affect the catalytic pathways. Reasons for controversial results reported previously are discussed. They lie in the lack of an adequate experimental approach and in the generally adopted rule to evaluate the catalytic activity at differential conditions in order to push the HCHO selectivity to high values. The approach presented here allows one to evaluate the catalytic activity by performing tests at quasi-zero conversion per mass but at a finite extent of conversion. The need to express the catalytic activity as space time yield (STY) to HCHO (g[center dot]kg[sub cat][sup [minus]1][center dot]h[sup [minus]1]) is presented. The reactivities of various commercial SiO[sub 2] samples obtained by precipitation, sol-gel, and pyrolysis methods have been determined. The fact that the nature and source of silica has a marked effect on STY, previously observed for reaction at 520[degrees]C, has been confirmed for operation at 550-650[degrees]C. Highest STYs are found with precipitated silica samples. In fact, at 650[degrees]C with such precipitated SiO[sub 2] a STY to HCHO of 303 g[center dot] kg[sub cat][sup [minus]1] [center dot] H[sup [minus]1] has been obtained. Incorporation of molybdena depresses the STY value for the precipitated silica but enhances the STY of bare fumed silica. In contrast, addition of vanadia to either precipitated or fumed silicas leads to higher STY values. 29 refs., 6 figs., 8 tabs.

  9. Highly active Ce 1- xCu xO 2 nanocomposite catalysts for the low temperature oxidation of CO

    Science.gov (United States)

    Mai, Hailing; Zhang, Dengsong; Shi, Liyi; Yan, Tingting; Li, Hongrui

    2011-06-01

    A series of Ce 1- xCu xO 2 nanocomposite catalysts with various copper contents were synthesized by a simple hydrothermal method at low temperature without any surfactants, using mixed solutions of Cu(II) and Ce(III) nitrates as metal sources. These bimetal oxide nanocomposites were characterized by means of XRD, TEM, HRTEM, EDS, N 2 adsorption, H 2-TPR and XPS. The influence of Cu loading (5-25 mol%) and calcination temperature on the surface area, particle size and catalytic behavior of the nanocomposites have been discussed. The catalytic activity of Ce 1- xCu xO 2 nanocomposites was investigated using the test of CO oxidation reaction. The optimized performance was achieved for the Ce 0.80Cu 0.20O 2 nanocomposite catalyst, which exhibited superior reaction rate of 11.2 × 10 -4 mmol g -1 s -1 and high turnover frequency of 7.53 × 10 -2 s -1 (1% CO balanced with air at a rate of 40 mL min -1, at 90 °C). No obvious deactivation was observed after six times of catalytic reactions for Ce 0.80Cu 0.20O 2 nanocomposite catalyst.

  10. A highly active and reusable copper(I)-tren catalyst for the "click" 1,3-dipolar cycloaddition of azides and alkynes.

    Science.gov (United States)

    Candelon, Nicolas; Lastécouères, Dominique; Diallo, Abdou Khadri; Aranzaes, Jaime Ruiz; Astruc, Didier; Vincent, Jean-Marc

    2008-02-14

    The copper(I) complex [Cu(C18(6)tren)]Br 1 (C18(6)tren = tris(2-dioctadecylaminoethyl)amine) which exhibits a good stability towards aerobic conditions is a versatile, highly reactive and recyclable catalyst for the Huisgen cycloaddition of azides with terminal or internal alkynes and is a useful catalyst for the preparation of "click" dendrimers.

  11. Copper iodide nanoparticles on poly(4-vinylpyridine): A new and efficient catalyst for the synthesis of 1,8-dioxooctahydroxanthenes under solvent-free conditions

    Indian Academy of Sciences (India)

    Jalal Albadi; Mosadegh Keshavarz; Masoumeh Abedini; Moloud Khoshakhlagh

    2013-03-01

    Poly(4-vinylpyridine)-supported nanoparticles of copper(I) iodide is reported as a new, efficient and recyclable catalyst for the synthesis of 1,8-dioxooctahydroxanthenes under solvent-free conditions. This catalyst can be recovered by simple filtration and recycled up to 10 consecutive runs without losing of its efficiency.

  12. Purity-enhanced bulk synthesis of thin single-wall carbon nanotubes using iron-copper catalysts

    Science.gov (United States)

    Lim, H. E.; Miyata, Y.; Nakayama, T.; Chen, S.; Kitaura, R.; Shinohara, H.

    2011-09-01

    We report high purity and high yield synthesis of single-wall carbon nanotubes (SWCNTs) of narrow diameter from iron-copper bimetal catalysts. The SWCNTs with diameter of 0.8-1.2 nm are synthesized using the zeolite-supported alcohol chemical vapour deposition method. Single metal and bimetal catalysts are systematically investigated to achieve both the enhancement of SWCNT yield and the suppression of the undesired formation of graphitic impurities. The relative yield and purity of SWCNTs are quantified using optical absorption spectroscopy with an ultracentrifuge-based purification technique. For the single metal catalyst, iron shows the highest catalytic activity compared with the other metals such as cobalt, nickel, molybdenum, copper, and platinum. It has been found that the addition of copper to iron results in the suppression of carbonaceous impurity formation without decreasing the SWCNT yield. The purity-enhanced SWCNT shows fairly low sheet resistance due to the improvement of inter-nanotube contacts. This scalable design of SWCNT synthesis with enhanced purity is therefore a promising tool for shaping future high performance devices.

  13. Scientific basis for process and catalyst design in the selective oxidation of methane to formaldehyde.

    Science.gov (United States)

    Arena, Francesco; Parmaliana, Adolfo

    2003-12-01

    The mechanism and kinetics of the gas-phase selective oxidation of methane to formaldehyde (MPO) are revised in the general context of catalytic oxidations. In agreement with ab initio calculations of the energy barrier for the activation of methane on transition metal oxide complexes, a formal Langmuir-Hinshelwood kinetic model is proposed which accounts for the "steady-state" conditions and activity-selectivity pattern of MPO catalysts, providing an original support to process design and catalyst development.

  14. Electrostatic immobilisation of copper(I) and copper(II) bis(oxazolinyl)pyridine catalysts on silica: application to the synthesis of propargylamines via direct addition of terminal alkynes to imines

    NARCIS (Netherlands)

    McDonagh, C.; O'Conghaile, P.; Klein Gebbink, R.J.M.; O'Leary, P.F.

    2007-01-01

    Copper(I) and copper(II) complexes of two bis(oxazolinyl)pyridines were immobilized on silica via electrostatic interactions. The catalytic activity of the immobilized catalysts in the direct addition of terminal alkynes to imines leading to propargylamines was investigated under a variety of reacti

  15. Investigation of the interaction of copper(II) oxide and electron beam irradiation crosslinkable polyethylene

    Energy Technology Data Exchange (ETDEWEB)

    Bee, Soo-Tueen, E-mail: direct.beest@gmail.com [Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000 Kajang, Selangor (Malaysia); Sin, Lee Tin, E-mail: direct.tinsin@gmail.com [Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000 Kajang, Selangor (Malaysia); Ratnam, C.T. [Radiation Processing Technology Division, Malaysian Nuclear Agency, Bangi, 43000 Kajang, Selangor (Malaysia); Haraveen, K.J.S.; Tee, Tiam-Ting [Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000 Kajang, Selangor (Malaysia); Rahmat, A.R. [Department of Polymer Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia)

    2015-10-01

    In this study, the effects of electron beam irradiation on the properties of copper(II) oxide when added to low-density polyethylene (LDPE) blends were investigated. It was found that the addition of low loading level of copper(II) oxide (⩽2 phr) to LDPE results in significantly poorer gel content and hot set results. However, the incorporation of higher loading level of copper(II) oxide (⩾3 phr) could slightly increase the degree of crosslinking in all irradiated LDPE composites. This is due to the fact that higher amounts of copper(II) oxide could slightly induce the formation of free radicals in LDPE matrix. Besides, increasing irradiation doses was also found to gradually increase the gel content of LDPE composites by generating higher amounts of free radicals. As a consequence, these higher amounts of free radicals released in the LDPE matrix could significantly increase the degree of crosslinking. The addition of copper(II) oxide could reduce the tensile strength and fracture strain (elongation at break) of LDPE composites because of poorer interfacial adhesion effect between copper(II) oxide particles and LDPE matrix. Meanwhile, increasing irradiation doses on all copper(II) oxide added LDPE composites could marginally increase the tensile strength. In addition, increasing irradiation dose could enhance the thermal stability of LDPE composites by increasing the decomposition temperature. The oxidation induction time (OIT) analysis showed that, because of the crosslinking network in the copper(II) oxide added LDPE composites, oxidation reaction is much delayed.

  16. Oxidation of elemental mercury vapor over gamma-Al2O3 supported CuCl2 catalyst for mercury emissions control

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Zhouyang; Liu, Xin; Lee, Joo-Youp; Bolin, Trudy B.

    2015-09-01

    In our previous studies, CuCl2 demonstrated excellent Hg(0) oxidation capability and holds potential for Hg(0) oxidation in coal-fired power plants. In this study, the properties and performances of CuCl2 supported onto gamma-Al2O3 with high surface area were investigated. From various characterization techniques using XPS, XAFS, XRD, TPR, SEM and TGA, the existence of multiple copper species was identified. At low CuCl2 loadings, CuCl2 forms copper aluminate species with gamma-Al2O3 and is inactive for Hg(0) oxidation. At high loadings, amorphous CuCl2 forms onto the gamma-Al2O3 surface, working as a redox catalyst for Hg(0) oxidation by consuming Cl to be converted into CuCl and then being regenerated back into CuCl2 in the presence of O-2 and HCl gases. The 10%(wt) CuCl2/gamma-Al2O3 catalyst showed excellent Hg(0) oxidation performance and SO2 resistance at 140 degrees C under simulated flue gas conditions containing 6%(v) O-2 and 10 ppmv HCl. The oxidized Hg(0) in the form of HgCl2 has a high solubility in water and can be easily captured by other air pollution control systems such as wet scrubbers in coal-fired power plants. The CuCl2/gamma-Al2O3 catalyst can be used as a low temperature Hg(0) oxidation catalyst. (C) 2015 Elsevier B.V. All rights reserved.

  17. Unraveling the Active Site in Copper-ceria Systems for the Water Gas Shift Reaction: In-situ Characterization of an Inverse Powder CeO2-x/CuO-Cu Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, J.A.; Barrio, L.; Estrella, M.; Zhou, G.; Wen, W.; Hanson, J.C.; Hungría, A.B.; Hornés, A.; Fernández-García, M.; Arturo Martínez-Arias, A.

    2010-03-04

    An inverse powder system composed of CeO{sub 2} nanoparticles dispersed over a CuO-Cu matrix is proposed as a novel catalyst for the water-gas shift reaction. This inverse CeO{sub 2}/CuO-Cu catalyst exhibits a higher activity than standard Cu/CeO{sub 2} catalysts. In situ synchrotron characterization techniques were employed to follow the structural changes of CeO{sub 2}/CuO-Cu under reaction conditions. Time-resolved X-ray diffraction experiments showed the transformation of CuO to metallic Cu via a Cu{sub 2}O intermediate. Short-order structural changes were followed by pair distribution function analysis and corroborated the results obtained by diffraction. Moreover, X-ray absorption spectroscopy also revealed oxidation state changes from Cu{sup 2+} to Cu{sup 0} and the partial reduction of CeOx nanoparticles. The activity data obtained by mass spectrometry revealed that hydrogen production starts once the copper has been fully reduced. The strong interaction of ceria and copper boosted the catalytic performance of the sample. The inverse catalyst was active at low temperatures, stable to several reaction runs and to redox cycles. These characteristics are highly valuable for mobile fuel cell applications. The active phases of the inverse CeO{sub 2}/CuO-Cu catalyst are partially reduced ceria nanoparticles strongly interacting with metallic copper. The nature and structure of the ceria nanoparticles are of critical importance because they are involved in processes related to water dissociation over the catalyst surface.

  18. Unraveling the Active Site in Copper-Ceria Systems for the Water-Gas Shift Reaction: In Situ Characterization of an Inverse Powder CeO2-x/CuO-Cu Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Barrio, L.; Estrella, M; Zhou, G; Wen, W; Hanson, J; Hungria, A; Hornes, A; Fernandez-Garcia, M; Martinez-Arias, A; Rodriguez, J

    2010-01-01

    An inverse powder system composed of CeO{sub 2} nanoparticles dispersed over a CuO-Cu matrix is proposed as a novel catalyst for the water-gas shift reaction. This inverse CeO{sub 2}/CuO-Cu catalyst exhibits a higher activity than standard Cu/CeO{sub 2} catalysts. In situ synchrotron characterization techniques were employed to follow the structural changes of CeO{sub 2}/CuO-Cu under reaction conditions. Time-resolved X-ray diffraction experiments showed the transformation of CuO to metallic Cu via a Cu{sub 2}O intermediate. Short-order structural changes were followed by pair distribution function analysis and corroborated the results obtained by diffraction. Moreover, X-ray absorption spectroscopy also revealed oxidation state changes from Cu{sup 2+} to Cu{sup 0} and the partial reduction of CeO{sub x} nanoparticles. The activity data obtained by mass spectrometry revealed that hydrogen production starts once the copper has been fully reduced. The strong interaction of ceria and copper boosted the catalytic performance of the sample. The inverse catalyst was active at low temperatures, stable to several reaction runs and to redox cycles. These characteristics are highly valuable for mobile fuel cell applications. The active phases of the inverse CeO{sub 2}/CuO-Cu catalyst are partially reduced ceria nanoparticles strongly interacting with metallic copper. The nature and structure of the ceria nanoparticles are of critical importance because they are involved in processes related to water dissociation over the catalyst surface.

  19. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

    Science.gov (United States)

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

    1993-01-01

    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 catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. 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.

  20. Incommensurate Magnetic Fluctuations in the Underdoped Copper Oxide Materials

    Institute of Scientific and Technical Information of China (English)

    YUAN Feng; FENG Shi-Ping; CHEN Wei-Yeu

    2001-01-01

    The doping dependence of magnetic fluctuations in the underdoped copper oxide materials are studied within the t-J model. It is shown that away from the half-filling, the magnetic Bragg peaks from the dynamical spin structure factor spectrum S(k, ω) are incommensurate with the lattice. Although the incommensurability δ(x) is almost energy-independent, the dynamical spin susceptibility x〃(k,ω) at the incommensurate wave vectors is changed dramatically with energies, which is consistent with the experiments.``

  1. Fracture toughness of oxide-dispersion strengthened copper

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, D.J. [Oak Ridge National Lab., TN (United States)

    1996-10-01

    The fracture toughness of an oxide-dispersion strengthened copper alloy AL-15 has been examined at room temperature and 250{degrees}C, in air and in vacuum (< 10{sup {minus}6} torr). Increasing test temperature causes a significant decrease in the fracture toughness of this material, in either air or vacuum environments. In addition, specimens oriented in the T-L orientation (crack growth parallel to the extrusion direction) show significantly lower toughness than those in the L-T orientation (crack growth perpendicular to the extrusion direction).

  2. Coming across a novel copper oxide 2D framework during the oxidation of Cu(111).

    Science.gov (United States)

    Matencio, Sonia; Barrena, Esther; Ocal, Carmen

    2016-12-07

    Two dimensional copper oxides obtained on Cu(111) by air-enriched argon sputtering plus annealing have been measured at room temperature by means of scanning tunneling microscopy (STM) and atomic force microscopy (AFM) under ultra-high vacuum (UHV) conditions. Depending on the oxygen content different oxide frameworks and diverse stoichiometric metal/oxide interfaces exist. In particular, we report on a novel open honeycomb structure with a large unit cell which is modeled as a two dimensional network made out of Cu3O units. This lattice coexists with other oxide structures richer in oxygen and is suggested to develop towards these denser phases by oxygen incorporation.

  3. I.C. Engine emission reduction by copper oxide catalytic converter

    Science.gov (United States)

    Venkatesan, S. P.; Shubham Uday, Desai; Karan Hemant, Borana; Rajarshi Kushwanth Goud, Kagita; Lakshmana Kumar, G.; Pavan Kumar, K.

    2017-05-01

    The toxic gases emitted from diesel engines are more than petrol engines. Predicting the use of diesel engines, even more in future, this system is developed and can be used to minimize the harmful gases. Toxic gases include NOX, CO, HC and Smoke which are harmful to the atmosphere as well as to the human beings. The main aim of this work is to fabricate system, where the level of intensity of toxic gases is controlled through chemical reaction to more agreeable level. This system acts itself as an exhaust system; hence there is no needs to fit separate the silencer. The whole assembly is fitted in the exhaust pipe from engine. In this work, catalytic converter with copper oxide as a catalyst, by replacing noble catalysts such as platinum, palladium and rhodium is fabricated and fitted in the engine exhaust. With and without catalytic converter, the experimentations are carried out at different loads such as 0%, 25%, 50%, 75%, and 100% of maximum rated load. From the experimental results it is found that the maximum reduction is 32%, 61% and 21% for HC, NOx and CO respectively at 100% of maximum rated load when compared to that of without catalytic converter. This catalytic converter system is cash effective and more economical than the existing catalytic converter.

  4. The removal of hydrogen sulfide from gas streams using an aqueous metal sulfate absorbent. Part 2. The regeneration of copper sulfide to copper oxide - An experimental study

    NARCIS (Netherlands)

    ter Maat, Hendrik; ter Maat, H.; Hogendoorn, Kees; Versteeg, Geert

    2005-01-01

    Aim of this study was to investigate the possibilities for a selective and efficient method to convert copper(II) sulfide (CuS) into copper(II) oxide (CuO). The oxidation of copper sulfide has been studied experimentally using a thermogravimetric analyzer (TGA) at temperatures ranging from 450 to

  5. The removal of hydrogen sulfide from gas streams using an aqueous metal sulfate absorbent : Part II. the regeneration of copper sulfide to copper oxide - An experimental study

    NARCIS (Netherlands)

    Ter Maat, H.; Hogendoorn, J. A.; Versteeg, G. F.

    2005-01-01

    Aim of this study was to investigate the possibilities for a selective and efficient method to convert copper(II) sulfide (CuS) into copper(II) oxide (CuO). The oxidation of copper sulfide has been studied experimentally using a thermogravimetric analyzer (TGA) at temperatures ranging from 450 to 75

  6. The removal of hydrogen sulfide from gas streams using an aqueous metal sulfate absorbent : Part II. the regeneration of copper sulfide to copper oxide - An experimental study

    NARCIS (Netherlands)

    Ter Maat, H.; Hogendoorn, J. A.; Versteeg, G. F.

    2005-01-01

    Aim of this study was to investigate the possibilities for a selective and efficient method to convert copper(II) sulfide (CuS) into copper(II) oxide (CuO). The oxidation of copper sulfide has been studied experimentally using a thermogravimetric analyzer (TGA) at temperatures ranging from 450 to

  7. Partial oxidation of methane to syngas catalyzed by a nickel nanowire catalyst

    Institute of Scientific and Technical Information of China (English)

    Xuebin Hong; Yaquan Wang

    2009-01-01

    A nickel nanowire catalyst was prepared by a hard template method,and characterized by transmission electron microscopy (TEM),N2 physical adsorption,X-ray photoelectron spectrometry (XPS),X-ray diffraction (XRD) and H2 temperature-programmed reduction (H2-TPR).The catalytic properties of the nanowire catalyst in the partial oxidation of methane to syngas were compared with a metallic Ni catalyst which was prepared with nickel sponge.The characterization results showed that the nickel nanowire catalyst had high specific surface area and there was more NiO phase in the nickel nanowire catalyst than in the metallic Ni catalyst.The reaction results showed that the nickel nanowire catalyst had high CH4 conversion and selectivities for H2 and CO under low space velocity.

  8. Recovery of copper as zero-valent phase and/or copper oxide nanoparticles from wastewater by ferritization.

    Science.gov (United States)

    Heuss-Aßbichler, Soraya; John, Melanie; Klapper, Daniel; Bläß, Ulrich W; Kochetov, Gennadii

    2016-10-01

    Recently the focus of interest changed from merely purification of the waste water to recover heavy metals. With the slightly modified ferritization process presented here it is possible to decrease initial Cu(2+) concentrations up to 10 g/l to values copper of all experiments are in the rage of 99.98 to almost 100%. Copper can be precipitated as oxide or zero valent metal (almost) free of hydroxide. All precipitates are exclusively of nanoparticle size. The phase assemblage depends strongly on experimental conditions as e.g. reaction temperature, pH-value, initial concentration and ageing time and condition. Three different options were developed depending on the reaction conditions. Option 1.) copper incorporation into the ferrite structure ((Cu,Fe)Fe2O4) and/or precipitation as cuprite (Cu2O) and zero-valent copper, option 2.) copper incorporation into the ferrite structure and/or precipitation as cuprite and/or tenorite (CuO) and option 3.) copper precipitation as tenorite. Ferrite is formed by the oxidation of GR in alkaline solution without additional oxygen supply. The chemistry reaches from pure magnetite up to 45% copper ferrite component. First experiments with wastewater from electroplating industry confirm the results obtained from synthetic solutions. In all cases the volume of the precipitates is extremely low compared to typical wastewater treatment by hydroxide precipitation. Therefore, pollution and further dissipation of copper can be avoided using this simple and economic process. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Simultaneous photoreductive removal of copper (II) and selenium (IV) under visible light over spherical binary oxide photocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Aman, Noor [ACC Division, National Metallurgical Laboratory, CSIR (Council of Scientific and Industrial Research), Jamshedpur-831007 (India); Mishra, T., E-mail: drtmishra@yahoo.com [ACC Division, National Metallurgical Laboratory, CSIR (Council of Scientific and Industrial Research), Jamshedpur-831007 (India); Hait, J.; Jana, R.K. [ACC Division, National Metallurgical Laboratory, CSIR (Council of Scientific and Industrial Research), Jamshedpur-831007 (India)

    2011-02-15

    Graphical abstract: Spherical zirconia mixed titania materials can reduce 100 ppm of Cu(II) and Se(VI) mixture within 40 min of reaction under visible light. - Abstract: Waste water of copper mines and copper processing plant contains both copper and selenium ions with other contaminants. In this paper simultaneous photoreductive removal of copper (II) and selenium (IV) is studied for the first time using spherical binary oxide photocatalysts under visible light. All the synthesized materials are found to be mesoporous in nature with reasonably high surface area. Among a range of hole scavengers, only EDTA (ethylene diamine tetraacetic acid) and formic acid are found to be the most active for the reduction reaction. A comparative study is carried out using both the hole scavengers varying reaction time, concentration, pH etc. For a single contaminant, EDTA is found to be the best for Cu(II) reduction whereas formic acid is the best for Se(IV) reduction. In a mixed solution both EDTA and formic acid perform very well under visible light irradiation. Highest photocatalytic reduction in a mixed solution is observed at pH 3. Among all the synthesized materials, TiZr-10 performs as the best photocatalyst for both Cu(II) and Se(IV) reduction. However under UV light, Degussa P25 performs slightly better than TiZr-10. Present study shows that 100 ppm of mixed solution can be removed under visible light in 40 min of reaction using TiZr-10 as catalyst. Photodeposited material is found to be copper selenide rather than pure copper and selenium metal. This indicates that the waste water containing copper and selenium ions can be efficiently treated under visible or solar light.

  10. Simultaneous photoreductive removal of copper (II) and selenium (IV) under visible light over spherical binary oxide photocatalyst.

    Science.gov (United States)

    Aman, Noor; Mishra, T; Hait, J; Jana, R K

    2011-02-15

    Waste water of copper mines and copper processing plant contains both copper and selenium ions with other contaminants. In this paper simultaneous photoreductive removal of copper (II) and selenium (IV) is studied for the first time using spherical binary oxide photocatalysts under visible light. All the synthesized materials are found to be mesoporous in nature with reasonably high surface area. Among a range of hole scavengers, only EDTA (ethylene diamine tetraacetic acid) and formic acid are found to be the most active for the reduction reaction. A comparative study is carried out using both the hole scavengers varying reaction time, concentration, pH etc. For a single contaminant, EDTA is found to be the best for Cu(II) reduction whereas formic acid is the best for Se(IV) reduction. In a mixed solution both EDTA and formic acid perform very well under visible light irradiation. Highest photocatalytic reduction in a mixed solution is observed at pH 3. Among all the synthesized materials, TiZr-10 performs as the best photocatalyst for both Cu(II) and Se(IV) reduction. However under UV light, Degussa P25 performs slightly better than TiZr-10. Present study shows that 100 ppm of mixed solution can be removed under visible light in 40 min of reaction using TiZr-10 as catalyst. Photodeposited material is found to be copper selenide rather than pure copper and selenium metal. This indicates that the waste water containing copper and selenium ions can be efficiently treated under visible or solar light.

  11. Comparison of LECO FP-228 "nitrogen determinator" with AOAC copper catalyst Kjeldahl method for crude protein.

    Science.gov (United States)

    Sweeney, R A; Rexroad, P R

    1987-01-01

    The LECO FP-228 "Nitrogen Determinator" was compared with the AOAC copper catalyst Kjeldahl method, 7.033-7.037, for the determination of crude protein in feed materials. The completely microprocessor-controlled instrument determines nitrogen by measuring the nitrogen gas following combustion of the sample; it was easy to operate and broadly applicable. A wide variety of feed materials of various nitrogen levels were analyzed in one mixed sequence. Results were precise, accurate, and rapid. Analysis time for one sample was approximately 3 min. Fourteen samples containing 2.5-15.5% N were selected for study and consisted of meals, grains, forages, and standard organic materials. The overall mean for the 14 samples by the LECO combustion method was 8.61% N compared with an overall mean of 8.58% N for the AOAC Kjeldahl method. Within-sample standard deviations for the LECO combustion method ranged from 0.013 to 0.052% N with a pooled standard deviation (SD) of 0.033% N for the 14 samples. Standard deviations for the AOAC Kjeldahl method ranged from 0.006 to 0.035% N with a pooled SD of 0.022% N. Combined average recovery of nitrogen from tryptophan, lysine-HCl, and EDTA determined by the LECO combustion method was 99.94% compared to 99.88% determined by the AOAC Kjeldahl method.

  12. Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems

    Energy Technology Data Exchange (ETDEWEB)

    Richard Rhudy

    2006-06-30

    This final report presents and discusses results from a mercury control process development project entitled ''Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems''. The objective of this project was to demonstrate at pilot scale a mercury control technology that uses solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. Oxidized mercury is removed in downstream wet flue gas desulfurization (FGD) absorbers and leaves with the FGD byproducts. The goal of the project was to achieve 90% oxidation of elemental mercury in the flue gas and 90% overall mercury capture with the downstream wet FGD system. The project was co-funded by EPRI and the U.S. Department of Energy's National Energy Technology Laboratory (DOE NETL) under Cooperative Agreement DE-FC26-01NT41185. Great River Energy (GRE) and City Public Service (now CPS Energy) of San Antonio were also project co-funders and provided host sites. URS Group, Inc. was the prime contractor. Longer-term pilot-scale tests were conducted at two sites to provide catalyst life data. GRE provided the first site, at their Coal Creek Station (CCS), which fires North Dakota lignite, and CPS Energy provided the second site, at their Spruce Plant, which fires Powder River Basin (PRB) coal. Mercury oxidation catalyst testing began at CCS in October 2002 and continued through the end of June 2004, representing nearly 21 months of catalyst operation. An important finding was that, even though the mercury oxidation catalyst pilot unit was installed downstream of a high-efficiency ESP, fly ash buildup began to plug flue gas flow through the horizontal catalyst cells. Sonic horns were installed in each catalyst compartment and appeared to limit fly ash buildup. A palladium-based catalyst showed initial elemental mercury oxidation percentages of 95% across the catalyst, declining to 67% after 21 months in service. A carbon

  13. A bentonite-gold nanohybrid as a heterogeneous green catalyst for selective oxidation of silanes.

    Science.gov (United States)

    Maya, R J; John, Jubi; Varma, R Luxmi

    2016-08-23

    A highly efficient, environmentally benign and reusable heterogeneous bentonite-gold nanohybrid catalyst was designed and synthesized. This heterogeneous catalyst could efficaciously catalyse the oxidation of organosilanes to silanols. The reaction is 98.7% atom economical and the products were obtained in excellent yield without the formation of disiloxanes as byproducts. The catalyst was also well applicable for the gram scale preparation of silanols.

  14. Transition metals supported on al-pilcs as catalysts for C6H5Cl oxidation

    OpenAIRE

    Oliveira, L. C. A.; Lago,R.M.; J. D. Fabris; Solar,C.; K. Sapag

    2003-01-01

    In the present work, clays pillared with aluminium and impregnated with transition metals (Fe, Co and Cr) were prepared, characterised and studied as catalysts in the oxidation of chlorobenzene. The pillared clay was synthesised using a natural montmorillonite from San Juan (Argentina) as the starting material and an aluminium polycation solution. The catalysts were prepared by impregnating the pillared clay and then calcinating at 500ºC. The catalysts were characterised by XRD, temperature-p...

  15. Low-temperature catalytic oxidation of NO over Mn-Ce-O_x catalyst

    Institute of Scientific and Technical Information of China (English)

    李华; 唐晓龙; 易红宏; 于丽丽

    2010-01-01

    A series of manganese-cerium oxide catalysts were prepared by different methods and used for low-temperature catalytic oxidation of NO in the presence of excess O2.Their surface properties were evaluated by means of BET and were characterized by using scanning electron microscopy(SEM) and X-ray diffractometer(XRD).The activity test of Mn-Ce-Ox catalysts showed that addition of Ce enhanced the activities of NO oxidation.The most active catalysts with a molar Ce/(Mn+Ce) ratio of 0.3 were prepared by co-precip...

  16. Conventional and microwave-assisted multicomponent reaction of alkyne, halide and sodium azide catalyzed by copper apatite as heterogeneous base and catalyst in water

    Directory of Open Access Journals (Sweden)

    Sandip Kale

    2012-04-01

    Full Text Available The conventional and microwave assisted multicomponent synthesis of disubstituted 1,2,3-triazoles from terminal alkynes and in situ generated organic azide using copper apatite catalyst in water is reported. The catalytic activity is intimately connected to the basicity of the catalyst. The best activities were observed with the copper hydroxyapatite. The catalyst could be used ten times without further treatment and activation under controlled microwave heating. The protocol was also applicable for various alkynes and halides which affords desired product in good to excellent yield.

  17. Supported Copper, Nickel and Copper-Nickel Nanoparticle Catalysts for Low Temperature Water-Gas-Shift Reaction

    Science.gov (United States)

    Lin, Jiann-Horng

    Hydrogen is being considered worldwide as a future replacement for gasoline, diesel fuel, natural gas in both the transportation and non-transportation sectors. Hydrogen is a versatile energy carrier that can be produced from a variety of widely available primary energy sources, including coal, natural gas, biomass, solar, wind, and nuclear power. Coal, the most abundant fossil fuel on the planet, is being looked at as the possible future major source of H2, due to the development of the integrated gasification combined cycle (IGCC) and integrated gasification fuel cell technologies (IGFC). The gasification of coal produces syngas consisting of predominately carbon monoxide and hydrogen with some remaining hydrocarbons, carbon dioxide and water. Then, the water-gas shift reaction is used to convert CO to CO2 and additional hydrogen. The present work describes the synthesis of model Cu, Ni and Cu-Ni catalysts prepared from metal colloids, and compares their behavior in the WGS reaction to that of traditional impregnation catalysts. Initially, we systematically explored the performance of traditional Cu, Ni and Cu-Ni WGS catalysts made by impregnation methods. Various bimetallic Cu-Ni catalysts were prepared by supported impregnation and compared to monometallic Cu and Ni catalysts. The presence of Cu in bimetallic catalysts suppressed undesirable methanation side reaction, while the Ni component was important for high WGS activity. Colloidal Cu, Ni and Cu-Ni alloy nanoparticles obtained by chemical reduction were deposited onto alumina to prepare supported catalysts. The resulting Cu and Ni nanoparticle catalysts were found to be 2.5 times more active in the WGS reaction per unit mass of active metal as compared to catalysts prepared by the conventional impregnation technique. The powder XRD and HAADF-STEM provided evidence supporting the formation of Cu-Ni particles containing the Cu core and Cu-Ni alloy shell. The XPS data indicated surface segregation of Cu in

  18. Copper oxide nanoparticles aggravate airway inflammation and mucus production in asthmatic mice via MAPK signaling.

    Science.gov (United States)

    Park, Ji-Won; Lee, In-Chul; Shin, Na-Rae; Jeon, Chan-Mi; Kwon, Ok-Kyoung; Ko, Je-Won; Kim, Jong-Choon; Oh, Sei-Ryang; Shin, In-Sik; Ahn, Kyung-Seop

    2016-01-01

    Copper oxide nanoparticles (CuONPs), metal oxide nanoparticles were used in multiple applications including wood preservation, antimicrobial textiles, catalysts for carbon monoxide oxidation and heat transfer fluid in machines. We investigated the effects of CuONPs on the respiratory system in Balb/c mice. In addition, to investigate the effects of CuONPs on asthma development, we used a murine model of ovalbumin (OVA)-induced asthma. CuONPs markedly increased airway hyper-responsiveness (AHR), inflammatory cell counts, proinflammatory cytokines and reactive oxygen species (ROS). CuONPs induced airway inflammation and mucus secretion with increases in phosphorylation of the MAPKs (Erk, JNK and p38). In the OVA-induced asthma model, CuONPs aggravated the increased AHR, inflammatory cell count, proinflammatory cytokines, ROS and immunoglobulin E induced by OVA exposure. In addition, CuONPs markedly increased inflammatory cell infiltration into the lung and mucus secretions, and MAPK phosphorylation was elevated compared to OVA-induced asthmatic mice. Taken together, CuONPs exhibited toxicity on the respiratory system, which was associated with the MAPK phosphorylation. In addition, CuONPs exposure aggravated the development of asthma. We conclude that CuONPs exposure has a potential toxicity in humans with respiratory disease.

  19. Dehydrogenation of propane in the presence of carbon dioxide over chromium and gallium oxides catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Agafonov, Yu.A.; Gaidai, N.A.; Nekrasov, N.V.; Menshova, M.V.; Kunusova, R.M. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry

    2011-07-01

    Effective chromium and gallium oxides supported catalysts were prepared and tested in longduration experiments for propane dehydrogenation in the presence of CO{sub 2}. The optimal concentrations of active metals were found. It was shown that the activity, selectivity and stability of chromium oxides catalysts were higher than these parameters for gallium ones. Mechanism of propane oxidative dehydrogenation was studied over both catalysts using unstationary and spectroscopic methods. The employment of these methods allowed to establish the differences in process mechanism. It was shown that surface hydroxides took participation in propene formation over Cr-catalysts and hydrides - over Ga-ones. Propane and carbon dioxide participated in the reaction from the adsorbed state over both catalysts but they were differed by the adsorption capacity of the reaction components: CO2 was tied more firmly than C{sub 3}H{sub 6} over both catalysts, CO{sub 2} and C{sub 3}H{sub 6} were tied more strongly with Cr-catalysts than with Ga-ones. It was shown that CO{sub 2} took active participation in reverse watergas shift reaction and in oxidation of catalyst surface over chromium oxides catalysts. The main role of CO{sub 2} in propane dehydrogenation over gallium catalysts consisted in a decrease of coke formation. Step-schemes of propene and cracking products formation were proposed on the basis of literature and obtained data: via the redox mechanism over Cr-catalysts and through a heterolytic dissociation reaction pathway over Ga-ones. (orig.)

  20. A trinuclear ruthenium complex as a highly efficient molecular catalyst for water oxidation.

    Science.gov (United States)

    Zhang, L L; Gao, Y; Liu, Z; Ding, X; Yu, Z; Sun, L C

    2016-03-01

    A trinuclear ruthenium complex, 3, was designed and synthesized with the ligand 2,2'-bipyridine-6,6'-dicarboxylic acid (bda) and we found that this complex could function as a highly efficient molecular catalyst for water oxidation in homogeneous systems. This trinuclear molecular water oxidation catalyst, 3, displayed much higher efficiencies in terms of turnover numbers and initial oxygen evolution rate than its counterparts, a binuclear catalyst, 2, and a mononuclear catalyst, 1, in both chemically driven and photochemically driven water oxidation based on either the whole catalytic molecules or just the active Ru centers. The reasons for the superior performance of catalyst 3 were discussed and we believe that multiple Ru centers in a single molecule are indeed beneficial for increasing the probability of the formation of O-O bonds through an intramolecular radical coupling pathway.

  1. STUDY OF EPOXIDE DECYCLISATION OF CARYOPHYLENE OXIDE WITH SYNTHETIC ZEOLITE AS CATALYSTS

    Directory of Open Access Journals (Sweden)

    Winarto Haryadi

    2010-06-01

    Full Text Available The reaction of epoxide ring opening of caryophillene oxide has been done using zeolite H-Y, H-sodalit, and H-ZSM-5 as catalysts. The reactions were done in two types, there were in dioxane solvent at temperature of 110 oC and without solvent at temperature of 175 oC. The catalyst weight was 10 % from caryophillene oxide weight, and the time of reaction was four hours. The product of reaction was analyzed using GC, FTIR, and GC-MS. The reactions of caryophillene oxide in dioxane solvent with the three kinds of zeolites did not give any targeted product. Whereas, the reactions without solvent gave three main products, there was one compound with one group of secondary hidroxyl (secondary alcohol, and two compounds of ketone from caryophillene. The reaction product of caryophillene oxide obtained without using solvent with the three type of catalysts were then compared. Conversion of three main products produced by H-ZSM-5 catalyst, H-sodalit catalyst and H-Y catalyst were 82.11 %, 54.92 % and 38.53 % respectively. For that reason, the transformation of caryophillene oxide using H-ZSM-5 catalyst was considered to be the best selective product. The alcohol product was resulted from reaction between caryophillene oxide and Bronsted acid, and  the ketone products was resulted from the reaction with Lewis acid in zeolite.   Keywords: Epoxide ring opening, HY, H-sodalit and HZSM-5

  2. Solvent-free microwave-assisted peroxidative oxidation of secondary alcohols to the corresponding ketones catalyzed by copper(ii) 2,4-alkoxy-1,3,5-triazapentadienato complexes.

    Science.gov (United States)

    Figiel, Paweł J; Kopylovich, Maximilian N; Lasri, Jamal; da Silva, M Fátima C Guedes; da Silva, João J R Fraústo; Pombeiro, Armando J L

    2010-04-28

    A facile, efficient and selective solvent-free synthesis of ketones from secondary alcohols with tert-butylhydroperoxide (TBHP) as the oxidant under microwave irradiation is achieved, where the copper(ii) 2,4-alkoxy-1,3,5-triazapentadienato complexes are efficient catalysts providing high yields (up to 100%), TONs (up to 890) and TOFs (up to 1780 h(-1)).

  3. Selective catalytic oxidation of H{sub 2}S over iron oxide supported on alumina-intercalated Laponite clay catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xin; Dou, Guangyu; Wang, Zhuo [Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Li, Li [Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD 4072 (Australia); Wang, Yufei; Wang, Hailin [Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Hao, Zhengping, E-mail: zpinghao@rcees.ac.cn [Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China)

    2013-09-15

    Graphical abstract: The catalytic reaction and deactivation mechanisms for H{sub 2}S selective oxidation over Fe/Al-Lap catalysts are shown in the illustration. The catalytic reaction follows Mars–van Krevelen mechanism. Moreover, the interaction between iron oxide and alumina, the strong acidity of the catalysts and the well dispersion of iron oxide improve the catalytic performance efficiently. Meanwhile, the catalyst deactivation is mainly due to the formation of Fe{sub 2}(SO{sub 4}){sub 3} and elemental sulfur deposits on the surface. -- Highlights: • Fe/Al-Lap catalysts with mesoporous structure were synthesized. • Iron oxide mainly exists in form of isolate Fe{sup 3+} in an oxidic environment. •Fe/Al-Lap catalysts show high catalytic activities at low temperature. •The high catalytic activities are ascribed to the interaction between iron oxide and alumina. •The formed Fe{sub 2}(SO{sub 4}){sub 3} and elemental sulfur deposits on surface cause catalyst deactivation. -- Abstract: A series of iron oxide supported on alumina-intercalated clay catalysts (named Fe/Al-Lap catalysts) with mesoporous structure and high specific surface area were prepared. The structural and chemical properties were studied by nitrogen sorption isotherms, X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (UV–vis DRS), X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FTIR), H{sub 2} temperature-programmed reduction (H{sub 2}-TPR) and NH{sub 3} temperature-programmed desorption (NH{sub 3}-TPD) techniques. It was realized that iron oxide mainly existed in the form of isolated Fe{sup 3+} in an oxidic environment. Fe/Al-Lap catalysts showed high catalytic activities in the temperature range of 120–200 °C without the presence of excessive O{sub 2}. This can be attributed to the interaction between iron oxide and alumina, which improve the redox property of Fe{sup 3+} efficiently. In addition, the strong acidity of catalysts and good

  4. Supported, Alkali-Promoted Cobalt Oxide Catalysts for NOx Removal from Coal Combustion Flue Gases

    Energy Technology Data Exchange (ETDEWEB)

    Morris D. Argyle

    2005-12-31

    A series of cobalt oxide catalysts supported on alumina ({gamma}-Al{sub 2}O{sub 3}) were synthesized with varying contents of cobalt and of added alkali metals, including lithium, sodium, potassium, rubidium, and cesium. Unsupported cobalt oxide catalysts and several cobalt oxide catalysts supported ceria (CeO{sub 2}) with varying contents of cobalt with added potassium were also prepared. The catalysts were characterized with UV-visible spectroscopy and were examined for NO{sub x} decomposition activity. The CoO{sub x}/Al{sub 2}O{sub 3} catalysts and particularly the CoO{sub x}/CeO{sub 2} catalysts show N{sub 2}O decomposition activity, but none of the catalysts (unsupported Co{sub 3}O{sub 4} or those supported on ceria or alumina) displayed significant, sustained NO decomposition activity. For the Al{sub 2}O{sub 3}-supported catalysts, N{sub 2}O decomposition activity was observed over a range of reaction temperatures beginning about 723 K, but significant (>50%) conversions of N{sub 2}O were observed only for reaction temperatures >900 K, which are too high for practical commercial use. However, the CeO{sub 2}-supported catalysts display N{sub 2}O decomposition rates similar to the Al{sub 2}O{sub 3}-supported catalysts at much lower reaction temperatures, with activity beginning at {approx}573 K. Conversions of >90% were achieved at 773 K for the best catalysts. Catalytic rates per cobalt atom increased with decreasing cobalt content, which corresponds to increasing edge energies obtained from the UV-visible spectra. The decrease in edge energies suggests that the size and dimensionality of the cobalt oxide surface domains increase with increasing cobalt oxide content. The rate data normalized per mass of catalyst that shows the activity of the CeO{sub 2}-supported catalysts increases with increasing cobalt oxide content. The combination of these data suggest that supported cobalt oxide species similar to bulk Co{sub 3}O{sub 4} are inherently more active than

  5. Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga; Lee, Sungsik; Cullen, David A.; Agrawal, Pradeep K.; Jones, Christopher W.

    2016-05-01

    The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the other catalysts, with promising activity compared to related catalysts in the literature. The use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.

  6. Dielectric Properties of Reduced Graphene Oxide/Copper Phthalocyanine Nanocomposites Fabricated Through π- π Interaction

    Science.gov (United States)

    Wang, Zicheng; Wei, Renbo; Liu, Xiaobo

    2017-01-01

    Reduced graphene oxide/copper phthalocyanine nanocomposites are successfully prepared through a simple and effective two-step method, involving preferential reduction of graphene oxide and followed by self-assembly with copper phthalocyanine. The results of photographs, ultraviolet visible, x-ray diffraction, x-ray photoelectron spectroscopy, and scanning electron microscopy show that the in situ blending method can effectively facilitate graphene sheets to disperse homogenously in the copper phthalocyanine matrix through π- π interactions. As a result, the reduction of graphene oxide and restoration of the sp 2 carbon sites in graphene can enhance the dielectric properties and alternating current conductivity of copper phthalocyanine effectively.

  7. Controlled electromigration and oxidation of free-standing copper wires

    Science.gov (United States)

    Hauser, J. S.; Schwichtenberg, J.; Marz, M.; Sürgers, C.; Seiler, A.; Gerhards, U.; Messerschmidt, F.; Hensel, A.; Dittmeyer, R.; Löhneysen, H. v.; Hoffmann-Vogel, R.

    2016-12-01

    We have studied controlled electromigration (EM) in free-standing copper wires. Besides electrical characterization by voltage-current measurements, structural analyses have been performed by means of scanning electron microscopy and cross-sectional microprobe measurements. We have found that oxidation during the EM in air stabilizes the free-standing wire against uncontrolled blowing, making it possible to thin the conductive part of the wire down to a conductance of a few conductance quanta G_0=2e^2{/}h. The decisive influence of oxidation by air on the EM process was confirmed by control experiments performed under ultra-high vacuum conditions. In line with these findings, free-standing Au wires were difficult to thin down reproducibly to a conductance of a few G_0. Estimates of the local temperature in the free-standing wire are obtained from finite element method calculations.

  8. Effect of Copper Nanoparticles Dispersion on Catalytic Performance of Cu/SiO2 Catalyst for Hydrogenation of Dimethyl Oxalate to Ethylene Glycol

    Directory of Open Access Journals (Sweden)

    Yajing Zhang

    2013-01-01

    Full Text Available Cu/SiO2 catalysts, for the synthesis of ethylene glycol (EG from hydrogenation of dimethyl oxalate (DMO, were prepared by ammonia-evaporation and sol-gel methods, respectively. The structure, size of copper nanoparticles, copper dispersion, and the surface chemical states were investigated by X-ray diffraction (XRD, transmission electron microscopy (TEM, temperature-programmed reduction (TPR, and X-ray photoelectron spectroscopy (XPS and N2 adsorption. It is found the structures and catalytic performances of the catalysts were highly affected by the preparation method. The catalyst prepared by sol-gel method had smaller average size of copper nanoparticles (about 3-4 nm, better copper dispersion, higher Cu+/C0 ratio and larger BET surface area, and higher DMO conversion and EG selectivity under the optimized reaction conditions.

  9. Flotation of cobalt bearing minerals from a mixed copper-cobalt oxidized ore

    OpenAIRE

    2012-01-01

    M.Tech. (Extraction Metallurgy) The techniques for the flotation of mixed copper and cobalt bearing oxide ores using the sulphidization method in order to recover the oxidized copper and cobalt bearing minerals have been well documented by previous researchers. These processes have been successfully implemented in many of the metallurgical plant operations in the Democratic Republic of Congo (DRC). The mixed copper and cobalt oxidised ores from this region present significant chal-lenges t...

  10. Partial Oxidation of Methane to Formaldehyde over Superfine Mo/ZrO2 Catalysts

    Institute of Scientific and Technical Information of China (English)

    Xin Zhang; Dehua He; Qijian Zhang; Qing Ye; Qiming Zhu

    2002-01-01

    Superfine Mo/ZrO2 catalysts were prepared for partial oxidation of methane to HCHO andcharacterized by BET, XRD, LRS, H2-TPR and XPS. Mo existed mainly in the form of Zr(MoO4)2, andthe catalytic performance and physicochemical properties of the Mo/ZrO2 catalysts were closely relatedto this species.

  11. Physico-Chemical and Structural Properties of DeNOx and SO2 Oxidation Catalysts

    DEFF Research Database (Denmark)

    Masters, Stephen Grenville; Oehlers, Cord; Nielsen, Kurt;

    1996-01-01

    Commercial catalysts for NOx removal and SO2 oxidation and their model systems have been investigated by spectroscopic, thermal, electrochemical and X-ray methods. Structural information on the vanadium complexes and compounds as well as physico-chemical properties for catalyst model systems have...... been obtained. The results are discussed in relation to proposed reaction mechanisms....

  12. The role of support and promoter on the oxidation of sulfur dioxide using platinum based catalysts

    DEFF Research Database (Denmark)

    Koutsopoulos, Sotiris; Rasmussen, Søren Birk; Eriksen, Kim Michael

    2006-01-01

    The catalytic oxidation of SO2 to SO3 was studied over platinum based catalysts in the absence and the presence of dopants. The active metal was supported on silica gel or titania (anatase) by impregnation. The activities of the silica supported catalysts were found to follow the order PtRh/SiO2...

  13. Nickel-oxido structure of a water-oxidizing catalyst film.

    Science.gov (United States)

    Risch, Marcel; Klingan, Katharina; Heidkamp, Jonathan; Ehrenberg, David; Chernev, Petko; Zaharieva, Ivelina; Dau, Holger

    2011-11-21

    The atomic structure of an electrodeposited Ni catalyst film is dominated by extensive di-μ-oxido bridging between Ni(III/IV) ions, as revealed by X-ray absorption spectroscopy. The structure is surprisingly similar to that of an analogous Co-based film and colloidal Mn-based catalysts. Structural requirements for water oxidation are discussed.

  14. Nickel/magnesium-lanthanum mixed oxide catalyst in the Kumada-coupling.

    Science.gov (United States)

    Kiss, Arpád; Hell, Zoltán; Bálint, Mária

    2010-01-21

    A new, heterogeneous, magnesium-lanthanum mixed oxide solid base-supported nickel(ii) catalyst was developed. The catalyst was used successfully in the Kumada coupling of aryl halides, especially aryl bromides. The optimal reaction conditions of the coupling were determined.

  15. The Sulfidation of gamma-Alumina and Titania Supported (Cobalt) Molybdenum Oxide Catalysts Monitored by EXAFS.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Leliveld, R.G.; Dillen, A.J. van; Geus, John W.

    1997-01-01

    The sulfidation of @c-alumina- and titania-supported(cobalt)molybdenum oxide catalysts has been studied with X-rayabsorption spectroscopy and temperature programmed sulfidation (TPS).The catalysts were stepwise sulfided at temperatures between 298 and673 K and their structure was determined with EXA

  16. Highly Efficient, Green Oxidation of Alcohols Using Novel Heterogeneous Ruthenium Catalyst

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    MnFe1.4Ruo.45Cu0.15O4 was an effective heterogeneous catalyst for the oxidation ofvarious types of alcohols to the corresponding carbonyl compounds using atmospheric pressure ofoxygen under mild conditions. Furthermore, this catalyst was also effective towards alcoholoxidation using water as solvent instead of toluene.

  17. Photocatalytic oxidation of cyclohexane by titanium dioxide: Catalyst deactivation and regeneration

    NARCIS (Netherlands)

    Carneiro, Joana T.; Moulijn, Jacob A.; Mul, Guido

    2010-01-01

    Two commercially available TiO2 catalysts were compared in the selective photocatalytic oxidation of cyclohexane: Hombikat UV100 (as received (H), and after calcination at 600 °C (H600)), and Solaronix, S450. Hombikat UV100 shows the highest initial activity on a g−1 catalyst basis, followed by H600

  18. Nano indium oxide as a recyclable catalyst for the synthesis of arylaminotetrazoles

    Indian Academy of Sciences (India)

    Siavash Bahari; Mehdi Ahmadi Sabegh

    2013-01-01

    Nano indium oxide is an effective heterogeneous catalyst for the reaction between aryl cyanamides and sodium azide to synthesize the arylaminotetrazoles in good yields. This method has advantages of high yields, simple methodology, short reaction times and easy work-up. The catalyst can be recovered and reused in good yields.

  19. A Highly Active and Selective Manganese Oxide Promoted Cobalt-on-Silica Fischer-Tropsch Catalyst

    NARCIS (Netherlands)

    den Breejen, Johan P.; Frey, Anne M.; Yang, Jia; Holmen, Anders; van Schooneveld, Matti M.; de Groot, Frank M. F.; Stephan, Odile; Bitter, Johannes H.; de Jong, Krijn P.

    2011-01-01

    A highly active and selective manganese oxide-promoted silica-supported cobalt catalyst for the Fischer-Tropsch reaction is reported. Co/MnO/SiO2 catalysts were prepared via impregnation of a cobalt nitrate and manganese nitrate precursor, followed by drying and calcination in an NO/He flow. The cat

  20. Synthesis of highly stable, water-dispersible copper nanoparticles as catalysts for nitrobenzene reduction.

    Science.gov (United States)

    Kaur, Ravneet; Giordano, Cristina; Gradzielski, Michael; Mehta, Surinder K

    2014-01-01

    We report an aqueous-phase synthetic route to copper nanoparticles (CuNPs) using a copper-surfactant complex and tests of their catalytic efficiency for a simple nitrophenol reduction reaction under atmospheric conditions. Highly stable, water-dispersed CuNPs were obtained with the aid of polyacrylic acid (PAA), but not with other dispersants like surfactants or polymethacrylic acid (PMAA). The diameter of the CuNPs could be controlled in the range of approximately 30-85 nm by modifying the ratio of the metal precursor to PAA. The catalytic reduction of p-nitrophenol to p-aminophenol takes place at the surface of CuNPs at room temperature and was accurately monitored by UV/Vis spectroscopy. The catalytic efficiency was found to be remarkably high for these PAA-capped CuNPs, given the fact that at the same time PAA is efficiently preventing their oxidation as well. The activity was found to increase as the size of the CuNPs decreased. It can therefore be concluded that the synthesized CuNPs are catalytically highly efficient in spite of the presence of a protective PAA coating, which provides them with a long shelf life and thereby enhances the application potential of these CuNPs. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Binary copper oxide semiconductors: From materials towards devices

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, B.K.; Polity, A.; Reppin, D.; Becker, M.; Hering, P.; Klar, P.J.; Sander, T.; Reindl, C.; Benz, J.; Eickhoff, M.; Heiliger, C.; Heinemann, M. [1. Physics Institute, Justus-Liebig University of Giessen (Germany); Blaesing, J.; Krost, A. [Institute of Experimental Physics (IEP), Otto-von-Guericke University Magdeburg (Germany); Shokovets, S. [Institute of Physics, Ilmenau University of Technology (Germany); Mueller, C.; Ronning, C. [Institute of Solid State Physics, Friedrich Schiller University Jena (Germany)

    2012-08-15

    Copper-oxide compound semiconductors provide a unique possibility to tune the optical and electronic properties from insulating to metallic conduction, from bandgap energies of 2.1 eV to the infrared at 1.40 eV, i.e., right into the middle of the efficiency maximum for solar-cell applications. Three distinctly different phases, Cu{sub 2}O, Cu{sub 4}O{sub 3}, and CuO, of this binary semiconductor can be prepared by thin-film deposition techniques, which differ in the oxidation state of copper. Their material properties as far as they are known by experiment or predicted by theory are reviewed. They are supplemented by new experimental results from thin-film growth and characterization, both will be critically discussed and summarized. With respect to devices the focus is on solar-cell performances based on Cu{sub 2}O. It is demonstrated by photoelectron spectroscopy (XPS) that the heterojunction system p-Cu{sub 2}O/n-AlGaN is much more promising for the application as efficient solar cells than that of p-Cu{sub 2}O/n-ZnO heterojunction devices that have been favored up to now. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. The effect of copper valence on catalytic combustion of styrene over the copper based catalysts in the absence and presence of water vapor☆

    Institute of Scientific and Technical Information of China (English)

    Hongyan Pan; Zhiyan He; Qian Lin; Fei Liu; Zhong Li

    2016-01-01

    Catalysts CuOx/γ-Al2O3-IH and CuOx/γ-Al2O3-IM were prepared, characterized, and tested for styrene combustion in the absence and presence of water vapor. The effect of copper valence of the catalysts on the catalytic activity for styrene combustion was discussed using the theory of hard soft acids and bases (HSAB). The results showed that the existence of water vapor in feed stream inhibited the catalytic activity for styrene combustion due to the competition adsorption of water molecule. HSAB theory confirmed that the local soft acidity of the catalyst CuOx/γ-Al2O3-IH was much stronger than that of the catalyst CuOx/γ-Al2O3-IM because of the higher content of soft acid Cu+on its surface, which increased the adsorption ability toward soft base of styrene and reduced the adsorption toward hard base of water vapor, and thus increased the catalytic activity for styrene combustion and weakened the negative influence of water vapor.

  3. Oxidation kinetics of nanoscale copper films studied by terahertz transmission spectroscopy

    NARCIS (Netherlands)

    Ramanandan, G.K.P.; Ramakrishnan, G.; Planken, P.C.M.

    2012-01-01

    Terahertz (THz) transmission spectroscopy is used to measure the oxidation kinetics of copper thin films evaporated on silicon substrates. The transmission of broadband THz pulses from 1 to 7 THz through the copper film is measured while it gets oxidized at an elevated temperature in ambient air. Th

  4. Copper-catalyzed oxidative alkynylation of diaryl imines with terminal alkynes: a facile synthesis of ynimines.

    Science.gov (United States)

    Laouiti, Anouar; Rammah, Mohamed M; Rammah, Mohamed B; Marrot, Jérome; Couty, François; Evano, Gwilherm

    2012-01-06

    An efficient copper-mediated method for the oxidative alkynylation of diaryl imines with terminal alkynes is reported. This reaction provides the first catalytic and general synthesis of ynimines and allows for an easy preparation of these useful building blocks. An improved copper-catalyzed oxidative dimerization of imines to azines and the synthesis of dienes and azadienes from ynimines are also described.

  5. Biogenic copper oxide nanoparticles synthesis using Tabernaemontana divaricate leaf extract and its antibacterial activity against urinary tract pathogen

    Science.gov (United States)

    Sivaraj, Rajeshwari; Rahman, Pattanathu K. S. M.; Rajiv, P.; Salam, Hasna Abdul; Venckatesh, R.

    2014-12-01

    This investigation explains the biosynthesis and characterization of copper oxide nanoparticles from an Indian medicinal plant by an eco-friendly method. The main objective of this study is to synthesize copper oxide nanoparticles from Tabernaemontana divaricate leaves through a green chemistry approach. Highly stable, spherical copper oxide nanoparticles were synthesized by using 50% concentration of Tabernaemontana leaf extract. Formation of copper oxide nanoparticles have been characterized by UV-Vis absorption spectroscopy, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX) and transmission electron microscopy (TEM) analysis. All the analyses revealed that copper oxide nanoparticles were 48 ± 4 nm in size. Functional groups and chemical composition of copper oxide were also confirmed. Antimicrobial activity of biogenic copper oxide nanoparticles were investigated and maximum zone of inhibition was found in 50 μg/ml copper oxide nanoparticles against urinary tract pathogen (Escherichia coli).

  6. Biogenic copper oxide nanoparticles synthesis using Tabernaemontana divaricate leaf extract and its antibacterial activity against urinary tract pathogen.

    Science.gov (United States)

    Sivaraj, Rajeshwari; Rahman, Pattanathu K S M; Rajiv, P; Salam, Hasna Abdul; Venckatesh, R

    2014-12-10

    This investigation explains the biosynthesis and characterization of copper oxide nanoparticles from an Indian medicinal plant by an eco-friendly method. The main objective of this study is to synthesize copper oxide nanoparticles from Tabernaemontana divaricate leaves through a green chemistry approach. Highly stable, spherical copper oxide nanoparticles were synthesized by using 50% concentration of Tabernaemontana leaf extract. Formation of copper oxide nanoparticles have been characterized by UV-Vis absorption spectroscopy, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX) and transmission electron microscopy (TEM) analysis. All the analyses revealed that copper oxide nanoparticles were 48±4nm in size. Functional groups and chemical composition of copper oxide were also confirmed. Antimicrobial activity of biogenic copper oxide nanoparticles were investigated and maximum zone of inhibition was found in 50μg/ml copper oxide nanoparticles against urinary tract pathogen (Escherichia coli).

  7. Propriedades texturais e catalíticas de óxidos de ferro contendo cromo e cobre Textural and catalytic properties of chromium and copper-doped iron oxides

    Directory of Open Access Journals (Sweden)

    Marluce Oliveira da Guarda Souza

    1998-07-01

    Full Text Available Chromium and copper-doped hematites were prepared with the aim of studying the synergistic effect of these dopants on the textural and on the catalytic properties of the iron oxides towards the high temperature shift reaction. It was found that the most active catalysts were those with the highest amount of copper. They had the Fe(II/Fe(III ratio near the stoichiometric value of magnetite, the highest surface areas under the reactional atmosphere and the greatest tendency to produce the active form; they also were poorly crystalline solids. The best performance was shown by the catalyst with Fe/Cu=10, heated at 300ºC. It can thus be concluded that copper acts both as textural and structural promoter in these catalysts.

  8. Study on Catalysts with Rhodium Loading on Different Cerium-Zirconium Mixed Oxides

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The catalysts with Rh loading on different cerium-zirconium mixed oxides were characterized by BET, H2-TPR and OSC. The effects of different cerium-zirconium mixed oxides on catalytic performance and thermal stability of Rh loaded catalyst were studied. The results show that: (1) Rh can enhance cerium-zirconium mixed oxides OSC and catalytic reaction rates; (2) cerium-zirconium mixed oxides with high Ce contents and low Zr contents are more favorable to the stability of catalysts. Moreover, the contents of CeO2 have important effect on catalysts characteristics, and the addition of some rare earth components, such as La, Pr and Nd also have some influences.

  9. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    Science.gov (United States)

    Corbea, Javier Jesus Concepcion; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

    2013-09-03

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  10. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Corbea, Javier Jesus Concepcion; Chen, Zoufeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

    2016-06-07

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  11. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    National Research Council Canada - National Science Library

    Zhuang, Zhongbin; Giles, Stephen A; Zheng, Jie; Jenness, Glen R; Caratzoulas, Stavros; Vlachos, Dionisios G; Yan, Yushan

    2016-01-01

    .... Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte...

  12. Propan-1-ol Oxidation Reaction on Au/TiO2 Catalysts

    African Journals Online (AJOL)

    MBI

    2014-11-27

    Nov 27, 2014 ... Department of pure and applied Chemistry, Bayero University, Kano P.M.B 3011, Kano State, Nigeria ... using Pulse Flow reactor, TPFRP, TPD, and XRD,. ... complete oxidation reaction of propan-1-ol on the catalysts.

  13. Electrochemical synthesis and characterization of copper (I oxide

    Directory of Open Access Journals (Sweden)

    Bugarinović Sanja J.

    2009-01-01

    Full Text Available The quest and need for clean and economical energy sources have increased interest in the development of thin film cells technologies. Electrochemical deposition is an attractive method for synthesis of thin films. It offers the advantages of low synthesis temperature, low cost and high purity. Copper (I oxide or cuprous oxide is an oxide semiconductor which is used as the anodic material in the form of thin film in lithium batteries and solar cells. The cathodic process of synthesis of cuprous oxide thin film is carried out in a potentiostatic mode from the organic electrolyte. The process parameters are chosen in that way to accomplish maximum difference between the potentials at which Cu2O and CuO are obtained. The electrochemical characterization was carried out by cyclic voltammetry. The electrodeposition techniques are particularly well suited for the deposition of single elements but it is also possible to carry out simultaneous depositions of several elements and syntheses of well-defined alternating layers of metals and oxides with thicknesses down to a few nm. Nanomaterials exhibit novel physical properties and play an important role in fundamental research. In addition, cuprous oxide is commonly used as a pigment, a fungicide, and an antifouling agent for marine paints. It is insoluble in water and organic solvents. This work presents the examinations of the influence of bath, temperature, pH and current density on the characteristics of electrochemically synthesized cuprous oxide. In the 'classic' process of synthesis, which is carried out under galvanostatic conditions on the anode, the grain size of the powder decreases with the increase in current density while the grain colour becomes lighter. The best commercial quality of the Cu2O (grain size, colour, content of choride was obtained at the temperature of 80°C, concentration of NaCl of 3 mol/dm3 and current density of 400 A/m2.

  14. Aerobic oxidation of aldehydes under ambient conditions using supported gold nanoparticle catalysts

    DEFF Research Database (Denmark)

    Marsden, Charlotte Clare; Taarning, Esben; Hansen, David

    2008-01-01

    A new, green protocol for producing simple esters by selectively oxidizing an aldehyde dissolved in a primary alcohol has been established, utilising air as the oxidant and supported gold nanoparticles as catalyst. The oxidative esterifications proceed with excellent selectivities at ambient...

  15. SnO2 nanospheres supported Pd catalyst with enhanced performance for formic acid oxidation

    Science.gov (United States)

    Lu, Haiting; Fan, Yang; Huang, Ping; Xu, Dongli

    2012-10-01

    SnO2 nanospheres were employed as the support material for Pd catalyst. The as-prepared Pd/SnO2 catalyst exhibited remarkably improved electrocatalytic activity and stability towards formic acid oxidation, in comparison with that of the Vulcan XC-72 carbon black and the commercial SnO2 nanopowder supported Pd catalyst. The enhanced catalytic performance may arise from the unique structure and surface properties of the SnO2 nanospheres, which process extraordinary promotional effect on Pd catalyst.

  16. A Facile Synthesis of Hollow Palladium/Copper Alloy Nanocubes Supported on N-Doped Graphene for Ethanol Electrooxidation Catalyst

    Directory of Open Access Journals (Sweden)

    Zhengyu Bai

    2015-04-01

    Full Text Available In this paper, a catalyst of hollow PdCu alloy nanocubes supported on nitrogen-doped graphene support (H-PdCu/ppy-NG is successfully synthesized using a simple one-pot template-free method. Two other catalyst materials such as solid PdCu alloy particles supported on this same nitrogen-doped graphene support (PdCu/ppy-NG and hollow PdCu alloy nanocubes supported on the reduced graphene oxide support (H-PdCu/RGO are also prepared using the similar synthesis conditions for comparison. It is found that, among these three catalyst materials, H-PdCu/ppy-NG gives the highest electrochemical active area and both the most uniformity and dispersibility of H-PdCu particles. Electrochemical tests show that the H-PdCu/ppy-NG catalyst can give the best electrocatalytic activity and stability towards the ethanol electrooxidation when compared to other two catalysts. Therefore, H-PdCu/ppy-NG should be a promising catalyst candidate for anodic ethanol oxidation in direct ethanol fuel cells.

  17. Fabrication of functional transition metal oxide and hydroxide used as catalysts and battery materials

    Science.gov (United States)

    Xu, Linping

    My research is focused on developing metal oxide and hydroxide nanomaterials which can be used as battery materials, organic transformation catalysts, and photocatalysts. This research involves studying ZnO with different morphologies as photocatalysts for phenol degradation, producing CuO as olefin epoxidation catalysts, developing V and Cu incorporated manganese oxides as cathode materials for Li-ion batteries, and fabricating alpha-nickel hydroxide for Li-air battery materials. The first part includes producing ZnO as a photocatalyst for phenol degradation. The goal of this study is the synthesis of ZnO with different morphologies using the solvothermal method. The influence of solvents has been studied in detail. Their properties and photocatalytic performances have been explored as well. The second part of the research is concerned with developing novel urchin-like CuO as an olefin epoxidation catalyst. The purpose of this study is to develop a new catalyst, CuO, for olefin epoxidation. The copper source and precipitators were optimized, and the possible self-assembly mechanism of the urchin-like morphology was proposed. The catalytic activity of CuO for olefin epoxidation was studied. The third part of this work includes developing V, Cu incorporated manganese oxide (V-Cu-OMS-2) as cathode materials for Li-ion batteries. The purpose of this project is to develop a new material with enhanced battery performance. V and Cu incorporated manganese oxide were developed using hydrothermal methods. Octahedral molecular sieve (OMS) materials show mixed valences of Mn 3+ and Mn4+, which produces novel properties in battery applications. Inexpensive starting materials make OMS materials more promising for commercial applications. How the incorporation of V and Cu affected OMS-2 materials was investigated in terms of their crystal structure, morphologies, and surface areas. The battery performance of the incorporated OMS-2 materials with different loading amounts of V

  18. Selective nano alumina supported vanadium oxide catalysts for oxidative dehydrogenation of ethylbenzene to styrene using CO2 as soft oxidant

    Directory of Open Access Journals (Sweden)

    A.M. Elfadly

    2013-12-01

    Full Text Available Nano alumina-supported V2O5 catalysts with different loadings have been tested for the dehydrogenation of ethylbenzene with CO2 as an oxidant. High surface area nano-alumina was prepared and used as support for V2O5 as the catalyst. The catalysts were synthesized by impregnation techniques followed by calcinations and microwave treatment, denoted as V2O5/γ-Al2O3-C and V2O5/γ-Al2O3-MW, respectively. The V2O5 loading was varied on nano-alumina from 5 to 30 wt%. The support and catalysts were characterized by X-ray diffraction (XRD, Barett–Joyner–Halenda (BJH pore-size distribution, N2-adsorption isotherms, Fourier transform infrared (FT-IR, scanning electron microscopy (SEM, transmission electron microscopy (TEM and temperature programed desorption (TPD-NH3. The characterization results indicated that V2O5 is highly dispersed on alumina up to 30%-V2O5/γ-Al2O3-MW prepared by MW method. The TPD studies indicated that there are significant differences in acid amount and strength for V2O5/γ-Al2O3-C and V2O5/γ-Al2O3-MW-catalysts. The catalytic activity of the prepared catalysts was evaluated in the temperature range 450–600 °C in relation to the physicochemical properties and surface acidity. The results revealed that optimum catalytic activity and selectivity (∼100% toward styrene production were obtained using 10% V2O5/γ-Al2O3-MW catalyst treated with microwave.

  19. Developing mononuclear copper-active-oxygen complexes relevant to reactive intermediates of biological oxidation reactions.

    Science.gov (United States)

    Itoh, Shinobu

    2015-07-21

    Active-oxygen species generated on a copper complex play vital roles in several biological and chemical oxidation reactions. Recent attention has been focused on the reactive intermediates generated at the mononuclear copper active sites of copper monooxygenases such as dopamine β-monooxygenase (DβM), tyramine β-monooxygenase (TβM), peptidylglycine-α-hydroxylating monooxygenase (PHM), and polysaccharide monooxygenases (PMO). In a simple model system, reaction of O2 and a reduced copper(I) complex affords a mononuclear copper(II)-superoxide complex or a copper(III)-peroxide complex, and subsequent H(•) or e(-)/H(+) transfer, which gives a copper(II)-hydroperoxide complex. A more reactive species such as a copper(II)-oxyl radical type species could be generated via O-O bond cleavage of the peroxide complex. However, little had been explored about the chemical properties and reactivity of the mononuclear copper-active-oxygen complexes due to the lack of appropriate model compounds. Thus, a great deal of effort has recently been made to develop efficient ligands that can stabilize such reactive active-oxygen complexes in synthetic modeling studies. In this Account, I describe our recent achievements of the development of a mononuclear copper(II)-(end-on)superoxide complex using a simple tridentate ligand consisting of an eight-membered cyclic diamine with a pyridylethyl donor group. The superoxide complex exhibits a similar structure (four-coordinate tetrahedral geometry) and reactivity (aliphatic hydroxylation) to those of a proposed reactive intermediate of copper monooxygenases. Systematic studies based on the crystal structures of copper(I) and copper(II) complexes of the related tridentate supporting ligands have indicated that the rigid eight-membered cyclic diamine framework is crucial for controlling the geometry and the redox potential, which are prerequisites for the generation of such a unique mononuclear copper(II)-(end-on)superoxide complex

  20. Hybrid Copper-Silver Conductive Tracks for Enhanced Oxidation Resistance under Flash Light Sintering.

    Science.gov (United States)

    Yim, Changyong; Sandwell, Allen; Park, Simon S

    2016-08-31

    We developed a simple method to prepare hybrid copper-silver conductive tracks under flash light sintering. The developed metal nanoparticle-based ink is convenient because its preparation process is free of any tedious washing steps. The inks were composed of commercially available copper nanoparticles which were mixed with formic acid, silver nitrate, and diethylene glycol. The role of formic acid is to remove the native copper oxide layer on the surface of the copper nanoparticles. In this way, it facilitates the formation of a silver outer shell on the surface of the copper nanoparticles through a galvanic replacement. In the presence of formic acid, the copper nanoparticles formed copper formate, which was present in the unsintered tracks. However, under illumination by a xenon flash light, the copper formate was then converted to copper. Moreover, the resistance of the copper-only films increased by 6 orders of magnitude when oxidized at high temperatures (∼220 °C). However, addition of silver nitrate to the inks suppressed the oxidation of the hybrid copper-silver films, and the resistance changes in these inks at high temperatures were greatly reduced. In addition, the hybrid inks proved to be advantageous for use in electrical circuits as they demonstrated a stable electrical conductivity after exposure to ambient air at 180 °C.