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Sample records for cu-based catalyst systems

  1. Orthogonal Pd- and Cu-Based Catalyst Systems for the C- and N-Arylation of Oxindoles

    PubMed Central

    Altman, Ryan A.; Hyde, Alan M.; Huang, Xiaohua; Buchwald, Stephen L.

    2008-01-01

    In the cross-coupling reactions of unprotected oxindoles with aryl halides, Pd- and Cu-based catalyst systems displayed orthogonal chemoselectivity. A Pd/dialkylbiarylphosphine-based catalyst system chemoselectively arylated oxindole at the 3-position, while arylation occurred exclusively at the nitrogen using a Cu/diamine-based catalyst system. Computational examination of the relevant L1Pd(Ar)(oxindolate) and diamine-Cu-(oxindolate) species were performed to gain mechanistic insight into the controlling features of the observed chemoselectivity. PMID:18588302

  2. Heterogeneous Catalytic Conversion of Dry Syngas to Ethanol and Higher Alcohols on Cu-Based Catalysts

    SciTech Connect

    Gupta, Mayank; Smith, Miranda L.; Spivey, James J.

    2011-04-19

    Ethanol and higher alcohols have been identified as potential fuel additives or hydrogen carriers for use in fuel cells. One method of ethanol production is catalytic conversion of syngas (a mixture of CO, H₂, CO₂, and H₂O), derived from biomass, coal, or natural gas. Thermodynamics of CO hydrogenation shows that ethanol is favored as the sole product at conditions of practical interest, but if methane is allowed as product in this analysis, essentially no ethanol is formed at equilibrium. The kinetics of ethanol formation must therefore be maximized. Although rhodium-based catalysts give C{sup 2+} oxygenates with high selectivity, their prohibitive cost has spurred research on less expensive copper-based alternatives. Copper-based catalysts require an optimum amount of promoter to suppress undesired reactions and maximize the yields of ethanol and higher alcohols. Common promoters include alkali, transition metals and their oxides, and rare earth oxides. Careful selection of operating variables is also necessary to achieve the desired activity and selectivity. This review describes the effects of promoters, supports, and operating conditions on the performance of copper-based catalysts for conversion of dry syngas to ethanol and higher alcohols. Proposed mechanisms from the literature for ethanol and higher-alcohol synthesis are outlined.

  3. System for reactivating catalysts

    SciTech Connect

    Ginosar, Daniel M.; Thompson, David N.; Anderson, Raymond P.

    2010-03-02

    A method of reactivating a catalyst, such as a solid catalyst or a liquid catalyst is provided. The method comprises providing a catalyst that is at least partially deactivated by fouling agents. The catalyst is contacted with a fluid reactivating agent that is at or above a critical point of the fluid reactivating agent and is of sufficient density to dissolve impurities. The fluid reactivating agent reacts with at least one fouling agent, releasing the at least one fouling agent from the catalyst. The at least one fouling agent becomes dissolved in the fluid reactivating agent and is subsequently separated or removed from the fluid reactivating agent so that the fluid reactivating agent may be reused. A system for reactivating a catalyst is also disclosed.

  4. Plasmatron-catalyst system

    SciTech Connect

    Bromberg, Leslie; Cohn, Daniel R.; Rabinovich, Alexander; Alexeev, Nikolai

    2007-10-09

    A plasmatron-catalyst system. The system generates hydrogen-rich gas and comprises a plasmatron and at least one catalyst for receiving an output from the plasmatron to produce hydrogen-rich gas. In a preferred embodiment, the plasmatron receives as an input air, fuel and water/steam for use in the reforming process. The system increases the hydrogen yield and decreases the amount of carbon monoxide.

  5. Plasmatron-catalyst system

    DOEpatents

    Bromberg, Leslie; Cohn, Daniel R.; Rabinovich, Alexander; Alexeev, Nikolai

    2004-09-21

    A plasmatron-catalyst system. The system generates hydrogen-rich gas and comprises a plasmatron and at least one catalyst for receiving an output from the plasmatron to produce hydrogen-rich gas. In a preferred embodiment, the plasmatron receives as an input air, fuel and water/steam for use in the reforming process. The system increases the hydrogen yield and decreases the amount of carbon monoxide.

  6. Catalyst system comprising a first catalyst system tethered to a supported catalyst

    DOEpatents

    Angelici, Robert J.; Gao, Hanrong

    1998-08-04

    The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilation, olefin oxidation, isomerization, hydrocyanation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical.

  7. Catalyst system comprising a first catalyst system tethered to a supported catalyst

    DOEpatents

    Angelici, R.J.; Gao, H.

    1998-08-04

    The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilication, olefin oxidation, isomerization, hydrocyanidation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical. 2 figs.

  8. Catalyst systems and uses thereof

    DOEpatents

    Ozkan, Umit S [Worthington, OH; Holmgreen, Erik M [Columbus, OH; Yung, Matthew M [Columbus, OH

    2012-07-24

    A method of carbon monoxide (CO) removal comprises providing an oxidation catalyst comprising cobalt supported on an inorganic oxide. The method further comprises feeding a gaseous stream comprising CO, and oxygen (O.sub.2) to the catalyst system, and removing CO from the gaseous stream by oxidizing the CO to carbon dioxide (CO.sub.2) in the presence of the oxidation catalyst at a temperature between about 20 to about 200.degree. C.

  9. HERFD-XANES and XES as complementary operando tools for monitoring the structure of Cu-based zeolite catalysts during NOx-removal by ammonia SCR

    NASA Astrophysics Data System (ADS)

    Günter, T.; Doronkin, D. E.; Carvalho, H. W. P.; Casapu, M.; Grunwaldt, J.-D.

    2016-05-01

    In this article, we demonstrate the potential of hard X-ray techniques to characterize catalysts under working conditions. Operando high energy resolution fluorescence detected (HERFD) XANES and valence to core (vtc) X-ray emission spectroscopy (XES) have been used in a spatially-resolved manner to study Cu-zeolite catalysts during the standard-SCR reaction and related model conditions. The results show a gradient in Cu oxidation state and coordination along the catalyst bed as the reactants are consumed. Vtc-XES gives complementary information on the direct adsorption of ammonia at the Cu sites. The structural information on the catalyst shows the suitability of X-ray techniques to understand catalytic reactions and to facilitate catalyst optimization.

  10. Catalyst for microelectromechanical systems microreactors

    DOEpatents

    Morse, Jeffrey D [Martinez, CA; Sopchak, David A [Livermore, CA; Upadhye, Ravindra S [Pleasanton, CA; Reynolds, John G [San Ramon, CA; Satcher, Joseph H [Patterson, CA; Gash, Alex E [Brentwood, CA

    2011-11-15

    A microreactor comprising a silicon wafer, a multiplicity of microchannels in the silicon wafer, and a catalyst coating the microchannels. In one embodiment the catalyst coating the microchannels comprises a nanostructured material. In another embodiment the catalyst coating the microchannels comprises an aerogel. In another embodiment the catalyst coating the microchannels comprises a solgel. In another embodiment the catalyst coating the microchannels comprises carbon nanotubes.

  11. Catalyst for microelectromechanical systems microreactors

    DOEpatents

    Morse, Jeffrey D [Martinez, CA; Sopchak, David A [Livermore, CA; Upadhye, Ravindra S [Pleasanton, CA; Reynolds, John G [San Ramon, CA; Satcher, Joseph H [Patterson, CA; Gash, Alex E [Brentwood, CA

    2010-06-29

    A microreactor comprising a silicon wafer, a multiplicity of microchannels in the silicon wafer, and a catalyst coating the microchannels. In one embodiment the catalyst coating the microchannels comprises a nanostructured material. In another embodiment the catalyst coating the microchannels comprises an aerogel. In another embodiment the catalyst coating the microchannels comprises a solgel. In another embodiment the catalyst coating the microchannels comprises carbon nanotubes.

  12. Thick film electroluminescent lamps on ZnS, Cu base and their application in safety systems

    NASA Astrophysics Data System (ADS)

    Ciez, Michal; Porada, Zbigniew W.

    2004-08-01

    The paper presents known for above 60 years phenomenon of intrinsic electroluminescence and its practical use in modern light sources called light emitting capacitors or electroluminescent lamps. Applying polymer thick film technology the authors have realized multilayer electroluminescent structures (Destriau cells). The influence of various constructional factors and exploitational conditions (supplying voltage, temperature) on luminance level of structures was determined. The test results achieved are presented in the diagrams and tables. A few examples of applications of electroluminescent lamps in emergency and warning systems are reported.

  13. Synergy in Lignin Upgrading by a Combination of Cu-Based Mixed Oxide and Ni-Phosphide Catalysts in Supercritical Ethanol

    PubMed Central

    2017-01-01

    The depolymerization of lignin to bioaromatics usually requires a hydrodeoxygenation (HDO) step to lower the oxygen content. A mixed Cu–Mg–Al oxide (CuMgAlOx) is an effective catalyst for the depolymerization of lignin in supercritical ethanol. We explored the use of Ni-based cocatalysts, i.e. Ni/SiO2, Ni2P/SiO2, and Ni/ASA (ASA = amorphous silica alumina), with the aim of combining lignin depolymerization and HDO in a single reaction step. While the silica-supported catalysts were themselves hardly active in lignin upgrading, Ni/ASA displayed comparable lignin monomer yield as CuMgAlOx. A drawback of using an acidic support is extensive dehydration of the ethanol solvent. Instead, combining CuMgAlOx with Ni/SiO2 and especially Ni2P/SiO2 proved to be effective in increasing the lignin monomer yield, while at the same time reducing the oxygen content of the products. With Ni2P/SiO2, the lignin monomer yield was 53 wt %, leading to nearly complete deoxygenation of the aromatic products. PMID:28405528

  14. Supported catalyst systems and method of making biodiesel products using such catalysts

    DOEpatents

    Kim, Manhoe; Yan, Shuli; Salley, Steven O.; Ng, K. Y. Simon

    2015-10-20

    A heterogeneous catalyst system, a method of preparing the catalyst system and a method of forming a biodiesel product via transesterification reactions using the catalyst system is disclosed. The catalyst system according to one aspect of the present disclosure represents a class of supported mixed metal oxides that include at least calcium oxide and another metal oxide deposited on a lanthanum oxide or cerium oxide support. Preferably, the catalysts include CaO--CeO.sub.2ZLa.sub.2O.sub.3 or CaO--La.sub.2O.sub.3/CeO.sub.2. Optionally, the catalyst may further include additional metal oxides, such as CaO--La.sub.2O.sub.3--GdOxZLa.sub.2O.sub.3.

  15. Process of activation of a palladium catalyst system

    SciTech Connect

    Sobolevskiy, Anatoly; Rossin, Joseph A.; Knapke, Michael J.

    2011-08-02

    Improved processes for activating a catalyst system used for the reduction of nitrogen oxides are provided. In one embodiment, the catalyst system is activated by passing an activation gas stream having an amount of each of oxygen, water vapor, nitrogen oxides, and hydrogen over the catalyst system and increasing a temperature of the catalyst system to a temperature of at least 180.degree. C. at a heating rate of from 1-20.degree./min. Use of activation processes described herein leads to a catalyst system with superior NOx reduction capabilities.

  16. Ba3Cr2O8, a new non-Cu based quantum s=1/2 spin singlet system

    NASA Astrophysics Data System (ADS)

    Kofu, Maiko

    2009-03-01

    Field-induced condensation of magnons has been experimentally observed in several weakly coupled quantum (s = 1/2) dimer systems that are based on Cu^2+ ions, such as TlCuCl3 and BaCuSi2O6, and it has been adequately described by the Bose-Einstein condensation (BEC) theory. However, the robustness of such descriptions can only be truly evaluated with investigation into complementary materials, in particular materials that are based on non-Cu^2+ ions. Recently, a new spin dimer system, Ba3Cr2O8 has been found, where Cr^5+ (s=1/2) ion with the unusual 5+ electronic valence forms quantum dimers along the c-axis and a frustrating triangular lattice in the ab-plane. Using elastic and inelastic neutron scattering measurements on single crystals and a powder sample, we have characterized the magnetic interactions to show that Ba3Cr2O8 is indeed an excellent model system of weakly coupled quantum dimers [1]. We have also investigated the field-induced condensation of magnons in this compound, using specific heat, bulk magnetization, and elastic neutron scattering measurements under an external magnetic field. The experimental results and comparison to the theories will be discussed. *This work is in collaboration with J.-H. Kim, S. Ji, S.-H. Lee (University of Virginia), H. Ueda, Y. Ueda (ISSP, University of Tokyo), H. Nojiri (IMR, Tohoku University), B. Lake, K. Rule (Helmholtz Centre Berlin). [4pt] [1] M. Kofu et al., cond-mat/0809.5069 (2008).

  17. Correlation between viscous-flow activation energy and phase diagram in four systems of Cu-based alloys

    NASA Astrophysics Data System (ADS)

    Ning, Shuang; Bian, Xiufang; Ren, Zhenfeng

    2010-09-01

    Activation energy is obtained from temperature dependence of viscosities by means of a fitting to the Arrhenius equation for liquid alloys of Cu-Sb, Cu-Te, Cu-Sn and Cu-Ag systems. We found that the changing trend of activation energy curves with concentration is similar to that of liquidus in the phase diagrams. Moreover, a maximum value of activation energy is in the composition range of the intermetallic phases and a minimum value of activation energy is located at the eutectic point. The correlation between the activation energy and the phase diagrams has been further discussed.

  18. Multi-stage catalyst systems and uses thereof

    DOEpatents

    Ozkan, Umit S [Worthington, OH; Holmgreen, Erik M [Columbus, OH; Yung, Matthew M [Columbus, OH

    2009-02-10

    Catalyst systems and methods provide benefits in reducing the content of nitrogen oxides in a gaseous stream containing nitric oxide (NO), hydrocarbons, carbon monoxide (CO), and oxygen (O.sub.2). The catalyst system comprises an oxidation catalyst comprising a first metal supported on a first inorganic oxide for catalyzing the oxidation of NO to nitrogen dioxide (NO.sub.2), and a reduction catalyst comprising a second metal supported on a second inorganic oxide for catalyzing the reduction of NO.sub.2 to nitrogen (N.sub.2).

  19. CATALYSTS NHI Thermochemical Systems FY 2009 Year-End Report

    SciTech Connect

    Daniel M. Ginosar

    2009-09-01

    Fiscal Year 2009 work in the Catalysts project focused on advanced catalysts for the decomposition of sulfuric acid, a reaction common to both the Sulfur-Iodine (S-I) cycle and the Hybrid Sulfur cycle. Prior years’ effort in this project has found that although platinum supported on titanium oxide will be an acceptable catalyst for sulfuric acid decomposition in the integrated laboratory scale (ILS) project, the material has short comings, including significant cost and high deactivation rates due to sintering and platinum evaporation. For pilot and larger scale systems, the catalyst stability needs to be improved significantly. In Fiscal Year 2008 it was found that at atmospheric pressure, deactivation rates of a 1 wt% platinum catalyst could be reduced by 300% by adding either 0.3 wt% iridium (Ir) or 0.3 wt% ruthenium (Ru) to the catalyst. In Fiscal Year 2009, work focused on examining the platinum group metal catalysts activity and stability at elevated pressures. In addition, simple and complex metal oxides are known to catalyze the sulfuric acid decomposition reaction. These metal oxides could offer activities comparable to platinum but at significantly reduced cost. Thus a second focus for Fiscal Year 2009 was to explore metal oxide catalysts for the sulfuric acid decomposition reaction. In Fiscal Year 2007 several commercial activated carbons had been identified for the HI decomposition reaction; a reaction specific to the S-I cycle. Those materials should be acceptable for the pilot scale project. The activated carbon catalysts have some disadvantages including low activity at the lower range of reactor operating temperature (350 to 400°C) and a propensity to generate carbon monoxide in the presence of water that could contaminate the hydrogen product, but due to limited funding, this area had low priority in Fiscal Year 2009. Fiscal Year 2009 catalyst work included five tasks: development, and testing of stabilized platinum based H2SO4 catalysts

  20. Stability of a Bifunctional Cu-Based Core@Zeolite Shell Catalyst for Dimethyl Ether Synthesis Under Redox Conditions Studied by Environmental Transmission Electron Microscopy and In Situ X-Ray Ptychography.

    PubMed

    Baier, Sina; Damsgaard, Christian D; Klumpp, Michael; Reinhardt, Juliane; Sheppard, Thomas; Balogh, Zoltan; Kasama, Takeshi; Benzi, Federico; Wagner, Jakob B; Schwieger, Wilhelm; Schroer, Christian G; Grunwaldt, Jan-Dierk

    2017-06-01

    When using bifunctional core@shell catalysts, the stability of both the shell and core-shell interface is crucial for catalytic applications. In the present study, we elucidate the stability of a CuO/ZnO/Al2O3@ZSM-5 core@shell material, used for one-stage synthesis of dimethyl ether from synthesis gas. The catalyst stability was studied in a hierarchical manner by complementary environmental transmission electron microscopy (ETEM), scanning electron microscopy (SEM) and in situ hard X-ray ptychography with a specially designed in situ cell. Both reductive activation and reoxidation were applied. The core-shell interface was found to be stable during reducing and oxidizing treatment at 250°C as observed by ETEM and in situ X-ray ptychography, although strong changes occurred in the core on a 10 nm scale due to the reduction of copper oxide to metallic copper particles. At 350°C, in situ X-ray ptychography indicated the occurrence of structural changes also on the µm scale, i.e. the core material and parts of the shell undergo restructuring. Nevertheless, the crucial core-shell interface required for full bifunctionality appeared to remain stable. This study demonstrates the potential of these correlative in situ microscopy techniques for hierarchically designed catalysts.

  1. Catalyst system for the polymerization of alkenes to polyolefins

    DOEpatents

    Miller, Stephen A.; Bercaw, John E.

    2002-01-01

    The invention provides metallocene catalyst systems for the controlled polymerization of alkenes to a wide variety of polyolefins and olefin coplymers. Catalyst systems are provided that specifically produce isotactic, syndiotactic and steroblock polyolefins. The type of polymer produced can be controlled by varying the catalyst system, specifically by varying the ligand substituents. Such catalyst systems are particularly useful for the polymerization of polypropylene to give elastomeric polypropylenes. The invention also provides novel elastomeric polypropylene polymers characterized by dyad (m) tacticities of about 55% to about 65%, pentad (mmmm) tacticities of about 25% to about 35%, molecular weights (M.sub.w)in the range of about 50,000 to about 2,000,000, and have mmrm+rrmr peak is less than about 5%.

  2. Catalyst system for the polymerization of alkenes to polyolefins

    DOEpatents

    Miller, Stephen A.; Bercaw, John E.

    2004-02-17

    The invention provides metallocene catalyst systems for the controlled polymerization of alkenes to a wide variety of polyolefins and olefin coplymers. Catalyst systems are provided that specifically produce isotactic, syndiotactic and steroblock polyolefins. The type of polymer produced can be controlled by varying the catalyst system, specifically by varying the ligand substituents. Such catalyst systems are particularly useful for the polymerization of polypropylene to give elastomeric polypropylenes. The invention also provides novel elastomeric polypropylene polymers characterized by dyad (m) tacticities of about 55% to about 65%, pentad (mmmm) tacticities of about 25% to about 35%, molecular weights (M.sub.W) in the range of about 50,000 to about 2,000,000, and have mmrm+rrmr peak is less than about 5%.

  3. Low temperature catalyst system for methanol production

    DOEpatents

    Sapienza, R.S.; Slegeir, W.A.; O'Hare, T.E.

    1984-04-20

    This patent discloses a catalyst and process useful at low temperatures (150/sup 0/C) and preferably in the range 80 to 120/sup 0/C used in the production of methanol from carbon monoxide and hydrogen. The catalyst components are used in slurry form and comprise (1) a complex reducing agent derived from the component structure NaH-ROH-M(OAc)/sub 2/ where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1 to 6 carbon atoms and (2) a metal carbonyl of a group VI (Mo, Cr, W) metal. For the first component, Nic is preferred (where M = Ni and R = tertiary amyl). For the second component, Mo(CO)/sub 6/ is preferred. The mixture is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

  4. Oxidation catalyst

    DOEpatents

    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.

  5. Cathodic catalysts in bioelectrochemical systems for energy recovery from wastewater.

    PubMed

    Liu, Xian-Wei; Li, Wen-Wei; Yu, Han-Qing

    2014-11-21

    Bioelectrochemical systems (BESs), in which microorganisms are utilized as a self-regenerable catalyst at the anode of an electrochemical cell to directly extract electrical energy from organic matter, have been widely recognized as a promising technology for energy-efficient wastewater treatment or even for net energy generation. However, currently BES performance is constrained by poor cathode reaction kinetics. Thus, there is a strong impetus to improve the cathodic catalysis performance through proper selection and design of catalysts. This review introduces the fundamentals and current development status of various cathodic catalysts (including electrocatalysts, photoelectrocatalysts and bioelectrocatalysts) in BES, identifies their limitations and influential factors, compares their catalytic performances in terms of catalytic efficiency, stability, selectivity, etc., and discusses the possible optimization strategies and future research directions. Special focus is given on the analysis of how the catalytic performance of different catalysts can be improved by fine tuning their physicochemical or physiological properties.

  6. Catalysts for portable, solid state hydrogen genration systems

    NASA Astrophysics Data System (ADS)

    Gabl, Jason Robert

    Hydrogen and air powered proton exchange membrane fuel cells are a potential alternative to batteries. In portable power systems, the design requirements often focus on cost efficiency, energy density, storability, as well as safety. Ammonia borane (AB), a chemical hydride containing 19.6 wt. % hydrogen, has a high hydrogen capacity and is a stable and non-toxic candidate for storing hydrogen in portable systems. Throughout this work, Department of Energy guidelines for low power portable hydrogen power systems were used as a baseline and comparison with commercially available systems. In order to make this comparison, the system parameters of a system using AB hydrolysis were estimated by developing capacity and cost correlations from the commercial systems and applying them to this work. Supporting experiments were designed to evaluate a system that would use a premixed solid storage bed of AB and a catalyst. This configuration would only require a user input of water in order to initiate the hydrogen production. Using ammonia borane hydrolysis, the hydrogen yield is ˜9 wt. %, when all reactants are considered. In addition to the simplicity of initiating the reaction, hydrolysis of AB has the advantage of suppressing the production of some toxic borazines that are present when AB is thermally decomposed. However, ammonia gas will be formed and this problem must be addressed, as ammonia is damaging to PEM fuel cells. The catalyst focused on throughout this work was Amberlyst - 15; an ion exchange resin with an acid capacity of 4.7 eq/kg and ammonia adsorbent. At less than 0.30/g, this is a cost effective alternative to precious metal catalysts. The testing with this catalyst was compared to a traditional catalyst in literature, 20% platinum in carbon, costing more than 40/g. The Amberlyst catalyst was found to reduce the formation of ammonia in the gas products from ˜3.71 wt. % with the Pt/C catalyst to <0.01 wt. %. Since Amberlyst adsorbs ammonia, it acts as a

  7. Methods of producing epoxides from alkenes using a two-component catalyst system

    SciTech Connect

    Kung, Mayfair C.; Kung, Harold H.; Jiang, Jian

    2013-07-09

    Methods for the epoxidation of alkenes are provided. The methods include the steps of exposing the alkene to a two-component catalyst system in an aqueous solution in the presence of carbon monoxide and molecular oxygen under conditions in which the alkene is epoxidized. The two-component catalyst system comprises a first catalyst that generates peroxides or peroxy intermediates during oxidation of CO with molecular oxygen and a second catalyst that catalyzes the epoxidation of the alkene using the peroxides or peroxy intermediates. A catalyst system composed of particles of suspended gold and titanium silicalite is one example of a suitable two-component catalyst system.

  8. A Primer for the NEWBASIC/CATALYST System.

    ERIC Educational Resources Information Center

    Dwyer, Thomas A.; And Others

    Assuming no previous experience with computers, this primer is designed to help students, teachers, scientists, and other scholars to learn how to use the NEWBASIC/CATALYST system (NBS). The primer contains nine sections: (1) instructions for establishing contact with the computer (logging on); (2) examples and problems to lead the student through…

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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Technical Reports Server (NTRS)

    Watkins, Anthony N. (Inventor); Leighty, Bradley D. (Inventor); Oglesby, Donald M. (Inventor); Ingram, 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.

  11. Reducing fischer-tropsch catalyst attrition losses in high agitation reaction systems

    DOEpatents

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    2001-01-01

    A method for reducing catalyst attrition losses in hydrocarbon synthesis processes conducted in high agitation reaction systems; a method of producing an attrition-resistant catalyst; a catalyst produced by such method; a method of producing an attrition-resistant catalyst support; and a catalyst support produced by such method. The inventive method of reducing catalyst attrition losses comprises the step of reacting a synthesis gas in a high agitation reaction system in the presence of a catalyst. In one aspect, the catalyst preferably comprises a .gamma.-alumina support including an amount of titanium effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support which has been treated, after calcination, with an acidic, aqueous solution. The acidic aqueous solution preferably has a pH of not more than about 5. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support wherein the cobalt has been applied to the .gamma.-alumina support by totally aqueous, incipient wetness-type impregnation. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support with an amount of a lanthana promoter effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support produced from boehmite having a crystallite size, in the 021 plane, in the range of from about 30 to about 55 .ANG.ngstrons. In another aspect, the inventive method of producing an attrition-resistant catalyst comprises the step of treating a .gamma.-alumina support, after calcination of and before adding catalytic material to the support, with an acidic solution effective for increasing the attrition resistance of the catalyst. In another aspect, the inventive method of producing an attrition-resistant catalyst support comprises the step of treating calcined .gamma.-alumina with an acidic, aqueous

  12. Photo-oxidation catalysts

    DOEpatents

    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.

  13. ENVIRONMENTAL TECHNOLOGY VERIFICATION, TEST REPORT OF MOBILE SOURCE EMISSIONS CONTROL DEVICES/CLEAN DIESEL TECHNOLOGIES FUEL BORNE CATALYST WITH CLEANAIR SYSTEM'S DIESEL OXIDATION CATALYST

    EPA Science Inventory

    The Environmental Technology Verification report discusses the technology and performance of the Fuel-Borne Catalyst with CleanAir System's Diesel Oxidation Catalyst manufactured by Clean Diesel Technologies, Inc. The technology is a fuel-borne catalyst used in ultra low sulfur d...

  14. ENVIRONMENTAL TECHNOLOGY VERIFICATION, TEST REPORT OF MOBILE SOURCE EMISSIONS CONTROL DEVICES/CLEAN DIESEL TECHNOLOGIES FUEL BORNE CATALYST WITH CLEANAIR SYSTEM'S DIESEL OXIDATION CATALYST

    EPA Science Inventory

    The Environmental Technology Verification report discusses the technology and performance of the Fuel-Borne Catalyst with CleanAir System's Diesel Oxidation Catalyst manufactured by Clean Diesel Technologies, Inc. The technology is a fuel-borne catalyst used in ultra low sulfur d...

  15. Self-Supported Cu-Based Nanowire Arrays as Noble-Metal-Free Electrocatalysts for Oxygen Evolution.

    PubMed

    Hou, Chun-Chao; Fu, Wen-Fu; Chen, Yong

    2016-08-23

    Crystalline Cu-based nanowire arrays (NWAs) including Cu(OH)2 , CuO, Cu2 O, and CuOx are facilely grown on Cu foil and are found to act as highly efficient, low-cost, and robust electrocatalysts for the oxygen evolution reaction (OER). Impressively, this noble-metal-free 3 D Cu(OH)2 -NWAs/Cu foil electrode shows the highest catalytic activity with a Tafel slope of 86 mV dec(-1) , an overpotential (η) of about 530 mV at ∼10 mA cm(-2) (controlled-potential electrolysis method without iR correction) and almost 100 % Faradic efficiency, paralleling the performance of the state-of-the-art RuO2 OER catalyst in 0.1 m NaOH solution (pH 12.8). To the best of our knowledge, this work represents one of the best results ever reported on Cu-based OER systems.

  16. CATALYST ACTIVITY MAINTENANCE FOR THE LIQUID PHASE SYNTHESIS GAS-TO-DIMETHYL ETHER PROCESS PART II: DEVELOPMENT OF ALUMINUM PHOSPHATE AS THE DEHYDRATION CATALYST FOR THE SINGLE-STEP LIQUID PHASE SYNGAS-TO-DME PROCESS

    SciTech Connect

    Xiang-Dong Peng

    2002-05-01

    At the heart of the single-step liquid phase syngas-to-DME process (LPDME{trademark}) is a catalyst system that can be active as well as stable. In the Alternative Fuels I program, a dual-catalyst system containing a Cu-based commercial methanol synthesis catalyst (BASF S3-86) and a commercial dehydration material ({gamma}-alumina) was demonstrated. It provided the productivity and selectivity expected from the LPDME process. However, the catalyst system deactivated too rapidly to warrant a viable commercial process [1]. The mechanistic investigation in the early part of the DOE's Alternative Fuels II program revealed that the accelerated catalyst deactivation under LPDME conditions is due to detrimental interaction between the methanol synthesis catalyst and methanol dehydration catalyst [2,3]. The interaction was attributed to migration of Cu- and/or Zn-containing species from the synthesis catalyst to the dehydration catalyst. Identification of a dehydration catalyst that did not lead to this detrimental interaction while retaining adequate dehydration activity was elusive. Twenty-nine different dehydration materials were tested, but none showed the desired performance [2]. The search came to a turning point when aluminum phosphate was tested. This amorphous material is prepared by precipitating a solution containing Al(NO{sub 3}){sub 3} and H{sub 3}PO{sub 4} with NH{sub 4}OH, followed by washing, drying and calcination. The aluminum phosphate catalyst has adequate dehydration activity and good stability. It can co-exist with the Cu-based methanol synthesis catalyst without negatively affecting the latter catalyst's stability. This report documents the details of the development of this catalyst. These include initial leads, efforts in improving activity and stability, investigation and development of the best preparation parameters and procedures, mechanistic understanding and resulting preparation guidelines, and the accomplishments of this work.

  17. Novel catalysts and photoelectrochemical system for solar fuel production

    NASA Astrophysics Data System (ADS)

    Zhang, Yan

    Solar fuel production from abundant raw chemicals such as CO2 and water is highly desired as a clean renewable energy solution for the future. Developing photoelectrochemical cells is viewed as a promising approach to realize this energy conversion and storage process. Efficient and robust oxygen evolution catalyst made from non-precious materials remains a major challenge for such a system. This thesis basically consists of three parts of work, including studies on enhancing the photocatalytic oxygen evolution activity of cobalt-based spinel nanoparticles by manganese3+ substitution, in situ formation of cobalt oxide nanocubanes as highly active catalyst for photocatalytic oxygen evolution reaction, and development of a photoanode-driven photoelectrochemical cell for CO2 reduction with water. The first part of this thesis work devotes efforts in the development and study on cobalt and other transition metal oxide based oxygen evolution catalyst. Photocatalytic oxygen evolution is a critical step for solar fuel production from abundant sources. It poses a significant challenge because it requires an efficient catalyst to bridge the one-electron photon capture process with the four-electron oxygen reaction. Among all the metal oxides, Co3O4 spinel exhibits a high activity as an oxygen evolution catalyst. The results of this work demonstrate that the photocatalytic oxygen evolution activity of Co3O4 spinel can be further enhanced by substituting Co with Mn in the spinel structure. Using a facile hydrothermal approach, Co3O4 spinel nanoparticles as well as Mn-substituted and Ni-substituted Co3O4 spinel nanoparticles with a typical particle size of 5-7 nm were successfully synthesized. The morphology and crystal structures of the as-synthesized nanoparticle catalysts have been carefully examined using various structural characterization techniques, including powder x-ray diffraction (PXRD), transmission electron microscope (TEM), gas adsorption, and x-ray absorption

  18. Application of a knowledge-based expert system for assisting in catalyst design

    SciTech Connect

    Koerting, E.; Baerns, M.

    1997-12-31

    The prototype expert system ESYCAD (expert system for catalyst design) was set up for assisting in the design of heterogeneous catalysts. It selects materials as catalyst components which have all required properties for the various (elementary) steps of a target reaction but which do not catalyze undesired side reactions. If necessary, also secondary catalytic components of promoters are selected; furthermore, reaction conditions are proposed if required by catalyst properties. The application of the system is illustrated by examples for CO-hydrogenation, alkane dehydrogenation, and for oxidative coupling of methane.

  19. Water-gas shift on gold catalysts: catalyst systems and fundamental studies.

    PubMed

    Tao, Franklin Feng; Ma, Zhen

    2013-10-07

    Since the pioneering finding by Haruta et al. that small gold nanoparticles on reducible supports can be highly active for low-temperature CO oxidation, the synthesis, characterization, and application of supported gold catalysts have attracted much attention. The water-gas shift reaction (WGSR: CO + H2O = CO2 + H2) is important for removing CO and upgrading the purity of H2 for fuel cell applications, ammonia synthesis, and selective hydrogenation processes. In recent years, much attention has been paid to exploration the possibility of using supported gold nanocatalysts for WGSR and understanding the fundamental aspects related to catalyst deactivation mechanisms, nature of active sites, and reaction mechanisms. Here we summarize recent advances in the development of supported gold catalysts for this reaction and fundamental insights that can be gained, and furnish our assessment on the status of research progress.

  20. Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations

    DOEpatents

    Elliot, Douglas C.; Werpy, Todd A.; Wang, Yong; Frye, Jr., John G.

    2001-01-01

    An essentially nickel- and rhenium-free catalyst is described comprising ruthenium on a titania support where the titania is greater than 75% rutile. A catalytic system containing a nickel-free catalyst comprising ruthenium on a titania support where the titania is greater than 75% rutile, and a method using this catalyst in the hydrogenation of an organic compound in the aqueous phase is also described.

  1. Low-temperature NOx reduction processes using combined systems of pulsed corona discharge and catalysts

    NASA Astrophysics Data System (ADS)

    Kim, H. H.; Takashima, K.; Katsura, S.; Mizuno, A.

    2001-02-01

    In this paper, we will report NOx removal via reduction processes using two types of combined system of pulse corona discharge and catalysts: the single-stage plasma-driven catalyst (PDC) system, and the two-stage plasma-enhanced selective catalytic reduction (PE-SCR) system. Several catalysts, such as γ-alumina catalysts, mechanically mixed catalysts of γ-alumina with BaTiO3 or TiO2, and Co-ZSM-5 were tested. In the PDC system, which is directly activated by the discharge plasma, it was found that the use of additives was necessary to achieve NOx removal by reduction. Removal rates of NO and NOx were linearly increased as the molar ratio of additive to NOx increased. The dependence of NO and NOx removal on the gas hourly space velocity (GHSV) at a fixed specific input energy (SIE) indicates that plasma-induced surface reaction on the catalyst plays an important role in the PDC system. It was found that the optimal GHSV of the PDC system with the γ-alumina catalyst was smaller than 6000 h-1. Mechanical mixing of γ-alumina with BaTiO3 or TiO2 did not enhance NO and NOx removal and γ-alumina alone was found to be the most suitable catalyst. The dielectric constant of the catalyst only influenced the plasma intensity, not the NOx removal. In the PE-SCR system, plasma-treated NOx (mostly NO2) was reduced effectively with NH3 over the Co-ZSM-5 catalyst at a relatively low temperature of 150 °C. Under optimal conditions the energy cost and energy yield were 25 eV/molecule and 21 g-N (kWh)-1, respectively.

  2. Non-precious bimetallic catalysts for selective dehydrogenation of an organic chemical hydride system.

    PubMed

    Al-ShaikhAli, Anaam H; Jedidi, Abdesslem; Cavallo, Luigi; Takanabe, Kazuhiro

    2015-08-21

    Methylcyclohexane (MCH)-toluene (TOL) chemical hydride cycles as hydrogen carrier systems are successful with the selective dehydrogenation of MCH to TOL, which has been achieved only using precious Pt-based catalysts. Herein, we report improved selectivity using non-precious metal nickel-based bimetallic catalysts, where the second metal occupies the unselective step sites.

  3. Development of micro-cogeneration system with porous catalyst microcombustor

    NASA Astrophysics Data System (ADS)

    Takahashi, S.; Tanaka, M.; Ieda, N.; Ihara, T.

    2015-10-01

    A self-standing micro-cogeneration system was developed by coupling a microcombustor, thermoelectric (TE) modules, and an air supply device. The microcombustor has a porous monolithic Pt catalyst layer, and a combustion efficiency of 90% was achieved. A microblower is used to supply air to the combustor, and it is driven by electricity from the Bi-Te TE modules through a dc-dc converter. We investigated the optimal point where the output became maximal and the system was self-standing. At the optimal point, the input fuel enthalpy was 13.2 W, and 440 mW of electricity was generated from the TE modules. The microblower consumed 280 mW, and the net generated electricity was 160 mW. Therefore, the final thermal efficiency was 1.21%. The net thermal efficiency of the developed system was the same magnitude as that of TeeDee01 (COX Co. Ltd.), the world’s smallest model plane engine (0.163 cc), even though the magnitude of the output power was less than 1/20 in comparison.

  4. Catalysts, systems and methods to reduce NOX in an exhaust gas stream

    DOEpatents

    Castellano, Christopher R.; Moini, Ahmad; Koermer, Gerald S.; Furbeck, Howard

    2010-07-20

    Catalysts, systems and methods are described to reduce NO.sub.x emissions of an internal combustion engine. In one embodiment, an emissions treatment system for an exhaust stream is provided having an SCR catalyst comprising silver tungstate on an alumina support. The emissions treatment system may be used for the treatment of exhaust streams from diesel engines and lean burn gasoline engines. An emissions treatment system may further comprise an injection device operative to dispense a hydrocarbon reducing agent upstream of the catalyst.

  5. PILOT TESTING OF MERCURY OXIDATION CATALYSTS FOR UPSTREAM OF WET FGD SYSTEMS

    SciTech Connect

    Gary M. Blythe

    2003-07-01

    This document summarizes progress on Cooperative Agreement DE-FC26-01NT41185, ''Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems,'' during the time-period April 1, 2003 through June 30, 2003. The objective of this project is to demonstrate at pilot scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. The project is being funded by the U.S. DOE National Energy Technology Laboratory under Cooperative Agreement DE-FC26-01NT41185. EPRI, Great River Energy (GRE), and City Public Service (CPS) of San Antonio are project cofunders. URS Group is the prime contractor. The mercury control process under development uses catalyst materials applied to honeycomb substrates to promote the oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone flue gas desulfurization (FGD) systems. Oxidized mercury is removed in the wet FGD absorbers and co-precipitates with the byproducts from the FGD system. The current project is testing previously identified, effective catalyst materials at a larger, pilot scale and in a commercial form, to provide engineering data for future full-scale designs. The pilot-scale tests will continue for approximately 14 months at each of two sites to provide longer-term catalyst life data. This is the seventh full reporting period for the subject Cooperative Agreement. During this period, project efforts included continued operation of the first pilot unit, conducting catalyst activity measurements, installing sonic horns for on-line catalyst cleaning, and installing the fourth catalyst, all for the GRE Coal Creek site. CPS began installation of the second mercury oxidation catalyst pilot unit at their Spruce Plant during the quarter. Laboratory efforts were conducted to support catalyst selection for that second pilot unit. This technical progress report provides an update on these efforts.

  6. PILOT TESTING OF MERCURY OXIDATION CATALYSTS FOR UPSTREAM OF WET FGD SYSTEMS

    SciTech Connect

    Gary M. Blythe

    2003-10-01

    This document summarizes progress on Cooperative Agreement DE-FC26-01NT41185, ''Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems,'' during the time-period July 1, 2003 through September 30, 2003. The objective of this project is to demonstrate at pilot scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. The project is being funded by the U.S. DOE National Energy Technology Laboratory under Cooperative Agreement DE-FC26-01NT41185. EPRI, Great River Energy (GRE), and City Public Service (CPS) of San Antonio are project cofunders. URS Group is the prime contractor. The mercury control process under development uses catalyst materials applied to honeycomb substrates to promote the oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone flue gas desulfurization (FGD) systems. Oxidized mercury is removed in the wet FGD absorbers and co-precipitates with the byproducts from the FGD system. The current project is testing previously identified, effective catalyst materials at a larger, pilot scale and in a commercial form, to provide engineering data for future full-scale designs. The pilot-scale tests will continue for approximately 14 months at each of two sites to provide longer-term catalyst life data. This is the eighth full reporting period for the subject Cooperative Agreement. During this period, project efforts included continued operation of the first pilot unit at the GRE Coal Creek site with all four catalysts in service and sonic horns installed for on-line catalyst cleaning. During the quarter, a catalyst activity measurement trip and mercury SCEM relative accuracy tests were completed, and catalyst pressure drop was closely monitored with the sonic horns in operation. CPS completed the installation of the second mercury oxidation catalyst pilot unit at their Spruce Plant during the quarter, and the four

  7. Reforming catalysts

    SciTech Connect

    Givens, E.N.; Plank, C.J.; Rosinski, E.J.

    1980-03-04

    Crystalline aluminosilicate zeolites are mixed with conventional reforming catalysts to produce new catalytic compositions with high catalytic activity and selectivity and excellent aging characteristics. These new catalytic compositions may be utilized alone or in conjunction with conventional reforming catalysts. The acidic activity of the total catalyst system is controlled within defined limits. When so controlled the utility of these catalyst systems in reforming hydrocarbon mixtures is to reduce the C1 and C2 concentrations in reformer gas product, while increasing the C3 and C4 concentrations and maintaining high liquid yield at high octane numbers.

  8. PILOT TESTING OF MERCURY OXIDATION CATALYSTS FOR UPSTREAM OF WET FGD SYSTEMS

    SciTech Connect

    Gary M. Blythe

    2003-05-01

    This document summarizes progress on Cooperative Agreement DE-FC26-01NT41185, ''Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems,'' during the time period January 1, 2003 through March 31, 2003. The objective of this project is to demonstrate at pilot scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. The project is being funded by the U.S. DOE National Energy Technology Laboratory under Cooperative Agreement DE-FC26-01NT41185. EPRI, Great River Energy (GRE), and City Public Service (CPS) of San Antonio are project cofunders. URS Group is the prime contractor. The mercury control process under development uses catalyst materials applied to honeycomb substrates to promote the oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone flue gas desulfurization (FGD) systems. Oxidized mercury is removed in the wet FGD absorbers and co-precipitates with the byproducts from the FGD system. The current project is testing previously identified, effective catalyst materials at a larger, pilot scale and in a commercial form, to provide engineering data for future full-scale designs. The pilot-scale tests will continue for up to 14 months at each of two sites to provide longer-term catalyst life data. This is the sixth full reporting period for the subject Cooperative Agreement. During this period, project efforts included continued operation of the pilot unit with three catalysts, conducting catalyst activity measurements, and procuring the fourth catalyst, all for the GRE Coal Creek pilot unit site. Laboratory efforts were also conducted to support catalyst selection for the second pilot unit site, at CPS' Spruce Plant. This technical progress report provides an update on these efforts.

  9. Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems

    SciTech Connect

    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-based catalyst began with almost 98

  10. Removal of ammonia from urine vapor by a dual-catalyst system

    NASA Technical Reports Server (NTRS)

    Budininkas, P.

    1977-01-01

    The feasibility of removing ammonia from urine vapor by a low-temperature dual-catalyst system has been demonstrated. The process is based on the catalytic oxidation of ammonia to a mixture of nitrogen, nitrous oxide, and water, followed by a catalytic decomposition of the nitrous oxide into its elements. Potential ammonia oxidation and nitrous oxide decomposition catalysts were first screened with artificial gas mixtures, then tested with the actual urine vapor produced by boiling untreated urine. A suitable dual-catalyst bed arrangement was found that achieved the removal of ammonia and also organic carbon, and recovered water of good quality from urine vapor.

  11. System and method for determining an ammonia generation rate in a three-way catalyst

    DOEpatents

    Sun, Min; Perry, Kevin L; Kim, Chang H

    2014-12-30

    A system according to the principles of the present disclosure includes a rate determination module, a storage level determination module, and an air/fuel ratio control module. The rate determination module determines an ammonia generation rate in a three-way catalyst based on a reaction efficiency and a reactant level. The storage level determination module determines an ammonia storage level in a selective catalytic reduction (SCR) catalyst positioned downstream from the three-way catalyst based on the ammonia generation rate. The air/fuel ratio control module controls an air/fuel ratio of an engine based on the ammonia storage level.

  12. Removal of ammonia from urine vapor by a dual-catalyst system

    NASA Technical Reports Server (NTRS)

    Budininkas, P.

    1977-01-01

    The feasibility of removing ammonia from urine vapor by a low-temperature dual-catalyst system has been demonstrated. The process is based on the catalytic oxidation of ammonia to a mixture of nitrogen, nitrous oxide, and water, followed by a catalytic decomposition of the nitrous oxide into its elements. Potential ammonia oxidation and nitrous oxide decomposition catalysts were first screened with artificial gas mixtures, then tested with the actual urine vapor produced by boiling untreated urine. A suitable dual-catalyst bed arrangement was found that achieved the removal of ammonia and also organic carbon, and recovered water of good quality from urine vapor.

  13. Exhaust system having a gold-platinum group metal catalyst

    DOEpatents

    Ragle, Christie Susan [Havana, IL; Silver, Ronald G [Peoria, IL; Zemskova, Svetlana Mikhailovna [Edelstein, IL; Eckstein, Colleen J [Metamora, IL

    2011-12-06

    A method of providing an exhaust treatment device is disclosed. The method includes applying a catalyst including gold and a platinum group metal to a particulate filter. The concentration of the gold and the platinum group metal is sufficient to enable oxidation of carbon monoxide and nitric oxide.

  14. Exhaust system having a gold-platinum group metal catalyst

    DOEpatents

    Ragle, Christie Susan; Silver, Ronald G.; Zemskova, Svetlana Mikhailovna; Eckstein, Colleen J.

    2012-08-07

    A method of providing an exhaust treatment device is disclosed. The method includes applying a catalyst including gold and a platinum group metal to a particulate filter. The concentration of the gold and the platinum group metal is sufficient to enable oxidation of carbon monoxide and nitric oxide.

  15. Hydrodemetallization and hydroconversion of Tia Juana heavy vacuum residue with dual catalyst systems

    SciTech Connect

    Zerpa, C.; Di Marco, M.P.; Galiasso, R.; Garcia, J.; Arias, B. )

    1987-04-01

    The current surplus of crude and lower prices may not last forever. In the long term, it is realized that there will be a decreasing supply of light oils, thus, it will be necessary to utilize the huge reserves of heavy crude available in Canada and Venezuela. The main drawback for the processing of these crudes is the high metal, sulfur and asphaltene content which make them not amenable for conventional refining. Metals such as nickel and vanadium, are undesirable contaminants for catalysts. As crude passes through the refinery, the metals congregate in the residues and, generally speaking, the heavier the crude the higher the metal content. In order to deal with high metals crude, they are engaged in the development of a process scheme for the upgrading of heavy crudes. The process consists of an up-flow fixed bed catalyst system with a first stage catalyst selective to hydrodemetallization followed by a thermal cracking zone and a second stage catalyst selective to hydroconversion. In the present paper, recent results of life tests to study the performance of dual catalyst systems are presented. Results of hydrodemetallization and hydroconversion of the 540{degree}c fraction of Tia Juana heavy resid are discussed. In addition, results of the screening study to select this dual catalyst system are also presented.

  16. PILOT TESTING OF MERCURY OXIDATION CATALYSTS FOR UPSTREAM OF WET FGD SYSTEMS

    SciTech Connect

    Gary M. Blythe

    2003-01-21

    This document summarizes progress on Cooperative Agreement DE-FC26-01NT41185, Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems, during the time period October 1, 2002 through December 31, 2002. The objective of this project is to demonstrate at pilot scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. The project is being funded by the U.S. DOE National Energy Technology Laboratory under Cooperative Agreement DE-FC26-01NT41185. EPRI, Great River Energy (GRE), and City Public Service (CPS) of San Antonio are project co-funders. URS Group is the prime contractor. The mercury catalytic oxidation process under development uses catalyst materials applied to honeycomb substrates to promote the oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone flue gas desulfurization (FGD) systems. Oxidized mercury is removed in the wet FGD absorbers and co-precipitates with the byproducts from the FGD system. The co-precipitated mercury does not appear to adversely affect the disposal or reuse properties of the FGD byproduct. The current project testing previously identified, effective catalyst materials at a larger, pilot scale and in a commercial form, to provide engineering data for future fullscale designs. The pilot-scale tests will continue for up to 14 months at each of two sites to provide longer-term catalyst life data. This is the fifth full reporting period for the subject Cooperative Agreement. During this period, project efforts included starting up the pilot unit with three catalysts at the first site, conducting catalyst activity measurements, completing comprehensive flue gas sampling and analyses, and procuring additional catalysts for the pilot unit. This technical progress report provides an update on these efforts.

  17. Evaluation of Bosch-Based Systems Using Non-Traditional Catalysts at Reduced Temperatures

    NASA Technical Reports Server (NTRS)

    Abney, Morgan B.; Mansell, J. Matthew

    2011-01-01

    Oxygen and water resupply make open loop atmosphere revitalization (AR) systems unfavorable for long-term missions beyond low Earth orbit. Crucial to closing the AR loop are carbon dioxide reduction systems with low mass and volume, minimal power requirements, and minimal consumables. For this purpose, NASA is exploring using Bosch-based systems. The Bosch process is favorable over state-of-the-art Sabatier-based processes due to complete loop closure. However, traditional operation of the Bosch required high reaction temperatures, high recycle rates, and significant consumables in the form of catalyst resupply due to carbon fouling. A number of configurations have been proposed for next-generation Bosch systems. First, alternative catalysts (catalysts other than steel wool) can be used in a traditional single-stage Bosch reactor to improve reaction kinetics and increase carbon packing density. Second, the Bosch reactor may be split into separate stages wherein the first reactor stage is dedicated to carbon monoxide and water formation via the reverse water-gas shift reaction and the second reactor stage is dedicated to carbon formation. A series system will enable maximum efficiency of both steps of the Bosch reaction, resulting in optimized operation and maximum carbon formation rate. This paper details the results of testing of both single-stage and two-stage Bosch systems with alternative catalysts at reduced temperatures. These results are compared to a traditional Bosch system operated with a steel wool catalyst.

  18. Mycobactericidal activity of hydrogen peroxide activated by a novel heterogeneous Fentons-like catalyst system.

    PubMed

    Price, S L; Huddersman, K D; Shen, J; Walsh, S E

    2013-02-01

    To investigate the potential activation of hydrogen peroxide by a novel catalyst, reducing the concentration of hydrogen peroxide required and the time taken for mycobactericidal activity. The mycobactericidal properties of an iron-based novel heterogeneous-modified polyacrylonitrile (PAN) catalyst in combination with hydrogen peroxide were examined against Mycobacterium chelonae using a modified version of the European suspension test. Mycobactericidal activity was significantly increased when the modified PAN catalyst was combined with hydrogen peroxide. The 0·5% w/v hydrogen peroxide and 2-g catalyst system resulted in average Log reductions of >5·80 for Myco. chelonae at 30-min exposure at room temperature. This was a significant increase in activity (P < 0·01) compared to 0·5% w/v hydrogen peroxide alone. This study has expanded on previous work and knowledge of the modified PAN catalyst and hydrogen peroxide system, by providing evidence for mycobactericidal activity when the novel PAN catalyst is combined with hydrogen peroxide. © 2012 The Society for Applied Microbiology.

  19. Full-Scale Testing of a Mercury Oxidation Catalyst Upstream of a Wet FGD System

    SciTech Connect

    Gary Blythe; Jennifer Paradis

    2010-06-30

    This document presents and discusses results from Cooperative Agreement DE-FC26-06NT42778, 'Full-scale Testing of a Mercury Oxidation Catalyst Upstream of a Wet FGD System,' which was conducted over the time-period July 24, 2006 through June 30, 2010. The objective of the project was to demonstrate at full scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in pulverized-coal-fired flue gas. Oxidized mercury is removed downstream in wet flue gas desulfurization (FGD) absorbers and collected with the byproducts from the FGD system. The project was co-funded by EPRI, the Lower Colorado River Authority (LCRA), who also provided the host site, Great River Energy, Johnson Matthey, Southern Company, Salt River Project (SRP), the Tennessee Valley Authority (TVA), NRG Energy, Ontario Power and Westar. URS Group was the prime contractor and also provided cofunding. The scope of this project included installing and testing a gold-based catalyst upstream of one full-scale wet FGD absorber module (about 200-MW scale) at LCRA's Fayette Power Project (FPP) Unit 3, which fires Powder River Basin coal. Installation of the catalyst involved modifying the ductwork upstream of one of three wet FGD absorbers on Unit 3, Absorber C. The FGD system uses limestone reagent, operates with forced sulfite oxidation, and normally runs with two FGD modules in service and one spare. The full-scale catalyst test was planned for 24 months to provide catalyst life data. Over the test period, data were collected on catalyst pressure drop, elemental mercury oxidation across the catalyst module, and mercury capture by the downstream wet FGD absorber. The demonstration period began on May 6, 2008 with plans for the catalyst to remain in service until May 5, 2010. However, because of continual increases in pressure drop across the catalyst and concerns that further increases would adversely affect Unit 3 operations, LCRA decided to end the demonstration early, during

  20. Recycling nanoparticle catalysts without separation based on a pickering emulsion/organic biphasic system.

    PubMed

    Liu, Huifang; Zhang, Zhiming; Yang, Hengquan; Cheng, Fangqin; Du, Zhiping

    2014-07-01

    A conceptually novel methodology is explored for in situ recycling of nanoparticle catalysts based on transforming a conventional organic/aqueous biphasic system into a Pickering emulsion/organic biphasic system (PEOBS). The suggested PEOBS exists as two phases, with the nanoparticle catalyst "anchored" in the Pickering emulsion phase, but is "continuous" between the organic phase and the continuous phase of the Pickering emulsion. Aqueous hydrogenations are used to evaluate the reaction performances of PEOBS, and the underlying principles of PEOBS are preliminarily elaborated. The unique properties of PEOBS lead to many intriguing findings, which are unlikely to be achieved in the reported biphasic systems. PEOBS exhibits more than a fourfold enhancement in catalysis efficiency in comparison with a conventional biphasic system. Impressively, PEOBS enables the organic product to be facilely isolated through simple decantation and the nanoparticle catalyst can be recycled in situ without the need for "separation". Its recycling effectiveness is justified by ten reaction cycles without significant catalyst loss. The simple protocol, in conjunction with the stability to simultaneously achieve high catalysis efficiency and excellent catalyst recyclability, makes PEOBS a promising methodology to develop more sustainable nanocatalysis.

  1. PILOT TESTING OF MERCURY OXIDATION CATALYSTS FOR UPSTREAM OF WET FGD SYSTEMS

    SciTech Connect

    Gary M. Blythe

    2002-10-04

    This document summarizes progress on Cooperative Agreement DE-FC26-01NT41185, Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems, during the time period July 1, 2002 through September 30, 2002. The objective of this project is to demonstrate at pilot scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. The project is being funded by the U.S. DOE National Energy Technology Laboratory under Cooperative Agreement DE-FC26-01NT41185. EPRI, Great River Energy (GRE), and City Public Service (CPS) of San Antonio are project co-funders. URS Group is the prime contractor. The mercury catalytic oxidation process under development uses catalyst materials applied to honeycomb substrates to promote the oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone flue gas desulfurization (FGD) systems. Oxidized mercury is removed in the wet FGD absorbers and co-precipitates in a stable form with the byproducts from the FGD system. The coprecipitated mercury does not appear to adversely affect the disposal or reuse properties of the FGD byproduct. The current project will test previously identified, effective catalyst materials at a larger, pilot scale and in a commercial form, so as to provide engineering data for future full-scale designs. The pilot-scale tests will continue for up to 14 months at each of two sites to provide longer-term catalyst life data. This is the fourth full reporting period for the subject Cooperative Agreement. During this period, most of the project efforts were related to completing, installing and starting up the pilot unit, completing laboratory runs to size catalysts, and procuring catalysts for the pilot unit. This technical progress report provides an update on these efforts.

  2. Environmentally-benign catalysts for the selective catalytic reduction of NO(x) from diesel engines: structure-activity relationship and reaction mechanism aspects.

    PubMed

    Liu, Fudong; Yu, Yunbo; He, Hong

    2014-08-11

    Selective catalytic reduction of NOx using NH3 or hydrocarbons (NH3-SCR or HC-SCR) in oxygen-rich exhaust from diesel engines remains a major challenge in environmental catalysis. The development of highly efficient, stable and environmentally-benign catalysts for SCR processes is very important for practical use. In this feature article, the structure-activity relationship of vanadium-free catalysts in the NH3-SCR reaction is discussed in detail, including Fe-, Ce-based oxide catalysts and Fe-, Cu-based zeolite catalysts, which is beneficial for catalyst redesign and activity improvement. Based on our research, a comprehensive mechanism contributing to the performance of Ag/Al2O3 in HC-SCR is provided, giving a clue to the design of a catalytic system with high efficiency.

  3. Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems

    SciTech Connect

    Gary M. Blythe

    2006-03-31

    This document summarizes progress on Cooperative Agreement DE-FC26-04NT41992, ''Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems'', during the time-period January 1 through March 31, 2006. The objective of this project is to demonstrate at pilot scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in flue gas from coal combustion, and the use of a wet flue gas desulfurization (FGD) system downstream to remove the oxidized mercury at high efficiency. The project is being co-funded by the U.S. DOE National Energy Technology Laboratory, EPRI, Great River Energy (GRE), TXU Generation Company LP, the Southern Company, and Duke Energy. URS Group is the prime contractor. The mercury control process under development uses honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone FGD systems. Oxidized mercury is removed in the wet FGD absorbers and leaves with the byproducts from the FGD system. The current project is testing previously identified catalyst materials at pilot scale and in a commercial form to provide engineering data for future full-scale designs. The pilot-scale tests will continue for approximately 14 months or longer at each of two sites to provide longer-term catalyst life data. Pilot-scale wet FGD tests are being conducted periodically at each site to confirm the ability to scrub the catalytically oxidized mercury at high efficiency. This is the ninth reporting period for the subject Cooperative Agreement. During this period, project efforts primarily consisted of operating the catalyst pilot units at the TXU Generation Company LP's Monticello Steam Electric Station and at Georgia Power's Plant Yates. Two catalyst activity measurement trips were made to Plant Yates during the quarter. This Technical Progress Report presents catalyst activity results from the oxidation catalyst pilot unit at Plant Yates and

  4. Catalyst system and process for benzyl ether fragmentation and coal liquefaction

    DOEpatents

    Zoeller, J.R.

    1998-04-28

    Dibenzyl ether can be readily cleaved to form primarily benzaldehyde and toluene as products, along with minor amounts of bibenzyl and benzyl benzoate, in the presence of a catalyst system comprising a Group 6 metal, preferably molybdenum, a salt, and an organic halide. Although useful synthetically for the cleavage of benzyl ethers, this cleavage also represents a key model reaction for the liquefaction of coal; thus this catalyst system and process should be useful in coal liquefaction with the advantage of operating at significantly lower temperatures and pressures.

  5. Effect of plasma-catalyst system on NO removal using M-Cu (M = Mn, Ce, Cr, Co, and Fe) catalysts

    NASA Astrophysics Data System (ADS)

    Wang, Tao; Liu, Han-Zi; Yang, Bin; Sun, Bao-Min; Xiao, Hai-Ping; Zhang, Yong-Sheng

    2016-11-01

    A series of M-Cu (M = Mn, Ce, Cr, Co, and Fe) bimetal oxide catalysts combined with plasma were prepared for NO x removal at various temperatures. All catalysts combined with plasma exhibited excellent deNO x activity. The Mn-Cu catalyst showed the highest selective catalytic reduction (SCR) activity; the NO removal efficiency of the Mn-Cu catalyst could reach 90% at a gas temperature of 25 °C. E/N increased as gas temperature increased; the mean electron energy and the proportion of high-energy electrons also increased considerably, producing more active radicals. Without any catalyst, the increase in temperature inhibited NO removal owing to O3 consumption. As the temperature increased, NO removal efficiency decreased below 100 °C however, it increased in the range of 100-300 °C, and then decreased above 300 °C in the plasma-catalyst system. NO2 concentration decreased markedly at 150 °C via the fast SCR reaction.

  6. A Highly Practical Copper(I)/TEMPO Catalyst System for Chemoselective Aerobic Oxidation of Primary Alcohols

    PubMed Central

    Hoover, Jessica M.; Stahl, Shannon S.

    2011-01-01

    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 O2 as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)CuI/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. PMID:21861488

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

    PubMed

    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. Metal-silicate catalysts: Single site, mesoporous systems without templates

    SciTech Connect

    Barnes, Craig E.; Sharp, Katherine; Albert, Austin A; Abbott, Joshua; Peretich, Michael E; Fulvio, Pasquale; Ciesielski, Peter N.; Donohoe, Bryon S.

    2015-06-01

    The textural properties of a family of silicate and mixed metal-silicate materials prepared by a nonaqueous sol-gel reaction involving the cubic silicate Si8O20(SnMe3)8 and metal chlorides MCl4 (M = Si, Ti, Zr) cross-linking reagents are described. Nitrogen adsorption isotherm data is presented and surface area and pore size distribution analyses for several examples of these materials are developed and correlated with the ratio of cross-linking reagent and the cubic silicate building block at the time of synthesis. Significant surface area and pore size distributions that shift to higher pore diameters are observed as the ratio of cross-linking reagent-to-cubic building block increases. A simple strategy for simultaneously controlling the porosity of these matrices while homogeneously dispersing identical metal centers on their surfaces for next generation catalysts is described.

  9. PILOT TESTING OF MERCURY OXIDATION CATALYSTS FOR UPSTREAM OF WET FGD SYSTEMS

    SciTech Connect

    Gary M. Blythe

    2002-07-17

    This document summarizes progress on Cooperative Agreement DE-FC26-01NT41185, Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems, during the time period April 1, 2002 through June 30, 2002. The objective of this project is to demonstrate at pilot scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. The project is being funded by the U.S. DOE National Energy Technology Laboratory under Cooperative Agreement DE-FC26-01NT41185. EPRI, Great River Energy (GRE), and City Public Service (CPS) of San Antonio are project co-funders. URS Group is the prime contractor. The mercury catalytic oxidation process under development uses catalyst materials applied to honeycomb substrates to promote the oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone flue gas desulfurization (FGD) systems. Oxidized mercury is removed in the wet FGD absorbers and co-precipitates in a stable form with the byproducts from the FGD system. The co-precipitated mercury does not appear to adversely affect the disposal or reuse properties of the FGD byproduct. The current project will test previously identified, effective catalyst materials at a larger, pilot scale and in a commercial form, so as to provide engineering data for future full-scale designs. The pilot-scale tests will continue for up to 14 months at each of two sites to provide longer-term catalyst life data. This is the third full reporting period for the subject Cooperative Agreement. During this period, most of the project efforts were related to constructing the pilot unit and conducting laboratory runs to help size catalysts for the pilot unit. This technical progress report provides an update on these two efforts.

  10. PremAir{trademark} catalyst systems: A new approach to clean air

    SciTech Connect

    Poles, T.; Anderson, D.R.; Durilla, M.; Heck, R.; Hoke, J.; Ober, R.; Rudy, W.

    1996-12-01

    PremAir{trademark} catalyst systems represents a new approach to air pollution control--one that focuses on destroying pollutants already in the air. PremAir is the trademark for a family of developmental catalysts capable of reducing ozone, carbon monoxide and potentially other pollutants in ambient air that comes into contact with catalyst-coated surfaces. The more air that comes into contact with the surface the more pollutants that can be destroyed. For this reason, Engelhard has focused its attention on heat-exchange equipment such as automotive radiators and air-conditioner condensers. It is because of advances in catalysis achieved at Engelhard that PremAir catalysts are active at the low temperatures found in these environments. In Los Angeles, which has the country`s worst smog problem, approximately one trillion cubic feet per day of air pass through car radiators and five trillion cubic feet per day pass through air conditioners. Most of the research, development and testing work performed to date has been on ozone catalysts and their application to car radiators. This paper discusses that work and the potential benefits associated with the PremAir technology. In addition, preliminary work on stationary applications of this new technology is discussed.

  11. Preparation of a magnetic N-Fe/AC catalyst for aqueous pharmaceutical treatment in heterogeneous sonication system.

    PubMed

    Zhang, Nan; Zhao, He; Zhang, Guangming; Chong, Shan; Liu, Yucan; Sun, Liyan; Chang, Huazhen; Huang, Ting

    2017-02-01

    High efficiency and facile separation are desirable for catalysts used in water treatment. In this study, a magnetic catalyst (nitrogen doped iron/activated carbon) was prepared and used for pharmaceutical wastewater treatment. The catalyst was characterized using BET, SEM, XRD, VSM and XPS. Results showed that iron and nitrogen were successfully loaded and doped, magnetic Fe2N was formed, large amount of active surface oxygen and Fe(II) were detected, and the catalyst could be easily separated from water. Diclofenac was then degraded using the catalyst in ultrasound system. The catalyst showed high catalytic activity with 95% diclofenac removal. Analysis showed that ·OH attack of diclofenac was a main pathway, and then ·OH generation mechanism was clarified. The effects of catalyst dosage, sonication time, ultrasonic density, initial pH, and inorganic anions on diclofenac degradation were studied. Sulfate anion enhanced the degradation of diclofenac. Mechanism in the catalytic ultrasonic process was analyzed and reactions were clarified. Large quantity of oxidants was generated on the catalyst surface, including ·OH, O2(-), O(-) and HO2·, which degraded diclofenac efficiently. In the solution and interior of cavitation bubbles, ·OH and "hot spot" effects contributed to the degradation of diclofenac. Reuse of the catalyst was further investigated to enhance its economy, and the catalyst maintained activity after seven uses. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. NO.sub.x catalyst and method of suppressing sulfate formation in an exhaust purification system

    DOEpatents

    Balmer-Millar, Mari Lou; Park, Paul W.; Panov, Alexander G.

    2006-08-22

    The activity and durability of a zeolite lean-bum NOx catalyst can be increased by loading metal cations on the outer surface of the zeolite. However, the metal loadings can also oxidize sulfur dioxide to cause sulfate formation in the exhaust. The present invention is a method of suppressing sulfate formation in an exhaust purification system including a NO.sub.x catalyst. The NO.sub.x catalyst includes a zeolite loaded with at least one metal. The metal is selected from among an alkali metal, an alkaline earth metal, a lanthanide metal, a noble metal, and a transition metal. In order to suppress sulfate formation, at least a portion of the loaded metal is complexed with at least one of sulfate, phosphate, and carbonate.

  13. An efficient palladium catalyst system for the oxidative carbonylation of glycerol to glycerol carbonate.

    PubMed

    Hu, Jianglin; Gu, Yanlong; Guan, Zhenhong; Li, Jinjin; Mo, Wanling; Li, Tao; Li, Guangxing

    2011-12-16

    Glycerol carbonate can be readily synthesized from the oxidative carbonylation of glycerol catalyzed by PdCl(2)(phen) (phen=1,10-phenanthroline) with the aid of CuI. High conversion (95 %) and selectivity (98 %) are achieved and the turnover frequency (TOF) reaches 455 h(-1). Furthermore, a new zeolite-Y-confined Pd catalyst, PdCl(2)(phen)@Y, has been successfully prepared by a ''flexible ligand'' method. The structure and composition of the heterogeneous catalyst have been characterized by atomic absorption spectroscopy, elemental analysis, N(2) sorption, XRD, FTIR, solid-state NMR, and X-ray photoelectron spectroscopy. This catalyst exhibits a comparable activity to its homogeneous counterpart and could be reused five times without significant decrease in activity. This is the most efficient heterogeneous system for synthesizing glycerol carbonate by the oxidative carbonylation of glycerol to date. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. NO.sub.x catalyst and method of suppressing sulfate formation in an exhaust purification system

    DOEpatents

    Balmer-Millar, Mari Lou; Park, Paul W.; Panov, Alexander G.

    2007-06-26

    The activity and durability of a zeolite lean-burn NOx catalyst can be increased by loading metal cations on the outer surface of the zeolite. However, the metal loadings can also oxidize sulfur dioxide to cause sulfate formation in the exhaust. The present invention is a method of suppressing sulfate formation in an exhaust purification system including a NO.sub.x catalyst. The NO.sub.x catalyst includes a zeolite loaded with at least one metal. The metal is selected from among an alkali metal, an alkaline earth metal, a lanthanide metal, a noble metal, and a transition metal. In order to suppress sulfate formation, at least a portion of the loaded metal is complexed with at least one of sulfate, phosphate, and carbonate.

  15. "Catalyst Data": Perverse Systemic Effects of Audit and Accountability in Australian Schooling

    ERIC Educational Resources Information Center

    Lingard, Bob; Sellar, Sam

    2013-01-01

    This paper examines the perverse effects of the new accountability regime central to the Labor government's national reform agenda in schooling. The focus is on National Assessment Program -- Literacy and Numeracy (NAPLAN) results that now act as "catalyst data" and are pivotal to school and system accountability. We offer a case study,…

  16. "Catalyst Data": Perverse Systemic Effects of Audit and Accountability in Australian Schooling

    ERIC Educational Resources Information Center

    Lingard, Bob; Sellar, Sam

    2013-01-01

    This paper examines the perverse effects of the new accountability regime central to the Labor government's national reform agenda in schooling. The focus is on National Assessment Program -- Literacy and Numeracy (NAPLAN) results that now act as "catalyst data" and are pivotal to school and system accountability. We offer a case study,…

  17. The synergistic effect in the Fe-Co bimetallic catalyst system for the growth of carbon nanotube forests

    SciTech Connect

    Hardeman, D.; Esconjauregui, S. Cartwright, R.; D'Arsié, L.; Robertson, J.; Bhardwaj, S.; Cepek, C.; Oakes, D.; Clark, J.; Ducati, C.

    2015-01-28

    We report the growth of multi-walled carbon nanotube forests employing an active-active bimetallic Fe-Co catalyst. Using this catalyst system, we observe a synergistic effect by which—in comparison to pure Fe or Co—the height of the forests increases significantly. The homogeneity in the as-grown nanotubes is also improved. By both energy dispersive spectroscopy and in-situ x-ray photoelectron spectroscopy, we show that the catalyst particles consist of Fe and Co, and this dramatically increases the growth rate of the tubes. Bimetallic catalysts are thus potentially useful for synthesising nanotube forests more efficiently.

  18. Evaluation of a novel catalyst system for producing jet fuel from whole crude shale oil. Final report 15 August 1982-31 December 1983

    SciTech Connect

    Tait, A.M.; Hensley, A.L.

    1984-02-01

    The purpose of this experimental study was to evaluate a novel catalyst system for the production of JP-4 jet fuels from a whole shale oil on a once-through basis. The dual-catalyst system consists of a pretreat catalyst specifically designed to remove nitrogen, as ammonia, from organo-nitrogen compounds, and the previously developed hydrocracking catalyst. Since hydrocracking activity is critically dependent upon almost total removal of contaminant nitrogen compounds, it was proposed that the use of the dual-catalyst system would significantly improve the process with respect to catalyst lifetimes and feed throughput.

  19. Enhancement of interfacial catalysis in a biphasic system using catalyst-binding ligands

    NASA Astrophysics Data System (ADS)

    Chaudhari, R. V.; Bhanage, B. M.; Deshpande, R. M.; Delmas, H.

    1995-02-01

    TO avoid the problem of separation of products from catalyst in homogeneous catalysis1, two-phase systems have been developed in which the catalytic complex (usually a water-soluble organo-metallic complex) remains in one (generally aqueous) phase while the products remain in a second, immiscible phase2. Catalysis relies on the transfer of organic substrates into the aqueous catalyst phase; but the limited solubility of these substrates in water leads to reaction rates much lower than those for conventional homo-geneous catalysis. Here we show that catalysis at the interface of a two-phase system can be enhanced by using a 'promoter ligand' which, although soluble in the organic phase, will bind to the organometallic catalyst and thus increase its concentration close to the interface in the aqueous phase. We demonstrate this approach for the hydroformylation of 1-octene using a rhodium-based catalyst. A rate enhancement by a factor of 10-50 is observed when we introduce the promoter ligand PPh3 in the organic phase.

  20. Method of preparing and utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream

    DOEpatents

    Berry, David A; Shekhawat, Dushyant; Smith, Mark; Haynes, Daniel

    2013-07-16

    The disclosure relates to a method of utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream with a mitigation of carbon accumulation. The system is comprised of a catalytically active phase deposited onto an oxygen conducting phase, with or without supplemental support. The catalytically active phase has a specified crystal structure where at least one catalytically active metal is a cation within the crystal structure and coordinated with oxygen atoms within the crystal structure. The catalyst system employs an optimum coverage ratio for a given set of oxidation conditions, based on a specified hydrocarbon conversion and a carbon deposition limit. Specific embodiments of the catalyst system are disclosed.

  1. A systems evaluation on the effectiveness of a catalyst retrofit program in China.

    PubMed

    Jones, M; Wilson, R; Norbeck, J M; Han, W; Hurley, R; Schuetzle, D

    2001-09-01

    A low-cost, rare-earth oxide (REO) catalyst has been recommended as part of China's retrofit program for Chinese carbureted vehicles. This study evaluated: (1) the emission reduction efficiency of the REO catalyst during chassis dynamometer testing on the FTP cycle; (2) the effect that fuel properties had on tailpipe emissions and catalyst efficiency; (3) the importance of vehicle premaintenance as part of a retrofit protocol; and (4) the emission reductions obtained following implementation of the program. Results also show that current in-use Chinese noncatalyst, carbureted vehicles operate excessively rich, resulting in extremely high emissions of CO, gaseous toxic compounds, and other non-methane hydrocarbon species (NMHC). Preretrofit maintenance alone has the potential to reduce these emissions by approximately 50%. Dynamometer emission tests showed emissions reductions of >95% for hydrocarbons, CO, and gaseous toxics after retrofit of the REO catalyst. In particular, the relative unit health risk associated with the decrease in emissions of airborne toxic compounds using unleaded Chinese fuel was reduced from 6.33 to 0.30. (Use of low-sulfur California Phase II gasoline rather than current in-use Chinese fuel reduced emissions further.) Following implementation of the program, a follow-up study showed that in-use emissions benefits were considerably less than anticipated, primarily because of poor quality control at the retrofit service centers, a less aggressive preretrofit maintenance procedure, and unauthorized modification to the recommended retrofit control system. Overall results indicate that a carefully controlled retrofit program using REO catalyst technology can reduce emissions significantly. However, well-defined implementation guidelines, and strict adherence to these guidelines are needed to achieve maximum benefits.

  2. High-throughput reactor system with individual temperature control for the investigation of monolith catalysts.

    PubMed

    Dellamorte, Joseph C; Vijay, Rohit; Snively, Christopher M; Barteau, Mark A; Lauterbach, Jochen

    2007-07-01

    A high-throughput parallel reactor system has been designed and constructed to improve the reliability of results from large diameter catalysts such as monoliths. The system, which is expandable, consists of eight quartz reactors, 23.5 mm in diameter. The eight reactors were designed with separate K type thermocouples and radiant heaters, allowing for the independent measurement and control of each reactor temperature. This design gives steady state temperature distributions over the eight reactors within 0.5 degrees C of a common setpoint from 50 to 700 degrees C. Analysis of the effluent from these reactors is performed using rapid-scan Fourier transform infrared (FTIR) spectroscopic imaging. The integration of this technique to the reactor system allows a chemically specific, truly parallel analysis of the reactor effluents with a time resolution of approximately 8 s. The capabilities of this system were demonstrated via investigation of catalyst preparation conditions on the direct epoxidation of ethylene, i.e., on the ethylene conversion and the ethylene oxide selectivity. The ethylene, ethylene oxide, and carbon dioxide concentrations were calibrated based on spectra from FTIR imaging using univariate and multivariate chemometric techniques. The results from this analysis showed that the calcination conditions significantly affect the ethylene conversion, with a threefold increase in the conversion when the catalyst was calcined for 3 h versus 12 h at 400 degrees C.

  3. Evaluation of a novel catalyst system for producing jet fuel from whole-crude shale oil. Final report, August 1982-December 1983

    SciTech Connect

    Tait, A.M.; Hensley, A.L.

    1984-02-01

    In a previous study the development of a single-catalyst system was reported which had the unique ability to sequentially saturate, denitrogenate, and hydrocrack a whole shale oil into high yields of jet fuel on a once-through basis. Examination of the kinetics suggested that improvements in the process and in catalyst activity could be achieved by using a dual-catalyst system. The dual-catalyst system would consist of the previously developed catalyst and a pretreat catalyst specifically designed to remove nitrogen as ammonia from organo-nitrogen compounds. The increased effectiveness of the dual-catalyst system was monitored in two six-month catalyst deactivation studies using fully automated, high-pressure, fixed-bed, minipilot plants. The results indicated that use of a dual-catalyst system gave significant improvements in catalyst lifetime and unit throug hput as compared to the single-catalyst system. Dual-catalyst system lifetimes were projected at approximately 2.0 years for production of 76 wt% JP-4 fuel material from whole-crude shale oil.

  4. Studying Zeolite Catalysts with a 2D Model System

    SciTech Connect

    Boscoboinik, Anibal

    2016-12-07

    Anibal Boscoboinik, a materials scientist at Brookhaven’s Center for Functional Nanomaterials, discusses the surface-science tools and 2D model system he uses to study catalysis in nanoporous zeolites, which catalyze reactions in many industrial processes.

  5. An Improved Catalyst System for the Pd-Catalyzed Fluorination of (Hetero)Aryl Triflates

    PubMed Central

    Buchwald, Stephen L.

    2013-01-01

    The stable Pd(0) species [(1,5-cyclooctadiene)(L•Pd)2] (L = AdBrettPhos) has been prepared and successfully evaluated as a precatalyst for the fluorination of aryl triflates derived from biologically active and heteroaryl phenols, challenging substrates for our previously reported catalyst system. Additionally, this precatalyst activates at room temperature under neutral conditions, generates 1,5-cyclooctadiene as the only byproduct, and leads to overall cleaner reaction profiles. PMID:24138611

  6. An efficient and convenient palladium catalyst system for the synthesis of amines from allylic alcohols.

    PubMed

    Banerjee, Debasis; Jagadeesh, Rajenahally V; Junge, Kathrin; Junge, Henrik; Beller, Matthias

    2012-10-01

    A novel catalyst system for efficient amination of allylic alcohols with aryl and alkyl amines is presented. By applying a convenient combination consisting of Pd(OAc)(2)/1,10-phenanthroline, a variety of allylic alcohols reacted smoothly to give the corresponding secondary and tertiary amines in good to excellent yields with high regioselectivity. The usefulness of our protocol is demonstrated in the one-step synthesis of the antifungal drug naftifine and the calcium channel blocker flunarizine.

  7. PILOT TESTING OF MERCURY OXIDATION CATALYSTS FOR UPSTREAM OF WET FGD SYSTEMS

    SciTech Connect

    Gary M. Blythe

    2002-04-26

    This document summarizes progress on Cooperative Agreement DE-FC26-01NT41185, Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems, during the time period January 1, 2002 through March 31, 2002. The objective of this project is to demonstrate at pilot scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. The project is being funded by the U.S. DOE National Energy Technology Laboratory under Cooperative Agreement DE-FC26-01NT41185. EPRI, Great River Energy (GRE) and City Public Service (CPS) of San Antonio are project co-funders. URS Group is the prime contractor. The mercury catalytic oxidation process under development uses catalyst materials applied to honeycomb substrates to promote the oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone flue gas desulfurization (FGD) systems. Oxidized mercury is removed in the wet FGD absorbers and co-precipitates in a stable form with the byproducts from the FGD system. The co-precipitated mercury does not appear to adversely affect the disposal or reuse properties of the FGD byproduct. The current project will test previously identified, effective catalyst materials at a larger, pilot scale and in a commercial form, so as to provide engineering data for future full-scale designs. The pilot-scale tests will continue for up to 14 months at each of two sites to provide longer-term catalyst life data. This is the second full reporting period for the subject Cooperative Agreement. During this period, most of the project efforts were related to pilot unit design and conducting laboratory runs to help select candidate catalysts. This technical progress report provides an update on these two efforts. A Test Plan for the upcoming pilot-scale evaluations was also prepared and submitted to NETL for review and comment. Since this document was already submitted under separate cover, this

  8. Studying Zeolite Catalysts with a 2D Model System

    ScienceCinema

    Boscoboinik, Anibal

    2016-12-14

    Anibal Boscoboinik, a materials scientist at Brookhaven’s Center for Functional Nanomaterials, discusses the surface-science tools and 2D model system he uses to study catalysis in nanoporous zeolites, which catalyze reactions in many industrial processes.

  9. PILOT TESTING OF MERCURY OXIDATION CATALYSTS FOR UPSTREAM OF WET FGD SYSTEMS

    SciTech Connect

    Gary M. Blythe

    2002-02-22

    The objective of this project is to demonstrate at pilot scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. The project is being funded by the U.S. DOE National Energy Technology Laboratory under Cooperative Agreement DE-FC26-01NT41185. EPRI, Great River Energy (GRE), and City Public Service (CPS) of San Antonio are project co-funders. URS Group is the prime contractor. The mercury catalytic oxidation process under development uses catalyst materials applied to honeycomb substrates to promote the oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone flue gas desulfurization (FGD) systems. Oxidized mercury is removed in the wet FGD absorbers and co-precipitates in a stable form with the byproducts from the FGD system. The co-precipitated mercury does not appear to adversely affect the disposal or reuse properties of the FGD byproduct. The current project will test previously identified, effective catalyst materials at a larger, pilot scale and in a commercial form, so as to provide engineering data for future full-scale designs. The pilot-scale tests will continue for up to 14 months at each of two sites to provide longer-term catalyst life data. This is the first full reporting period for the subject Cooperative Agreement. During this period, most of the project efforts were related to project initiation and planning. There is no significant technical progress to report for the current period.

  10. Fe-N-doped carbon catalysts prepared by hybrid PECVD/sputtering system for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Hotozuka, Kozue; Yoshie, Ryo; Murata, Hidenobu; Tateno, Akira; Ito, Gen; Kawaguchi, Norihito; Matsuo, Takahiro; Ito, Hitomi; Kinoshita, Ikuo; Tachibana, Masaru

    2017-07-01

    A hybrid plasma-enhanced chemical vapor deposition (PECVD)/sputtering system was developed to prepare iron (Fe)-nitrogen (N)-doped carbon catalysts for oxygen reduction reaction (ORR). This hybrid system combines PECVD effective for the synthesis of nanocarbons with sputtering technique for the doping of metals such as Fe where the amount of the doping can be independently controlled during synthesizing nanocarbons. By using this system, Fe-N-doped carbon catalysts are directly synthesized on carbon papers which have been widely used as a gas diffusion layer in fuel cells. The synthesized catalysts with carbon papers exhibit high ORR activity. This is attributed to Fe-N coordination bonds which are stably formed in the synthesized catalysts.

  11. Synthesis of dimethyl ether and alternative fuels in the liquid phase from coal-derived synthesis gas. Task 2.2: Definition of preferred catalyst system; Task 2.3: Process variable scans on the preferred catalyst system; Task 2.4: Life-test on the preferred catalyst system

    SciTech Connect

    Bhatt, B.L.

    1992-09-01

    As part of the DOE-sponsored contract for the Synthesis of Dimethyl Ether (DME) and Alternative Fuels in the Liquid Phase from Coal- Derived Syngas, the single-step, slurry phase DME synthesis process was developed. The development involved screening of catalyst systems, process variable studies, and catalyst life studies in two 300 ml stirred autoclaves. As a spin-off of the Liquid Phase Methanol (LPMEOH*) process, the new process significantly improves the syngas conversion efficiency of the LPMEOH process. This improvement can be achieved by replacing a portion of methanol catalyst with a dehydration catalyst in the reactor, resulting in the product methanol being converted to DME, thus avoiding the thermodynamic equilibrium constraint of the methanol reaction. Overall, this increases syngas conversion per-pass. The selectivity and productivity of DME and methanol are affected by the catalyst system employed as well as operating conditions. A preferred catalyst system, consisting of a physical mixture of a methanol catalyst and a gamma alumina, was identified. An improvement of about 50% in methanol equivalent productivity was achieved compared to the LPMEOH process. Results from the process variable study indicate that higher pressure and CO{sub 2} removal benefit the process significantly. Limited life studies performed on the preferred catalyst system suggest somewhat higher than expected deactivation rate for the methanol catalyst. Several DME/methanol mixtures were measured for their key properties as transportation fuels. With small amounts of DME added, significant improvements in both flash points and Reid Vapor Pressure (RVP) were observed over the corresponding values of methanol alone.

  12. System and method for controlling an engine based on ammonia storage in multiple selective catalytic reduction catalysts

    DOEpatents

    Sun, MIn; Perry, Kevin L.

    2015-11-20

    A system according to the principles of the present disclosure includes a storage estimation module and an air/fuel ratio control module. The storage estimation module estimates a first amount of ammonia stored in a first selective catalytic reduction (SCR) catalyst and estimates a second amount of ammonia stored in a second SCR catalyst. The air/fuel ratio control module controls an air/fuel ratio of an engine based on the first amount, the second amount, and a temperature of a substrate disposed in the second SCR catalyst.

  13. Development of a ruthenium/phosphite catalyst system for domino hydroformylation-reduction of olefins with carbon dioxide.

    PubMed

    Liu, Qiang; Wu, Lipeng; Fleischer, Ivana; Selent, Detlef; Franke, Robert; Jackstell, Ralf; Beller, Matthias

    2014-06-02

    An efficient domino ruthenium-catalyzed reverse water-gas-shift (RWGS)-hydroformylation-reduction reaction of olefins to alcohols is reported. Key to success is the use of specific bulky phosphite ligands and triruthenium dodecacarbonyl as the catalyst. Compared to the known ruthenium/chloride system, the new catalyst allows for a more efficient hydrohydroxymethylation of terminal and internal olefins with carbon dioxide at lower temperature. Unwanted hydrogenation of the substrate is prevented. Preliminary mechanism investigations uncovered the homogeneous nature of the active catalyst and the influence of the ligand and additive in individual steps of the reaction sequence.

  14. Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems

    SciTech Connect

    Gary Blythe; Conor Braman; Katherine Dombrowski; Tom Machalek

    2010-12-31

    This document is the final technical report for Cooperative Agreement DE-FC26-04NT41992, 'Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems,' which was conducted over the time-period January 1, 2004 through December 31, 2010. The objective of this project has been to demonstrate at pilot scale the use of solid catalysts and/or fixed-structure mercury sorbents to promote the removal of total mercury and oxidation of elemental mercury in flue gas from coal combustion, followed by wet flue gas desulfurization (FGD) to remove the oxidized mercury at high efficiency. The project was co-funded by the U.S. DOE National Energy Technology Laboratory (DOE-NETL), EPRI, Great River Energy (GRE), TXU Energy (now called Luminant), Southern Company, Salt River Project (SRP) and Duke Energy. URS Group was the prime contractor. The mercury control process under development uses fixed-structure sorbents and/or catalysts to promote the removal of total mercury and/or oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone FGD systems. Oxidized mercury not adsorbed is removed in the wet FGD absorbers and leaves with the byproducts from the FGD system. The project has tested candidate materials at pilot scale and in a commercial form, to provide engineering data for future full-scale designs. Pilot-scale catalytic oxidation tests have been completed for periods of approximately 14 to19 months at three sites, with an additional round of pilot-scale fixed-structure sorbent tests being conducted at one of those sites. Additionally, pilot-scale wet FGD tests have been conducted downstream of mercury oxidation catalysts at a total of four sites. The sites include the two of three sites from this project and two sites where catalytic oxidation pilot testing was conducted as part of a previous DOE-NETL project. Pilot-scale wet FGD tests were also conducted at a fifth site, but with no catalyst or fixed

  15. Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

    DOEpatents

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

    2011-07-12

    A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

  16. A Versatile Catalyst System for Suzuki-Miyaura Cross-Coupling Reactions of C(sp2)-Tosylates and Mesylates

    PubMed Central

    Bhayana, Brijesh; Fors, Brett P.

    2009-01-01

    A catalyst system for the Suzuki-Miyaura cross-coupling reactions of aryl and vinyl tosylates and mesylates has been developed. This catalyst displays excellent functional group tolerance and allows the coupling of heteroarylboronic acids with aryl tosylates and mesylates to be performed in high yields. Moreover, reactions employing alkylboronic acids, as well as heteroaryl, vinyl, and allylic pinacol boronate esters were conducted with high efficiencies. PMID:19663467

  17. Catalyst by Design

    SciTech Connect

    Narula, Chaitanya Kumar; DeBusk, Melanie Moses

    2014-01-01

    The development of new catalytic materials is still dominated by trial and error methods. Although it has been successful, the empirical development of catalytic materials is time consuming and expensive with no guarantee of success. In our laboratories, we are developing a comprehensive catalysts by design that involves state-of-the-art first principle density functional theory calculations, experimental design of catalyst sites, and sub- ngstr m resolution imaging with an aberration-corrected electron microscope to characterize the microstructure. In this chapter, we focus on supported platinum cluster catalyst systems which are one of the most important industrial catalysts and attempt to demonstrate the feasibility of the catalyst by design concept.

  18. Practical Aerobic Oxidations of Alcohols and Amines with Homogeneous Cu/TEMPO and Related Catalyst Systems

    PubMed Central

    Ryland, Bradford L.; Stahl, Shannon S.

    2014-01-01

    Alcohol and amine oxidations are common reactions in laboratory and industrial synthesis of organic molecules. 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. PMID:25044821

  19. Nanolithographic Fabrication and Heterogeneous Reaction Studies ofTwo-Dimensional Platinum Model Catalyst Systems

    SciTech Connect

    Contreras, Anthony Marshall

    2006-05-20

    In order to better understand the fundamental components that govern catalytic activity, two-dimensional model platinum nanocatalyst arrays have been designed and fabricated. These catalysts arrays are meant to model the interplay of the metal and support important to industrial heterogeneous catalytic reactions. Photolithography and sub-lithographic techniques such as electron beam lithography, size reduction lithography and nanoimprint lithography have been employed to create these platinum nanoarrays. Both in-situ and ex-situ surface science techniques and catalytic reaction measurements were used to correlate the structural parameters of the system to catalytic activity.

  20. Hydrogenolysis of cellulose over Cu-based catalysts-analysis of the reaction network.

    PubMed

    Tajvidi, Kameh; Hausoul, Peter J C; Palkovits, Regina

    2014-05-01

    A series of polyols, carbohydrates, and cellulose were tested in the aqueous, CuO/ZnO/Al2O3-catalyzed hydrogenolysis reaction at 245 °C and 50 bar H2. The compositions of liquid-phase products were analyzed; based on these results a unified reaction mechanism is proposed that accounts for the observed product distribution. Elementary transformations such as dehydration, dehydrogenation/hydrogenation, Lobry de Bruyn-van Ekenstein isomerization and retro-aldol cleavage were identified as most important for controlling the selectivity of simple polyols and carbohydrates. For cellulose the product distribution is considerably different than for glucose or sorbitol, indicating a change in the reaction pathway. Therefore, next to the traditional hydrolysis of the glycosidic bond, an additional depolymerization mechanism involving only the reducing ends of cellulose oligomers is proposed to account for this observation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Initial stages of oxidation for Cu-based catalysts using density functional theory

    NASA Astrophysics Data System (ADS)

    Zuo, Zhi-Jun; Li, Na; Liu, Shi-Zhong; Han, Pei-De; Huang, Wei

    2016-03-01

    The adsorption, dissociation, and desorption of O2 on Cu(111), Cu(110), and Cu(100) surfaces at different coverages were studied at the molecular level. The dissociation energies of O2 molecules increase with the increase in coverage of adsorbed O2. The saturated coverage of O atoms from dissociation of O2 molecules on Cu(111), Cu(110), and Cu(100) surfaces are 0.25, 0.75, and 0.375 ML, respectively. Based on the computed Gibbs free energies, the relationships between O atoms/O2 molecules and temperature, as well as O2 partial pressure, on these surfaces are established. Cu(111), Cu(110), and Cu(100) surfaces are covered by O atoms under ultra-high vacuum at 298 K, with O atom coverage of 0.25, 0.625, and 0.375 ML, respectively. Phase diagrams provide useful information on phase transition from Cu to Cu2O in terms of temperature and O2 partial pressure. Results of this study may provide guidance in investigating the interaction between O2 and transition metals.

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

    DOEpatents

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

    2011-08-02

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

  3. Catalytic and surface properties of nanocrystalline gold water gas shift catalysts

    NASA Astrophysics Data System (ADS)

    Kim, Chang Hwan

    A series of CeO2 supported gold catalysts were prepared and found to possess a high activities for the water gas shift reaction (WGS), a critical step in the production of H2 for use in petroleum refining, chemicals synthesis, and proton exchange membrane fuel cells. The deposition-precipitation method was employed in synthesizing these highly active, nanocrystalline gold catalysts. X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and dynamic sorption analyses were performed to characterize the gold catalysts. While some of these catalysts were initially four times more active than a commercial Cu-based catalyst, they were susceptible to deactivation. Characterization using techniques including temperature programmed oxidation, XPS, and FT-IR indicated that the deactivation was caused primarily by blockage of the active sites by carbonates and/or formates. Formation of these carbonaceous species appeared to be facilitated by oxygen deficient sites on the ceria surface and may have been associated with hydroxyl groups formed on the nanocrystalline gold particles under the H2 rich conditions. The deactivation could be managed by conditioning the CeO2 surface or adding constituents to minimize oxygen deficiency. The catalytic activity was fully recovered by calcining the deactivated materials in flowing air at elevated temperatures. The gold catalyst was washcoated onto microporous Fe-Al alloy foams for use in a micro-channel WGS reactor. The performance of these coated foams was inferior to that of the powder catalyst; however, a two stage micro-channel WGS reactor employing the gold catalyst was sufficient for a 100 W fuel processor system.

  4. Strong, ductile, and thermally stable Cu-based metal-intermetallic nanostructured composites

    PubMed Central

    Dusoe, Keith J.; Vijayan, Sriram; Bissell, Thomas R.; Chen, Jie; Morley, Jack E.; Valencia, Leopolodo; Dongare, Avinash M.; Aindow, Mark; Lee, Seok-Woo

    2017-01-01

    Bulk metallic glasses (BMGs) and nanocrystalline metals (NMs) have been extensively investigated due to their superior strengths and elastic limits. Despite these excellent mechanical properties, low ductility at room temperature and poor microstructural stability at elevated temperatures often limit their practical applications. Thus, there is a need for a metallic material system that can overcome these performance limits of BMGs and NMs. Here, we present novel Cu-based metal-intermetallic nanostructured composites (MINCs), which exhibit high ultimate compressive strengths (over 2 GPa), high compressive failure strain (over 20%), and superior microstructural stability even at temperatures above the glass transition temperature of Cu-based BMGs. Rapid solidification produces a unique ultra-fine microstructure that contains a large volume fraction of Cu5Zr superlattice intermetallic compound; this contributes to the high strength and superior thermal stability. Mechanical and microstructural characterizations reveal that substantial accumulation of phase boundary sliding at metal/intermetallic interfaces accounts for the extensive ductility observed. PMID:28067334

  5. Strong, ductile, and thermally stable Cu-based metal-intermetallic nanostructured composites

    NASA Astrophysics Data System (ADS)

    Dusoe, Keith J.; Vijayan, Sriram; Bissell, Thomas R.; Chen, Jie; Morley, Jack E.; Valencia, Leopolodo; Dongare, Avinash M.; Aindow, Mark; Lee, Seok-Woo

    2017-01-01

    Bulk metallic glasses (BMGs) and nanocrystalline metals (NMs) have been extensively investigated due to their superior strengths and elastic limits. Despite these excellent mechanical properties, low ductility at room temperature and poor microstructural stability at elevated temperatures often limit their practical applications. Thus, there is a need for a metallic material system that can overcome these performance limits of BMGs and NMs. Here, we present novel Cu-based metal-intermetallic nanostructured composites (MINCs), which exhibit high ultimate compressive strengths (over 2 GPa), high compressive failure strain (over 20%), and superior microstructural stability even at temperatures above the glass transition temperature of Cu-based BMGs. Rapid solidification produces a unique ultra-fine microstructure that contains a large volume fraction of Cu5Zr superlattice intermetallic compound; this contributes to the high strength and superior thermal stability. Mechanical and microstructural characterizations reveal that substantial accumulation of phase boundary sliding at metal/intermetallic interfaces accounts for the extensive ductility observed.

  6. Using reduced catalysts for oxidation reactions: mechanistic studies of the "Periana-Catalytica" system for CH4 oxidation.

    PubMed

    Mironov, Oleg A; Bischof, Steven M; Konnick, Michael M; Hashiguchi, Brian G; Ziatdinov, Vadim R; Goddard, William A; Ahlquist, Mårten; Periana, Roy A

    2013-10-02

    Designing oxidation catalysts based on CH activation with reduced, low oxidation state species is a seeming dilemma given the proclivity for catalyst deactivation by overoxidation. This dilemma has been recognized in the Shilov system where reduced Pt(II) is used to catalyze methane functionalization. Thus, it is generally accepted that key to replacing Pt(IV) in that system with more practical oxidants is ensuring that the oxidant does not over-oxidize the reduced Pt(II) species. The "Periana-Catalytica" system, which utilizes (bpym)Pt(II)Cl2 in concentrated sulfuric acid solvent at 200 °C, is a highly stable catalyst for the selective, high yield oxy-functionalization of methane. In lieu of the over-oxidation dilemma, the high stability and observed rapid oxidation of (bpym)Pt(II)Cl2 to Pt(IV) in the absence of methane would seem to contradict the originally proposed mechanism involving CH activation by a reduced Pt(II) species. Mechanistic studies show that the originally proposed mechanism is incomplete and that while CH activation does proceed with Pt(II) there is a solution to the over-oxidation dilemma. Importantly, contrary to the accepted view to minimize Pt(II) overoxidation, these studies also show that increasing that rate could increase the rate of catalysis and catalyst stability. The mechanistic basis for this counterintuitive prediction could help to guide the design of new catalysts for alkane oxidation that operate by CH activation.

  7. Continuous Production of Carbon-Supported Cubic and Octahedral Platinum-Based Catalysts Using Conveyor Transport System.

    PubMed

    Tsao, Kai-Chieh; Yang, Hong

    2016-09-01

    A conveyor transport system is developed for the continuous production of carbon-supported uniform Pt nanocubes, and Pt3 Ni nanocubes and octahedra in a single-reaction system under hot carbon monoxide environment. Oleylamine is critical for the high loading and even the dispersion of Pt nanocubes on a carbon support. The metal catalyst shows high performance in electrocatalytic oxidation of methanol.

  8. Efficient solar-to-fuels production from a hybrid microbial-water-splitting catalyst system.

    PubMed

    Torella, Joseph P; Gagliardi, Christopher J; Chen, Janice S; Bediako, D Kwabena; Colón, Brendan; Way, Jeffery C; Silver, Pamela A; Nocera, Daniel G

    2015-02-24

    Photovoltaic cells have considerable potential to satisfy future renewable-energy needs, but efficient and scalable methods of storing the intermittent electricity they produce are required for the large-scale implementation of solar energy. Current solar-to-fuels storage cycles based on water splitting produce hydrogen and oxygen, which are attractive fuels in principle but confront practical limitations from the current energy infrastructure that is based on liquid fuels. In this work, we report the development of a scalable, integrated bioelectrochemical system in which the bacterium Ralstonia eutropha is used to efficiently convert CO2, along with H2 and O2 produced from water splitting, into biomass and fusel alcohols. Water-splitting catalysis was performed using catalysts that are made of earth-abundant metals and enable low overpotential water splitting. In this integrated setup, equivalent solar-to-biomass yields of up to 3.2% of the thermodynamic maximum exceed that of most terrestrial plants. Moreover, engineering of R. eutropha enabled production of the fusel alcohol isopropanol at up to 216 mg/L, the highest bioelectrochemical fuel yield yet reported by >300%. This work demonstrates that catalysts of biotic and abiotic origin can be interfaced to achieve challenging chemical energy-to-fuels transformations.

  9. Efficient solar-to-fuels production from a hybrid microbial–water-splitting catalyst system

    PubMed Central

    Torella, Joseph P.; Gagliardi, Christopher J.; Chen, Janice S.; Bediako, D. Kwabena; Colón, Brendan; Way, Jeffery C.; Silver, Pamela A.; Nocera, Daniel G.

    2015-01-01

    Photovoltaic cells have considerable potential to satisfy future renewable-energy needs, but efficient and scalable methods of storing the intermittent electricity they produce are required for the large-scale implementation of solar energy. Current solar-to-fuels storage cycles based on water splitting produce hydrogen and oxygen, which are attractive fuels in principle but confront practical limitations from the current energy infrastructure that is based on liquid fuels. In this work, we report the development of a scalable, integrated bioelectrochemical system in which the bacterium Ralstonia eutropha is used to efficiently convert CO2, along with H2 and O2 produced from water splitting, into biomass and fusel alcohols. Water-splitting catalysis was performed using catalysts that are made of earth-abundant metals and enable low overpotential water splitting. In this integrated setup, equivalent solar-to-biomass yields of up to 3.2% of the thermodynamic maximum exceed that of most terrestrial plants. Moreover, engineering of R. eutropha enabled production of the fusel alcohol isopropanol at up to 216 mg/L, the highest bioelectrochemical fuel yield yet reported by >300%. This work demonstrates that catalysts of biotic and abiotic origin can be interfaced to achieve challenging chemical energy-to-fuels transformations. PMID:25675518

  10. Incorporation of Water-Oxidation Catalysts into Photoinduced Electron Transfer Systems: Toward Solar Fuel Generation via Artificial Photosynthesis

    NASA Astrophysics Data System (ADS)

    Vagnini, Michael Thomas

    mechanisms and probing highly-reactive intermediates, and it also establishes a basis in systems design for photodriving catalytic processes. Covalent dye-catalyst assemblies have been gaining recognition as a useful motif for incorporation into dye-sensitized photoanodes for photoelectrochemical water-splitting cells, and the PMI-Ir catalyst unit is well-poised, both in the energetics and kinetics of its electron transfer properties, to improve upon current solar-driven fuel-forming devices.

  11. Copper(I)/ABNO-catalyzed aerobic alcohol oxidation: alleviating steric and electronic constraints of Cu/TEMPO catalyst systems.

    PubMed

    Steves, Janelle E; Stahl, Shannon S

    2013-10-23

    Cu/TEMPO catalyst systems promote efficient aerobic oxidation of sterically unhindered primary alcohols and electronically activated substrates, but they show reduced reactivity with aliphatic and secondary alcohols. Here, we report a catalyst system, consisting of ((MeO)bpy)Cu(I)(OTf) and ABNO ((MeO)bpy = 4,4'-dimethoxy-2,2'-bipyridine; ABNO = 9-azabicyclo[3.3.1]nonane N-oxyl), that mediates aerobic oxidation of all classes of alcohols, including primary and secondary allylic, benzylic, and aliphatic alcohols with nearly equal efficiency. The catalyst exhibits broad functional group compatibility, and most reactions are complete within 1 h at room temperature using ambient air as the source of oxidant.

  12. Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

    NASA Astrophysics Data System (ADS)

    González, J.; Chen, L. F.; Wang, J. A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J. L.

    2016-08-01

    A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H2O2 as oxidant. ODS activity was found to be proportional to the V5+/(V4+ + V5+) values of the catalysts, indicating that the surface vanadium pentoxide (V2O5) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V2O5) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V2O5/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

  13. Aldol reaction catalyzed by a hydrophilic catalyst in aqueous micelle as an enzyme mimic system.

    PubMed

    Zhang, Hefeng; Zhao, Wenshan; Zou, Jun; Liu, Yi; Li, Runtao; Cui, Yuanchen

    2009-05-01

    Chitosan-supported L-proline complex was synthesized and applied as a catalyst for the direct asymmetric aldol reaction in various organic solvents and water as well. It was found that the novel synthesized catalyst was able to efficiently catalyze the aldol reaction in various media. The catalytic capacity and stereoselectivity of the catalyst were obviously improved with the introduction of aqueous micelle, possibly because the micelle functioned as a hydrophobic pocket, like the hydrophobic portion in enzymes. Moreover, the present synthetic catalyst showed performance similar to that of enzymes and could be used as a model of enzyme catalysis to help better understand the mystic mechanism of enzymes.

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

    PubMed

    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. Perfectly alternating copolymerization of CO2 and epichlorohydrin using cobalt(III)-based catalyst systems.

    PubMed

    Wu, Guang-Peng; Wei, Sheng-Hsuan; Ren, Wei-Min; Lu, Xiao-Bing; Xu, Tie-Qi; Darensbourg, Donald J

    2011-09-28

    Selective transformations of carbon dioxide and epoxides into biodegradable polycarbonates by the alternating copolymerization of the two monomers represent some of the most well-studied and innovative technologies for potential large-scale utilization of carbon dioxide in chemical synthesis. For the most part, previous studies of these processes have focused on the use of aliphatic terminal epoxides or cyclohexene oxide derivatives, with only rare reports concerning the synthesis of CO(2) copolymers from epoxides containing electron-withdrawing groups such as styrene oxide. Herein we report the production of the CO(2) copolymer with more than 99% carbonate linkages from the coupling of CO(2) with epichlorohydrin, employing binary and bifunctional (salen)cobalt(III)-based catalyst systems. Comparative kinetic studies were performed via in situ infrared measurements as a function of temperature to assess the activation barriers for the production of cyclic carbonate versus copolymer involving two electronically different epoxides: epichlorohydrin and propylene oxide. The relative small activation energy difference between copolymer versus cyclic carbonate formation for the epichlorohydrin/CO(2) process (45.4 kJ/mol) accounts in part for the selective synthesis of copolymer to be more difficult in comparison with the propylene oxide/CO(2) case (53.5 kJ/mol). Direct observation of the propagating polymer-chain species from the binary (salen)CoX/MTBD (X = 2,4-dinitrophenoxide and MTBD = 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene) catalyst system by means of electrospray ionization mass spectrometry confirmed the perfectly alternating nature of the copolymerization process. This observation in combination with control experiments suggests possible intermediates involving MTBD in the CO(2)/epichlorohydrin copolymerization process.

  16. System and method for controlling ammonia levels in a selective catalytic reduction catalyst using a nitrogen oxide sensor

    DOEpatents

    None

    2017-07-25

    A system according to the principles of the present disclosure includes an air/fuel ratio determination module and an emission level determination module. The air/fuel ratio determination module determines an air/fuel ratio based on input from an air/fuel ratio sensor positioned downstream from a three-way catalyst that is positioned upstream from a selective catalytic reduction (SCR) catalyst. The emission level determination module selects one of a predetermined value and an input based on the air/fuel ratio. The input is received from a nitrogen oxide sensor positioned downstream from the three-way catalyst. The emission level determination module determines an ammonia level based on the one of the predetermined value and the input received from the nitrogen oxide sensor.

  17. Molecular Photocatalytic Systems for Solar Energy Conversion: Catalysts for the Evolution of Hydrogen and Oxygen from Water

    NASA Astrophysics Data System (ADS)

    Zamaraev, Kirill I.; Parmon, Valentin N.

    1983-09-01

    This review is devoted to recent advances in the development and study of homogeneous and heterogeneous catalysts for the reduction of water to molecular hydrogen and its oxidation to molecular oxygen. The production of micro-heterogeneous systems for photocatalytic charge separation is also discussed. 114 references.

  18. Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

    SciTech Connect

    Tanuwijaya, V. V.; Hidayat, N. N. Agusta, M. K. Dipojono, H. K.

    2015-09-30

    One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) and LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO{sub 3} sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.

  19. Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

    NASA Astrophysics Data System (ADS)

    Tanuwijaya, V. V.; Hidayat, N. N.; Agusta, M. K.; Dipojono, H. K.

    2015-09-01

    One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) and LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO3 sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.

  20. Complex catalysts from self-repairing ensembles to highly reactive air-based oxidation systems

    Treesearch

    Craig L. Hill; Laurent Delannoy; Dean C. Duncan; Ira A. Weinstock; Roman F. Renneke; Richard S. Reiner; Rajai H. Atalla; Jong Woo Han; Daniel A. Hillesheim; Rui Cao; Travis M. Anderson; Nelya M. Okun; Djamaladdin G. Musaev; Yurii V. Geletii

    2007-01-01

    Progress in four interrelated catalysis research efforts in our laboratory are summarized: (1) catalytic photochemical functionalization of unactivated CeH bonds by polyoxometalates (POMs); (2) self-repairing catalysts; (3) catalysts for air-based oxidations under ambient conditions; and (4) terminal oxo complexes of the late-transition metal elements and their...

  1. Reformer assisted lean NO.sub.x catalyst aftertreatment system and method

    DOEpatents

    Kalyanaraman, Mohan [Media, PA; Park, Paul W [Peoria, IL; Ragle, Christie S [Havana, IL

    2010-06-29

    A method and apparatus for catalytically processing a gas stream passing therethrough to reduce the presence of NO.sub.x therein, wherein the apparatus includes a first catalyst composed of a silver-containing alumina that is adapted for catalytically processing the gas stream at a first temperature range, a second catalyst composed of a copper-containing zeolite located downstream from the first catalyst, wherein the second catalyst is adapted for catalytically processing the gas stream at a lower second temperature range relative to the first temperature range, a hydrocarbon compound for injection into the gas stream upstream of the first catalyst to provide a reductant, and a reformer for reforming a portion of the hydrocarbon compound into H.sub.2 and/or oxygenated hydrocarbon for injection into the gas stream upstream of the first catalyst. The second catalyst is adapted to facilitate the reaction of reducing NOx into N.sub.2, whereby the intermediates are produced via the first catalyst reacting with NOx and hydrocarbons.

  2. Glass formation, chemical properties and surface analysis of Cu-based bulk metallic glasses.

    PubMed

    Qin, Chunling; Zhao, Weimin; Inoue, Akihisa

    2011-01-01

    This paper reviews the influence of alloying elements Mo, Nb, Ta and Ni on glass formation and corrosion resistance of Cu-based bulk metallic glasses (BMGs). In order to obtain basic knowledge for application to the industry, corrosion resistance of the Cu-Hf-Ti-(Mo, Nb, Ta, Ni) and Cu-Zr-Ag-Al-(Nb) bulk glassy alloy systems in various solutions are reported in this work. Moreover, X-ray photoelectron spectroscopy (XPS) analysis is performed to clarify the surface-related chemical characteristics of the alloy before and after immersion in the solutions; this has lead to a better understanding of the correlation between the surface composition and the corrosion resistance.

  3. Glass Formation, Chemical Properties and Surface Analysis of Cu-Based Bulk Metallic Glasses

    PubMed Central

    Qin, Chunling; Zhao, Weimin; Inoue, Akihisa

    2011-01-01

    This paper reviews the influence of alloying elements Mo, Nb, Ta and Ni on glass formation and corrosion resistance of Cu-based bulk metallic glasses (BMGs). In order to obtain basic knowledge for application to the industry, corrosion resistance of the Cu–Hf–Ti–(Mo, Nb, Ta, Ni) and Cu–Zr–Ag–Al–(Nb) bulk glassy alloy systems in various solutions are reported in this work. Moreover, X-ray photoelectron spectroscopy (XPS) analysis is performed to clarify the surface-related chemical characteristics of the alloy before and after immersion in the solutions; this has lead to a better understanding of the correlation between the surface composition and the corrosion resistance. PMID:21731441

  4. A New Energy-Saving Catalytic System: Carbon Dioxide Activation by a Metal/Carbon Catalyst.

    PubMed

    Yun, Danim; Park, Dae Sung; Lee, Kyung Rok; Yun, Yang Sik; Kim, Tae Yong; Park, Hongseok; Lee, Hyunjoo; Yi, Jongheop

    2017-09-22

    The conversion of CO2 into useful chemicals is an attractive method to reduce greenhouse gas emissions and to produce sustainable chemicals. However, the thermodynamic stability of CO2 means that a lot of energy is required for its conversion into chemicals. Here, we suggest a new catalytic system with an alternative heating system that allows minimal energy consumption during CO2 conversion. In this system, electrical energy is transferred as heat energy to the carbon-supported metal catalyst. Fast ramping rates allow high operating temperatures (Tapp =250 °C) to be reached within 5 min, which leads to an 80-fold decrease of energy consumption in methane reforming using CO2 (DRM). In addition, the consumed energy normalized by time during the DRM reaction in this current-assisted catalysis is sixfold lower (11.0 kJ min(-1) ) than that in conventional heating systems (68.4 kJ min(-1) ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. On the Origin of DNA Genomes: Evolution of the Division of Labor between Template and Catalyst in Model Replicator Systems

    PubMed Central

    Takeuchi, Nobuto; Hogeweg, Paulien; Koonin, Eugene V.

    2011-01-01

    The division of labor between template and catalyst is a fundamental property of all living systems: DNA stores genetic information whereas proteins function as catalysts. The RNA world hypothesis, however, posits that, at the earlier stages of evolution, RNA acted as both template and catalyst. Why would such division of labor evolve in the RNA world? We investigated the evolution of DNA-like molecules, i.e. molecules that can function only as template, in minimal computational models of RNA replicator systems. In the models, RNA can function as both template-directed polymerase and template, whereas DNA can function only as template. Two classes of models were explored. In the surface models, replicators are attached to surfaces with finite diffusion. In the compartment models, replicators are compartmentalized by vesicle-like boundaries. Both models displayed the evolution of DNA and the ensuing division of labor between templates and catalysts. In the surface model, DNA provides the advantage of greater resistance against parasitic templates. However, this advantage is at least partially offset by the disadvantage of slower multiplication due to the increased complexity of the replication cycle. In the compartment model, DNA can significantly delay the intra-compartment evolution of RNA towards catalytic deterioration. These results are explained in terms of the trade-off between template and catalyst that is inherent in RNA-only replication cycles: DNA releases RNA from this trade-off by making it unnecessary for RNA to serve as template and so rendering the system more resistant against evolving parasitism. Our analysis of these simple models suggests that the lack of catalytic activity in DNA by itself can generate a sufficient selective advantage for RNA replicator systems to produce DNA. Given the widespread notion that DNA evolved owing to its superior chemical properties as a template, this study offers a novel insight into the evolutionary origin of DNA

  6. Effects of particulates, heavy metals and acid gas on the removals of NO and PAHs by V2O5-WO3 catalysts in waste incineration system.

    PubMed

    Chang, Feng-Yim; Chen, Jyh-Cherng; Wey, Ming-Yen; Tsai, Shih-An

    2009-10-15

    This study investigated the activities of prepared and commercial V(2)O(5)-WO(3) catalysts for simultaneous removals of NO and polycyclic aromatic hydrocarbons (PAHs) and the influences of particulates, heavy metals, SO(2), and HCl on the performances of catalysts. The experiments were carried out in a laboratory-scale waste incineration system equipped with a catalyst reactor. The DREs of PAHs by prepared and commercial V(2)O(5)-WO(3) catalysts were 64% and 72%, respectively. Increasing the particulate concentrations in flue gas suppressed the DRE of PAHs, but increasing the carbon content on surface of catalysts promotes the NO conversions. The DRE of PAHs by the catalysts was significantly decreased by the increased concentrations of heavy metal Cd, but was promoted by high concentration of Pb. The influence level of SO(2) was higher than HCl on the performances of V(2)O(5)-WO(3) catalysts for PAHs removal, but was lower than HCl for NO removal. Prepared and commercial V(2)O(5)-WO(3) catalysts have similar trends on the effects of particulates, heavy metals, SO(2), and HCl. The results of ESCA analysis reveal that the presence of these pollutants on the surface of catalysts did not change the chemical state of V and W.

  7. A feasible process for furfural production from the pre-hydrolysis liquor of corncob via biochar catalysts in a new biphasic system.

    PubMed

    Deng, Aojie; Lin, Qixuan; Yan, Yuhuan; Li, Huiling; Ren, Junli; Liu, Chuanfu; Sun, Runcang

    2016-09-01

    A feasible approach was developed to produce furfural from the pre-hydrolysis liquor of corncob via biochar catalysts as the solid acid catalyst in a new biphasic system with dichloromethane (DCM) as the organic phase and the concentrated pre-hydrolysis liquor (CPHL) containing NaCl as the aqueous phase. The biochar catalyst possessing many acidity groups (SO3H, COOH and phenolic OH groups) was prepared by the carbonization and sulfonation process of the corncob hydrolyzed residue. The influence of the catalytic condition on furfural yield and selectivity was comparatively studied. It was found that 81.14% furfural yield and 83.0% furfural selectivity were obtained from CPHL containing 5wt% xylose using this biochar catalyst in the CPHL-NaCl/DCM biphasic system at 170°C for 60min. In addition, with the regeneration process, this catalyst displayed the high performance and excellent recyclability. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. A simple and effective catalytic system for epoxidation of aliphatic terminal alkenes with manganese(II) as the catalyst.

    PubMed

    Ho, Kam-Piu; Wong, Wing-Leung; Lam, Kin-Ming; Lai, Cheuk-Piu; Chan, Tak Hang; Wong, Kwok-Yin

    2008-01-01

    A simple catalytic system that uses commercially available manganese(II) perchlorate as the catalyst and peracetic acid as the oxidant is found to be very effective in the epoxidation of aliphatic terminal alkenes with high product selectivity at ambient temperature. Many terminal alkenes are epoxidised efficiently on a gram scale in less than an hour to give excellent yields of isolated product (>90 %) of epoxides in high purity. Kinetic studies with some C9-alkenes show that the catalytic system is more efficient in epoxidising terminal alkenes than internal alkenes, which is contrary to most commonly known epoxidation systems. The reaction rate for epoxidation decreases in the order: 1-nonene>cis-3-nonene>trans-3-nonene. ESI-MS and EPR spectroscopic studies suggest that the active form of the catalyst is a high-valent oligonuclear manganese species, which probably functions as the oxygen atom-transfer agent in the epoxidation reaction.

  9. Polypyrrole-functionalized ruthenium carbene catalysts as efficient heterogeneous systems for olefin epoxidation.

    PubMed

    Dakkach, Mohamed; Fontrodona, Xavier; Parella, Teodor; Atlamsani, Ahmed; Romero, Isabel; Rodríguez, Montserrat

    2014-07-14

    New Ru complexes containing the bpea-pyr ligand (bpea-pyr stands for N,N-bis(pyridin-2-ylmethyl)-3-(1H-pyrrol-1-yl)propan-1-amine), with the formula [RuCl2(bpea-pyr)(dmso)] (isomeric complexes 2a and 2b) or [Ru(CN-Me)(bpea-pyr)X)](n+) (CN-Me = 3-methyl-1-(pyridin-2-yl)-1H-imidazol-3-ium-2-ide; X = Cl, 3, or X = H2O, 4), have been prepared and fully characterized. Complexes 3 and 4 have been anchored onto an electrode surface through electropolymerization of the attached pyrrole group, yielding stable polypyrrole films. The electrochemical behaviour of 4, which displays a bielectronic Ru(IV/II) redox pair in solution, is dramatically affected by the electropolymerization process leading to the occurrence of two monoelectronic Ru(IV/III) and Ru(III/II) redox pairs in the heterogeneous system. A carbon felt modified electrode containing complex 4 (C-felt/poly-4) has been evaluated as a heterogeneous catalyst in the epoxidation of various olefin substrates using PhI(OAc)2 as an oxidant, displaying TON values of several thousands in all cases and good selectivity for the epoxide product.

  10. Catalyst separation method reduces Platformer turnaround costs

    SciTech Connect

    Blashka, S.R.; Welch, J.G.; Nite, K.; Furfaro, A.P.

    1995-09-18

    A catalyst separation technology that segregates catalyst particles by density has proved successful in recovering CCR (continuous catalyst regeneration) Platforming catalyst that had been contaminated with heel catalyst, non-flowing catalyst. UOP`s CCR Platforming process converts naphtha to high-octane gasoline components and aromatics for petrochemical use. The reforming reactions take place in a series of Platforming reactors loaded with platinum-containing reforming catalyst. CCR Platforming technology incorporates a moving catalyst bed in a system that permits addition and withdrawal of catalyst from the reactor while the unit is operating. As the catalyst circulates through the reactors, it builds up typical carbon levels of 5%. Over time, the heel catalyst will build up carbon levels as high as 50%. When the catalyst is unloaded, heel catalyst is released, contaminating the last fraction of catalyst removed from the reactor. The heel-contaminated catalyst should not be reused because only a small fraction of the carbon on the heel catalyst is removed in the regeneration section. If returned to inventory, the carbon would react rapidly, causing temperature excursions. If heel-contaminated catalyst is reused, there is a high potential for damage to the unit. Density grading was used, after ex situ regeneration to recover the uncontaminated catalyst for reuse.

  11. Orthogonal Cu- and Pd-Based Catalyst Systems for the O- and N-Arylation of Aminophenols

    PubMed Central

    Maiti, Debabrata; Buchwald, Stephen L.

    2009-01-01

    O- or N-arylated aminophenol products constitute a common structural motif in various potentially useful therapeutic agents and/or drug candidates. We have developed a complementary set of Cu- and Pd-based catalyst systems for the selective O- and N-arylation of unprotected aminophenols using aryl halides. Selective O-arylation of 3- and 4-aminophenols is achieved with copper-catalyzed methods employing picolinic acid or CyDMEDA, trans-N,N′-dimethyl-1,2-cyclohexanediamine, respectively, as the ligand. The selective formation of N-arylated products of 3- and 4-aminophenols can be obtained with BrettPhos precatalyst, a biarylmonophosphine-based palladium catalyst. 2-Aminophenol can be selectively N-arylated with CuI, although no system for the selective O-arylation could be found. Coupling partners with diverse electronic properties and a variety of functional groups can be selectively transformed under these conditions. PMID:19899753

  12. Modified Fe3O4- hydroxyapatite nanocomposites as heterogeneous catalysts in three UV, Vis and Fenton like degradation systems

    NASA Astrophysics Data System (ADS)

    Valizadeh, S.; Rasoulifard, M. H.; Dorraji, M. S. Seyed

    2014-11-01

    The magnetite-hydroxyapatite (M-HAP) nanocomposites were prepared by a chemical co- precipitation procedure and characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and diffuse reflectance spectra (DRS). The ability of the synthesized catalyst for photocatalytic degradation of Acid Blue 25 (AB25), as an organic dye, under UV irradiation was studied. The catalyst was modified employing transition metals (Mn, Fe, Co, Ni, Cu and Zn) trying to improve the catalytic performance of HAP in absence of UV irradiation and in the presence of hydrogen peroxide i.e. a Fenton like reaction. The best results obtained for Cu and Co modified M-HAPs and the effect of operational parameters such pH, amount of catalyst and hydrogen peroxide concentration was studied. In order to investigate the performance of HAP based photocatalyst in visible light region, M-HAP was modified with silver ions. At the end, Langmuir-Hinshelwood kinetic expression used to evaluate and compare the catalytic systems. The strongest degradation activity was observed for Ag-M-HAP/Vis system because of Ag3PO4 formation. Apparent reaction rate constant (Kapp) by Ag-M-HAP/Vis was 63, 36 and 19 times faster than Cu-M-HAP(II)/H2O2, Co-M-HAP(II)/H2O2 and M-HAP (I)/UV systems, respectively.

  13. Advanced cathode materials for polymer electrolyte fuel cells based on pt/ metal oxides: from model electrodes to catalyst systems.

    PubMed

    Fabbri, Emiliana; Pătru, Alexandra; Rabis, Annett; Kötz, Rüdiger; Schmidt, Thomas J

    2014-01-01

    The development of stable catalyst systems for application at the cathode side of polymer electrolyte fuel cells (PEFCs) requires the substitution of the state-of-the-art carbon supports with materials showing high corrosion resistance in a strongly oxidizing environment. Metal oxides in their highest oxidation state can represent viable support materials for the next generation PEFC cathodes. In the present work a multilevel approach has been adopted to investigate the kinetics and the activity of Pt nanoparticles supported on SnO2-based metal oxides. Particularly, model electrodes made of SnO2 thin films supporting Pt nanoparticles, and porous catalyst systems made of Pt nanoparticles supported on Sb-doped SnO2 high surface area powders have been investigated. The present results indicate that SnO2-based supports do not modify the oxygen reduction reaction mechanism on the Pt nanoparticle surface, but rather lead to catalysts with enhanced specific activity compared to Pt/carbon systems. Different reasons for the enhancement in the specific activity are considered and discussed.

  14. Correction: A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

    PubMed

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

    2016-12-22

    Correction for 'A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide' by Chee Koon Ng et al., Chem. Commun., 2016, 52, 11842-11845.

  15. Recent Progress on Nazarov Cyclizations: The Use of Iron Salts as Catalysts in Ionic Liquid Solvent Systems.

    PubMed

    Itoh, Toshiyuki; Nokami, Toshiki; Kawatsura, Motoi

    2016-06-01

    Nazarov cyclization is an important and versatile method for the synthesis of five-membered carbocycles, and extensive studies have been conducted to optimize the reaction. Among recent studies, several trends are recognized. One is the combination of different reactions with Nazarov cyclization in a one-pot reaction system which enables the preparation of unique cyclization products. The second is the use of a transition-metal catalyst, though Lewis or Brønsted acids have generally been used for the reaction. The third is the realization of the asymmetric Nazarov cyclization. The fourth is the base-catalyzed Nazarov cyclization. Furthermore, several useful protocols for realizing Nazarov cyclization have also been developed. The recent progress on Nazarov cyclizations is summarized in Section 2. Section 3 is our chronicle in this field. We focused on the use of iron as the catalyst in Nazarov cyclizations and ionic liquids as solvents: Nazarov cyclization of thiophene derivatives using FeCl3 as the catalyst was accomplished and we succeeded in demonstrating the first example of an iron-catalyzed asymmetric Nazarov reaction. We next established Nazarov cyclization of pyrrole or indole derivatives using Fe(ClO4 )3 ·Al2 O3 as the catalyst with high trans selectivities in excellent yields. Since the cyclized product was reacted with a vinyl ketone in the presence of the same iron salt, the system allowed realization of the sequential type of Nazarov/Michael reaction of pyrrole derivatives. Furthermore, we demonstrated the recyclable use of the iron catalyst and obtained the desired Nazarov/Michael reaction products in good yields for five repetitions of the reactions without any addition of the catalyst using an ionic liquid, [bmim][NTf2 ], as the solvent. We expect that the iron-catalyzed Nazarov cyclization, in particular, in an ionic liquid solvent might become a useful method to synthesize functional molecules that include cycloalkene moieties. © 2016 The

  16. Transition Metal Catalyzed Hydroarylation of Multiple Bonds: Exploration of Second Generation Ruthenium Catalysts and Extension to Copper Systems

    SciTech Connect

    T. Brent Gunnoe

    2011-02-17

    Catalysts provide foundational technology for the development of new materials and can enhance the efficiency of routes to known materials. New catalyst technologies offer the possibility of reducing energy and raw material consumption as well as enabling chemical processes with a lower environmental impact. The rising demand and expense of fossil resources has strained national and global economies and has increased the importance of accessing more efficient catalytic processes for the conversion of hydrocarbons to useful products. The goals of the research are to develop and understand single-site homogeneous catalysts for the conversion of readily available hydrocarbons into useful materials. A detailed understanding of these catalytic reactions could lead to the development of catalysts with improved activity, longevity and selectivity. Such transformations could reduce the environmental impact of hydrocarbon functionalization, conserve energy and valuable fossil resources and provide new technologies for the production of liquid fuels. This project is a collaborative effort that incorporates both experimental and computational studies to understand the details of transition metal catalyzed C-H activation and C-C bond forming reactions with olefins. Accomplishments of the current funding period include: (1) We have completed and published studies of C-H activation and catalytic olefin hydroarylation by TpRu{l_brace}P(pyr){sub 3}{r_brace}(NCMe)R (pyr = N-pyrrolyl) complexes. While these systems efficiently initiate stoichiometric benzene C-H activation, catalytic olefin hydroarylation is hindered by inhibition of olefin coordination, which is a result of the steric bulk of the P(pyr){sub 3} ligand. (2) We have extended our studies of catalytic olefin hydroarylation by TpRu(L)(NCMe)Ph systems to L = P(OCH{sub 2}){sub 3}CEt. Thus, we have now completed detailed mechanistic studies of four systems with L = CO, PMe{sub 3}, P(pyr){sub 3} and P(OCH{sub 2}){sub 3}CEt

  17. Assessment of microcapsule—catalyst particles healing system in high performance fibre reinforced polymer composite

    NASA Astrophysics Data System (ADS)

    Bolimowski, P. A.; Wass, D. F.; Bond, I. P.

    2016-08-01

    Autonomous self-healing in carbon fibre reinforced polymer (CFRP) is demonstrated using epoxy resin filled microcapsules and a solid-state catalyst. Microcapsules filled with oligomeric epoxy resin (20-450 μm) and particles of Sc(OTf)3 are embedded in an interleave region of a unidirectional CFRP laminate and tested under mode I loading. Double cantilever beam (DCB) test specimens containing variable concentrations of microcapsules and catalyst were prepared, tested and compared to those healed by manual injection with corresponding healing resin formulation. The healing efficiency was evaluated by comparing the maximum peak load recorded on load-displacement curves for pristine and healed specimens. A 44% maximum recovery was observed for specimens containing 10 wt% of solid phase catalyst and 11 wt% of epoxy microcapsules. However, a significant (80%) decrease in initial strain energy release rate (G IC) was observed for specimens with the embedded healing chemistries.

  18. Tuning the properties of copper-based catalysts based on molecular in situ studies of model systems.

    PubMed

    Stacchiola, Darío J

    2015-07-21

    Studying catalytic processes at the molecular level is extremely challenging, due to the structural and chemical complexity of the materials used as catalysts and the presence of reactants and products in the reactor's environment. The most common materials used on catalysts are transition metals and their oxides. The importance of multifunctional active sites at metal/oxide interfaces has been long recognized, but a molecular picture of them based on experimental observations is only recently emerging. The initial approach to interrogate the surface chemistry of catalysts at the molecular level consisted of studying metal single crystals as models for reactive metal centers, moving later to single crystal or well-defined thin film oxides. The natural next iteration consisted in the deposition of metal nanoparticles on well-defined oxide substrates. Metal nanoparticles contain undercoordinated sites, which are more reactive. It is also possible to create architectures where oxide nanoparticles are deposited on top of metal single crystals, denominated inverse catalysts, leading in this case to a high concentration of reactive cationic sites in direct contact with the underlying fully coordinated metal atoms. Using a second oxide as a support (host), a multifunctional configuration can be built in which both metal and oxide nanoparticles are located in close proximity. Our recent studies on copper-based catalysts are presented here as an example of the application of these complementary model systems, starting from the creation of undercoordinated sites on Cu(111) and Cu2O(111) surfaces, continuing with the formation of mixed-metal copper oxides, the synthesis of ceria nanoparticles on Cu(111) and the codeposition of Cu and ceria nanoparticles on TiO2(110). Catalysts have traditionally been characterized before or after reactions and analyzed based on static representations of surface structures. It is shown here how dynamic changes on a catalyst's chemical state

  19. A highly versatile catalyst system for the cross-coupling of aryl chlorides and amines.

    PubMed

    Lundgren, Rylan J; Sappong-Kumankumah, Antonia; Stradiotto, Mark

    2010-02-08

    The syntheses of 2-(di-tert-butylphosphino)-N,N-dimethylaniline (L1, 71%) and 2-(di-1-adamantylphosphino)-N,N-dimethylaniline (L2, 74 %), and their application in Buchwald-Hartwig amination, are reported. In combination with [Pd(allyl)Cl](2) or [Pd(cinnamyl)Cl](2), these structurally simple and air-stable P,N ligands enable the cross-coupling of aryl and heteroaryl chlorides, including those bearing as substituents enolizable ketones, ethers, esters, carboxylic acids, phenols, alcohols, olefins, amides, and halogens, to a diverse range of amine and related substrates that includes primary alkyl- and arylamines, cyclic and acyclic secondary amines, N-H imines, hydrazones, lithium amide, and ammonia. In many cases, the reactions can be performed at low catalyst loadings (0.5-0.02 mol % Pd) with excellent functional group tolerance and chemoselectivity. Examples of cross-coupling reactions involving 1,4-bromochlorobenzene and iodobenzene are also reported. Under similar conditions, inferior catalytic performance was achieved when using Pd(OAc)(2), PdCl(2), [PdCl(2)(cod)] (cod = 1,5-cyclooctadiene), [PdCl(2)(MeCN)(2)], or [Pd(2)(dba)(3)] (dba = dibenzylideneacetone) in combination with L1 or L2, or by use of [Pd(allyl)Cl](2) or [Pd(cinnamyl)Cl](2) with variants of L1 and L2 bearing less basic or less sterically demanding substituents on phosphorus or lacking an ortho-dimethylamino fragment. Given current limitations associated with established ligand classes with regard to maintaining high activity across the diverse possible range of C-N coupling applications, L1 and L2 represent unusually versatile ligand systems for the cross-coupling of aryl chlorides and amines.

  20. Influence of phosphorus element on direct laser sintering of multicomponent Cu-based metal powder

    NASA Astrophysics Data System (ADS)

    Gu, D. D.; Shen, Y. F.

    2006-12-01

    This article presents a detailed investigation on the influence of the phosphorus element upon the laser sintering of a multicomponent Cu-based metal powder system consisting of Cu, Cu-10Sn, and Cu-8.4P. Powder systems containing 0, 10, 15, and 20 wt pct CuP were sintered in atmosphere at room temperature using the following optimal processing parameters: laser power of 350 W, scan speed of 0.04 m/s, scan line spacing of 0.15 mm, and layer thickness of 0.25 mm. It was found that the relative density of the sintered sample with 15 wt pct CuP increased by 24,4 pct as compared with the sample without phosphorus addition. A further increase in the CuP content (≥20 wt pct), however, resulted in a poor densification with a serious delamination. The exact metallurgical roles of the phosphorus element in the laser sintering process were addressed as follows. First, the phosphorus could prevent the sintering system from oxidation by forming CuPO3, thereby improving the wetting characteristics and the sintering kinetics. Second, the phosphorus could decrease the surface tension of molten materials, leading to a successive transition from highly discontinuous sintered tracks to fairly coherent ones with increasing the phosphorus content. Third, the phosphorus could lower the melt viscosity, thereby improving the microstructural homogeneity of the laser-sintered samples.

  1. Bimetallic Catalysts.

    ERIC Educational Resources Information Center

    Sinfelt, John H.

    1985-01-01

    Chemical reaction rates can be controlled by varying composition of miniscule clusters of metal atoms. These bimetallic catalysts have had major impact on petroleum refining, where work has involved heterogeneous catalysis (reacting molecules in a phase separate from catalyst.) Experimentation involving hydrocarbon reactions, catalytic…

  2. Bimetallic Catalysts.

    ERIC Educational Resources Information Center

    Sinfelt, John H.

    1985-01-01

    Chemical reaction rates can be controlled by varying composition of miniscule clusters of metal atoms. These bimetallic catalysts have had major impact on petroleum refining, where work has involved heterogeneous catalysis (reacting molecules in a phase separate from catalyst.) Experimentation involving hydrocarbon reactions, catalytic…

  3. Oxyhydrochlorination catalyst

    DOEpatents

    Taylor, Charles E.; Noceti, Richard P.

    1992-01-01

    An improved catalyst and method for the oxyhydrochlorination of methane is disclosed. The catalyst includes a pyrogenic porous support on which is layered as active material, cobalt chloride in major proportion, and minor proportions of an alkali metal chloride and of a rare earth chloride. On contact of the catalyst with a gas flow of methane, HCl and oxygen, more than 60% of the methane is converted and of that converted more than 40% occurs as monochloromethane. Advantageously, the monochloromethane can be used to produce gasoline boiling range hydrocarbons with the recycle of HCl for further reaction. This catalyst is also of value for the production of formic acid as are analogous catalysts with lead, silver or nickel chlorides substituted for the cobalt chloride.

  4. Enhanced High- and Low-Temperature Performance of NOx Reduction Catalyst Materials

    SciTech Connect

    Gao, Feng; Muntean, George G.; Peden, Charles HF; Howden, Ken; Currier, Neal; Kamasamudram, Krishna; Kumar, Ashok; Li, Junhui; Luo, Jinyong; Stafford, Randy; Yezerets, Aleksey; Castagnola, Mario; Chen, Hai-Ying; Hess, Howard ..

    2014-12-09

    In this annual CRADA program report, we will briefly highlight results from our recent studies of the stability of candidate K-based high temperature NSR materials, and comparative studies of low temperature performance of SSZ-13 and SAPO-34 CHA catalysts; in particular, recent results comparing Fe- and Cu-based CHA materials.

  5. Direct transformation of xylan-type hemicelluloses to furfural via SnCl₄ catalysts in aqueous and biphasic systems.

    PubMed

    Wang, Wenju; Ren, Junli; Li, Huiling; Deng, Aojie; Sun, Runcang

    2015-05-01

    Direct catalytic transformation of xylan-type hemicelluloses to furfural in the aqueous system and the biphasic system were comparatively investigated under mild conditions. Screening of several promising chlorides for conversion of beech xylan in the aqueous system revealed the Lewis acid SnCl4 was the most effective catalyst. Comparing to the single aqueous system, the bio-based 2-methyltetrahydrofuran (2-MTHF)/H2O biphasic system was more conducive to the synthesis of furfural, in which the highest furfural yield of 78.1% was achieved by using SnCl4 as catalysts under the optimized reaction conditions (150°C, 120 min). Additionally, the influences of xylan-type hemicelluloses with different chemical and structural features from beech, corncob and bagasse on the furfural production were studied. It was found that furfural yield to some extent was determined by the xylose content in hemicelluloses and also had relationships with the molecular weight of hemicelluloses and the degree of crystallization. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. High-Activity Dealloyed Catalysts

    SciTech Connect

    Kongkanand, Anusorn

    2014-09-30

    Reduction of costly Pt usage in proton exchange membrane fuel cell electrodes is one of the major challenges towards development and commercialization of fuel cell vehicles. Although few have met the initial-kinetic activity requirements in a realistic fuel cell device, no catalyst material has ever met the demanding fuel cell durability targets set by DOE. In this project, a team of 4 universities and 2 companies came together to investigate a concept that appeared promising in preliminary non-fuel cell tests then to further develop the catalyst to a mature level ready for vehicle implementation. The team consists of academia with technical leadership in their respective areas, a catalyst supplier, and a fuel cell system integrator.The tightly collaborative project enabled development of a highly active and durable catalyst with performance that significantly exceeds that of previous catalysts and meets the DOE targets for the first time (Figure 1A). The catalyst was then further evaluated in full-active-area stack in a realistic vehicle operating condition (Figure 1B). This is the first public demonstration that one can realize the performance benefit and Pt cost reduction over a conventional pure Pt catalyst in a long-term realistic PEMFC system. Furthermore, systematic analyses of a range of catalysts with different performance after fuel cell testing allowed for correlation between catalyst microstructure and its electrocatalytic activity and durability. This will in turn aid future catalyst development.

  7. Synthetic Catalysts for CO2 Storage: Catalytic Improvement of Solvent Capture Systems

    SciTech Connect

    2010-08-15

    IMPACCT Project: LLNL is designing a process to pull CO2 out of the exhaust gas of coal-fired power plants so it can be transported, stored, or utilized elsewhere. Human lungs rely on an enzyme known as carbonic anhydrase to help separate CO2 from our blood and tissue as part of the normal breathing process. LLNL is designing a synthetic catalyst with the same function as this enzyme. The catalyst can be used to quickly capture CO2 from coal exhaust, just as the natural enzyme does in our lungs. LLNL is also developing a method of encapsulating chemical solvents in permeable microspheres that will greatly increase the speed of binding of CO2. The goal of the project is an industry-ready chemical vehicle that can withstand the harsh environments found in exhaust gas and enable new, simple process designs requiring less capital investment.

  8. Key structure-activity relationships in the vanadium phosphorus oxide catalyst system

    SciTech Connect

    Thompson, M.R. ); Ebner, J.R. )

    1990-04-01

    The crystal structure of vanadyl pyrophosphate has been redetermined using single crystals obtained from a near solidified melt of a microcrystalline catalyst sample. Crystals that index as vanadyl pyrophosphate obtained from this melt are variable in color. Crystallographic refinement of the single crystal x-ray diffraction data indicates that structural differences among these materials can be described in terms of crystal defects associated with linear disorder of the vanadium atoms. The importance of the disorder is outlined in the context of its effect on the proposed surface topology parallel to (1,0,0). Models of the surface topology simply and intuitively account for the non-stoichometric surface atomic P/V ratio exhibited by selective catalysts of this phase. These models also point to the possible role of the excess phosphorus in providing site isolation of reactive centers at the surface. 33 refs., 7 figs.

  9. Experimental reactor system for investigation of indirect liquefaction catalysts in slurry phase operation

    SciTech Connect

    Zarochak, M.F.; Pennline, H.W.; Schehl, R.R.

    1984-02-01

    A detailed description of the slurry (three-phase) reactor scheme employed at the Pittsburgh Energy Technology Center for Fischer-Tropsch synthesis is reported. Emphasis is placed on materials of construction, equipment operation, and product collection and analysis. The unit's functional limits and safety features are also provided. Operational problems and the resolving remedial action are discussed. The reactor scheme now operates such that near isothermal conditions exist over the reactor internal length. Thus, with excellent temperature control assured, reliable information for evaluation of potential catalyst candidates for slurry phase Fischer-Tropsch synthesis is possible within a wide range of operating conditions. Test results with a fused-iron catalyst suspended in a paraffinic liquid medium are given as an example.

  10. SU-E-T-350: Verification of Gating Performance of a New Elekta Gating Solution: Response Kit and Catalyst System

    SciTech Connect

    Xie, X; Cao, D; Housley, D; Mehta, V; Shepard, D

    2014-06-01

    Purpose: In this work, we have tested the performance of new respiratory gating solutions for Elekta linacs. These solutions include the Response gating and the C-RAD Catalyst surface mapping system.Verification measurements have been performed for a series of clinical cases. We also examined the beam on latency of the system and its impact on delivery efficiency. Methods: To verify the benefits of tighter gating windows, a Quasar Respiratory Motion Platform was used. Its vertical-motion plate acted as a respiration surrogate and was tracked by the Catalyst system to generate gating signals. A MatriXX ion-chamber array was mounted on its longitudinal-moving platform. Clinical plans are delivered to a stationary and moving Matrix array at 100%, 50% and 30% gating windows and gamma scores were calculated comparing moving delivery results to the stationary result. It is important to note that as one moves to tighter gating windows, the delivery efficiency will be impacted by the linac's beam-on latency. Using a specialized software package, we generated beam-on signals of lengths of 1000ms, 600ms, 450ms, 400ms, 350ms and 300ms. As the gating windows get tighter, one can expect to reach a point where the dose rate will fall to nearly zero, indicating that the gating window is close to beam-on latency. A clinically useful gating window needs to be significantly longer than the latency for the linac. Results: As expected, the use of tighter gating windows improved delivery accuracy. However, a lower limit of the gating window, largely defined by linac beam-on latency, exists at around 300ms. Conclusion: The Response gating kit, combined with the C-RAD Catalyst, provides an effective solution for respiratorygated treatment delivery. Careful patient selection, gating window design, even visual/audio coaching may be necessary to ensure both delivery quality and efficiency. This research project is funded by Elekta.

  11. Design and synthesis of a new type of ferrocene-based planar chiral DMAP analogues. A new catalyst system for asymmetric nucleophilic catalysis.

    PubMed

    Seitzberg, Jimmi Gerner; Dissing, Carsten; Søtofte, Inger; Norrby, Per-Ola; Johannsen, Mogens

    2005-10-14

    A new first-generation catalyst system for nucleophilic catalysis has been developed. It is based on a planar chiral ferrocene skeleton with either the potent nucleophile 4-(dimethylamino)pyridine (DMAP) or the related 4-nitropyridine N-oxide attached in either the 2- or the 3-position. The syntheses are short, efficient, and enantioselective and X-ray crystal structures of both DMAP-derived catalysts are presented. The DMAP-based catalysts were tested in asymmetric reactions and the 3-derivative 14 showed good activity and a moderate level of enantioselectivity. The sense of induction (selectivity) was studied using molecular modeling and the results pointed at new directions for future generations of catalysts based on this design.

  12. Evaluation of PEMFC System Contaminants on the Performance of Pt Catalyst via Cyclic Voltammetry: Preprint

    SciTech Connect

    Wang, H.; Macomber, C.; Dinh, H. N.

    2012-07-01

    Using electrochemical cyclic voltammetry as a quick ex-situ screening tool, the impact of the extracted solution and the individual leachable constituents from prospective BOP component materials on the performance and recoverability of the platinum catalyst were evaluated. Taking an extract from Zytel{trademark} HTN51G35HSLR (PPA) as an example, the major leachable organic components are caprolactam and 1,6 hexanediol. While these organic compounds by themselves do poison the Pt catalyst to some extent, such influence is mostly recoverable by means of potential holding and potential cycling. The extracted solution, however, shows a more drastic poisoning effect and it was not recoverable. Therefore the non-recoverable poisoning effect observed for the extracted solution is not from the two organic species studied. This demonstrates the complexity of such a contaminant study. Inorganic compounds that are known poisons like sulfur even in very low concentrations, may have a more dominant effect on the Pt catalyst and the recoverability.

  13. Catalyst mixtures

    DOEpatents

    Masel, Richard I.; Rosen, Brian A.

    2017-02-14

    Catalysts that include at least one catalytically active element and one helper catalyst can be used to increase the rate or lower the overpotential of chemical reactions. The helper catalyst can simultaneously act as a director molecule, suppressing undesired reactions and thus increasing selectivity toward the desired reaction. These catalysts can be useful for a variety of chemical reactions including, in particular, the electrochemical conversion of CO.sub.2 or formic acid. The catalysts can also suppress H.sub.2 evolution, permitting electrochemical cell operation at potentials below RHE. Chemical processes and devices using the catalysts are also disclosed, including processes to produce CO, OH.sup.-, HCO.sup.-, H.sub.2CO, (HCO.sub.2).sup.-, H.sub.2CO.sub.2, CH.sub.3OH, CH.sub.4, C.sub.2H.sub.4, CH.sub.3CH.sub.2OH, CH.sub.3COO.sup.-, CH.sub.3COOH, C.sub.2H.sub.6, O.sub.2, H.sub.2, (COOH).sub.2, or (COO.sup.-).sub.2, and a specific device, namely, a CO.sub.2 sensor.

  14. Insights into the Mechanism of a Covalently Linked Organic Dye-Cobaloxime Catalyst System for Dye-Sensitized Solar Fuel Devices.

    PubMed

    Pati, Palas Baran; Zhang, Lei; Philippe, Bertrand; Fernández-Terán, Ricardo; Ahmadi, Sareh; Tian, Lei; Rensmo, Håkan; Hammarström, Leif; Tian, Haining

    2017-06-09

    A covalently linked organic dye-cobaloxime catalyst system based on mesoporous NiO is synthesized by a facile click reaction for mechanistic studies and application in a dye-sensitized solar fuel device. The system is systematically investigated by photoelectrochemical measurements, density functional theory, time-resolved fluorescence, transient absorption spectroscopy, and photoelectron spectroscopy. The results show that irradiation of the dye-catalyst on NiO leads to ultrafast hole injection into NiO from the excited dye, followed by a fast electron transfer process to reduce the catalyst. Moreover, the dye adopts different structures with different excited state energies, and excitation energy transfer occurs between neighboring molecules on the semiconductor surface. The photoelectrochemical experiments also show hydrogen production by this system. The axial chloride ligands of the catalyst are released during photocatalysis to create the active sites for proton reduction. A working mechanism of the dye-catalyst system on the photocathode is proposed on the basis of this study. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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

    PubMed

    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.

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

    PubMed Central

    2017-01-01

    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. PMID:28470049

  17. Colorimetric quantification of galactose using a nanostructured multi-catalyst system entrapping galactose oxidase and magnetic nanoparticles as peroxidase mimetics.

    PubMed

    Kim, Moon Il; Shim, Jongmin; Li, Taihua; Woo, Min-Ah; Cho, Daeyeon; Lee, Jinwoo; Park, Hyun Gyu

    2012-03-07

    A colorimetric method for quantification of galactose, which utilizes a nanostructured multi-catalyst system consisting of Fe(3)O(4) magnetic nanoparticles (MNPs) and galactose oxidase (Gal Ox) simultaneously entrapped in large pore sized mesocellular silica, is described. Gal Ox, immobilized in a silica matrix, promotes reaction of galactose to generate H(2)O(2) that subsequently activates MNPs in silica mesopores to convert a colorimetric substrate into a colored product. By using this colorimetric method, galactose can be specifically detected. Along with excellent reusability via application of simple magnetic capturing, enhanced operational stability was achieved by employing a cross-linked enzyme aggregate (CLEA) method for Gal Ox immobilization. This protocol leads to effective prevention of enzyme leaching from the pores of mesocellular silica. The analytical utility of the new colorimetric biosensor was demonstrated by its use in diagnosing galactosemia, a genetic metabolic disorder characterized by the inability to utilize galactose, through analysis of clinical dried blood spot specimens. A microscale well-plate format was employed that possesses a multiplexing capability. The multi-catalyst system entrapping Gal Ox and MNPs represents a new approach for rapid, convenient, and cost-effective quantification of galactose in human blood and it holds promise as an alternative method for galactosemia diagnosis, replacing the laborious procedures that are currently in use.

  18. Multifunctional catalysts based on carbon nanotubes and titanate nanotubes for oxidation of organic compounds in biphasic systems.

    PubMed

    Santos, S R A; Jardim, I S; Bicalho, H A; Binatti, I; Sousa, E M B; Peres, A M; Resende, R R; Lorençon, E

    2016-12-01

    Amphiphilic catalysts composed of carbon nanotubes (CNTs) and titanate nanotubes (TiNTs) have been successfully synthesized by refluxing anatase TiO2 and functionalised CNTs in concentrated NaOH solution. The prepared materials were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, thermogravimetric analysis (TGA), and N2 physisorption isotherms. The catalytic activity of the synthesized composites was first evaluated in the oxidation of methyl yellow (MY) using H2O2 as oxidant in a single liquid phase system and in a biphasic water/oil mixture. The results of these experiments indicated that the catalytic activities of nanocomposites were very similar in the single liquid-phase oxidation. However, the modification of TiNTs with CNTs led to a substantially enhanced MY oxidation in the biphasic system. The nanocomposites show excellent interaction with both hydrophilic and hydrophobic compounds and thus stabilise emulsions. Under biphasic conditions, the catalysts can be easily separated and recycled, retaining catalytic activity even after eight runs. Additionally, the hybrid materials show superior catalytic activity and selectivity in the biphasic oxidation of benzyl alcohol with H2O2, as compared to pure TiNTs.

  19. Stabilized rhodium(0) nanoparticles: a reusable hydrogenation catalyst for arene derivatives in a biphasic water-liquid system.

    PubMed

    Schulz, J; Roucoux, A; Patin, H

    2000-02-18

    A colloidal system based on an aqueous suspension of rhodium(o) nanoparticles proved to be an efficient catalyst for the hydrogenation of arene derivatives under biphasic conditions. The rhodium nanoparticles (2-2.5 nm) were synthesized by the reduction of RhCl3 x 3H2O with sodium borohydride and were stabilized by highly water-soluble N-alkyl-N-(2-hydroxyethyl)ammonium salts (HEA-Cn). These surfactant molecules were characterized by measurements of the surface tension and the aqueous dispersions with rhodium were observed by transmission electron cryomicroscopy. The catalytic system is efficient under ultramild conditions, namely room temperature and 1 atm H2 pressure. The aqueous phase which contains the protected rhodium(0) colloids can be reused without significant loss of activity. The microheterogeneous behavior of this catalytic system was confirmed on a mercury poisoning experiment.

  20. Development of Optimal Catalyst Designs and Operating Strategies for Lean NOx Reduction in Coupled LNT-SCR Systems

    SciTech Connect

    Harold, Michael; Crocker, Mark; Balakotaiah, Vemuri; Luss, Dan; Choi, Jae-Soon; Dearth, Mark; McCabe, Bob; Theis, Joe

    2013-09-30

    Oxides of nitrogen in the form of nitric oxide (NO) and nitrogen dioxide (NO{sub 2}) commonly referred to as NO{sub x}, is one of the two chemical precursors that lead to ground-level ozone, a ubiquitous air pollutant in urban areas. A major source of NO{sub x} is generated by equipment and vehicles powered by diesel engines, which have a combustion exhaust that contains NO{sub x} in the presence of excess O{sub 2}. Catalytic abatement measures that are effective for gasoline-fueled engines such as the precious metal containing three-way catalytic converter (TWC) cannot be used to treat O2-laden exhaust containing NO{sub x}. Two catalytic technologies that have emerged as effective for NO{sub x} abatement are NO{sub x} storage and reduction (NSR) and selective catalytic reduction (SCR). NSR is similar to TWC but requires much larger quantities of expensive precious metals and sophisticated periodic switching operation, while SCR requires an on-board source of ammonia which serves as the chemical reductant of the NO{sub x}. The fact that NSR produces ammonia as a byproduct while SCR requires ammonia to work has led to interest in combining the two together to avoid the need for the cumbersome ammonia generation system. In this project a comprehensive study was carried out of the fundamental aspects and application feasibility of combined NSR/SCR. The project team, which included university, industry, and national lab researchers, investigated the kinetics and mechanistic features of the underlying chemistry in the lean NOx trap (LNT) wherein NSR was carried out, with particular focus on identifying the operating conditions such as temperature and catalytic properties which lead to the production of ammonia in the LNT. The performance features of SCR on both model and commercial catalysts focused on the synergy between the LNT and SCR converters in terms of utilizing the upstream-generated ammonia and alternative reductants such as propylene, representing the

  1. Vacuum Brazing Diamond Grits with Cu-based or Ni-based Filler Metal

    NASA Astrophysics Data System (ADS)

    Qi, Wenchun; Lu, Jinbin; Li, Yang; Xu, Shuai; Zhong, Sujuan; Wang, Bangfu; Qiu, Xinkai

    2017-08-01

    Diamond grits were brazed using Cu-Sn-Cr and Ni-Cr-B-Si filler metals, and the brazed grits were examined for microstructure (SEM, EDS, XRD), microhardness, and compression strength. Results showed that the microstructure of the Cu-based filler metal was uniform and consisted of α-Cu + (α-Cu + δ). Its wettability to the diamond was better than Ni-based filler due to the formation of a thin carbide reaction layer that improved the bond strength between the diamond and steel. The Cu-based filler led to reduced thermal damage to the diamond. The Cr in the filler metal diffused to the steel substrate to form a reaction layer at the filler/steel substrate interface. The microhardness of the Ni filler metal (810-830 HV0.3) was significantly higher than that of Cu filler metal (170-230 HV0.3). The compressive load values of the diamond grits brazed with Cu-based or Ni-based filler metal were 93.7 and 49.2% of the original diamond, and the TI values were 83.7 and 59.8% of the original diamond. Grinding experiments for failure mode in monolayer tools revealed that the tools brazed with Cu-based filler metal had a lower macro-fracture ratio than those brazed using the Ni-based filler.

  2. Vacuum Brazing Diamond Grits with Cu-based or Ni-based Filler Metal

    NASA Astrophysics Data System (ADS)

    Qi, Wenchun; Lu, Jinbin; Li, Yang; Xu, Shuai; Zhong, Sujuan; Wang, Bangfu; Qiu, Xinkai

    2017-06-01

    Diamond grits were brazed using Cu-Sn-Cr and Ni-Cr-B-Si filler metals, and the brazed grits were examined for microstructure (SEM, EDS, XRD), microhardness, and compression strength. Results showed that the microstructure of the Cu-based filler metal was uniform and consisted of α-Cu + (α-Cu + δ). Its wettability to the diamond was better than Ni-based filler due to the formation of a thin carbide reaction layer that improved the bond strength between the diamond and steel. The Cu-based filler led to reduced thermal damage to the diamond. The Cr in the filler metal diffused to the steel substrate to form a reaction layer at the filler/steel substrate interface. The microhardness of the Ni filler metal (810-830 HV0.3) was significantly higher than that of Cu filler metal (170-230 HV0.3). The compressive load values of the diamond grits brazed with Cu-based or Ni-based filler metal were 93.7 and 49.2% of the original diamond, and the TI values were 83.7 and 59.8% of the original diamond. Grinding experiments for failure mode in monolayer tools revealed that the tools brazed with Cu-based filler metal had a lower macro-fracture ratio than those brazed using the Ni-based filler.

  3. Exploring the cooperation effect of DBD byproducts and Ag/TiO2 catalyst for water treatment in an APPJ system

    NASA Astrophysics Data System (ADS)

    Guangliang, Chen; Wei, Hu; Jinsong, Yu; Wenxia, Chen; Jun, Huang

    2017-01-01

    In this paper, the collective effects of combining heterogeneous Ag/TiO2 nanocomposite catalyst with the byproducts (primarily the irradiation and the O3 species) of an atmospheric pressure plasma jet (APPJ) system on the degradation of methyl orange (MO) were explored. The heterostructured Ag/TiO2 nanocomposite was achieved via decorating the Ag quantum dots (QDs) on the commercially available TiO2 catalyst (P25) through a hydrothermal method. The x-ray diffraction analysis of the nanocomposite catalyst showed the diffraction peaks at 44.3°, 64.4°, and 77.5°, corresponding to the Ag planes of (200), (220) and (311), respectively. The high resolution transmission electron microscope characterization of the nanocomposite catalyst indicated that the Ag QDs with an average diameter of 5 nm were homogeneously distributed on the P25 surface. The experimental results on the MO photodegradation showed that the APPJ irradiation had a marginal effect on the cleavage of the MO molecules. When the Ag/TiO2 nanocomposite catalyst was used, the photodegradation rate of MO increased about 5 times. When both the APPJ byproducts and the Ag/TiO2 nanocomposite catalyst were used, however, over 90% of the MO in the tested solution was cleaved within 15 min, and the energy efficiency was about 0.6 g/kW h. Moreover, an optimal Ag dosage value was determined (6 wt%). The catalytic results indicated that combining the DBD plasma byproducts with heterogeneous nanocomposite catalysts may be an effect protocol for decreasing the application cost of the DBD system and mitigating the environment pollution by organic dyes in the textile industry.

  4. Exploring the cooperation effect of DBD byproducts and Ag/TiO2 catalyst for water treatment in an APPJ system

    NASA Astrophysics Data System (ADS)

    Chen, Guangliang; Hu, Wei; Yu, Jinsong; Chen, Wenxia; Huang, Jun

    2017-01-01

    In this paper, the collective effects of combining heterogeneous Ag/TiO2 nanocomposite catalyst with the byproducts (primarily the irradiation and the O3 species) of an atmospheric pressure plasma jet (APPJ) system on the degradation of methyl orange (MO) were explored. The heterostructured Ag/TiO2 nanocomposite was achieved via decorating the Ag quantum dots (QDs) on the commercially available TiO2 catalyst (P25) through a hydrothermal method. The x-ray diffraction analysis of the nanocomposite catalyst showed the diffraction peaks at 44.3°, 64.4°, and 77.5°, corresponding to the Ag planes of (200), (220) and (311), respectively. The high resolution transmission electron microscope characterization of the nanocomposite catalyst indicated that the Ag QDs with an average diameter of 5 nm were homogeneously distributed on the P25 surface. The experimental results on the MO photodegradation showed that the APPJ irradiation had a marginal effect on the cleavage of the MO molecules. When the Ag/TiO2 nanocomposite catalyst was used, the photodegradation rate of MO increased about 5 times. When both the APPJ byproducts and the Ag/TiO2 nanocomposite catalyst were used, however, over 90% of the MO in the tested solution was cleaved within 15 min, and the energy efficiency was about 0.6 g/kW h. Moreover, an optimal Ag dosage value was determined (6 wt%). The catalytic results indicated that combining the DBD plasma byproducts with heterogeneous nanocomposite catalysts may be an effect protocol for decreasing the application cost of the DBD system and mitigating the environment pollution by organic dyes in the textile industry.

  5. Synthesis of silicon-germanium axial nanowire heterostructures in a solvent vapor growth system using indium and tin catalysts.

    PubMed

    Mullane, E; Geaney, H; Ryan, K M

    2015-03-14

    Here we describe a relatively facile synthetic protocol for the formation of Si-Ge and Si-Ge-Si1-xGex axial nanowire heterostructures. The wires are grown directly on substrates with an evaporated catalytic layer placed in the vapour zone of a high boiling point solvent with the silicon and germanium precursors injected as liquids sequentially. We show that these heterostructures can be formed using either indium or tin as the catalyst seeds which form in situ during the thermal anneal. There is a direct correlation between growth time and segment length allowing good control over the wire composition. The formation of axial heterostructures of Si-Ge-Si1-xGex nanowires using a triple injection is further discussed with the alloyed Si1-xGex third component formed due to residual Ge precursor and its greater reactivity in comparison to silicon. It was found that the degree of tapering at each hetero-interface varied with both the catalyst type and composition of the NW. The report shows the versatility of the solvent vapour growth system for the formation of complex Si-Ge NW heterostructures.

  6. Alkylation of xylenes with acetaldehyde/paraldehyde with sulfuric acid as catalyst in a two-phase system

    SciTech Connect

    Vasudevan, T.V.; Sharma, M.M.

    1983-01-01

    The kinetics of alkylation of xylenes with acetaldehyde/paraldehyde, with sulfuric acid (86.5-98% w/w) as a catalyst in a two-phase system to give dixylylethanes, was studied in the temperature range of -13 to -3/sup 0/C. Two mechanically agitated contactors, one of 8.5 cm i.d. and the other of 11 cm i.d., were used and it was possible to eliminate mass transfer resistance. Experiments were conducted in batch as well as continuous modes of operation. The reaction was found to be first order with respect to xylene as well as acetaldehyde (concentration < 2.9 M). Some novel features of this reaction system have been brought out, including the remarkable effect of the concentration of sulfuric acid on the pseudo-second-order rate constant, which increases by a factor of about 25 as the strength of sulfuric acid is increased from 86.5 to 98 wt %.

  7. Highly dispersed metal catalyst

    DOEpatents

    Xiao, Xin; West, William L.; Rhodes, William D.

    2016-11-08

    A supported catalyst having an atomic level single atom structure is provided such that substantially all the catalyst is available for catalytic function. A process of forming a single atom catalyst unto a porous catalyst support is also provided.

  8. Versatile photocatalytic systems for H2 generation in water based on an efficient DuBois-type nickel catalyst.

    PubMed

    Gross, Manuela A; Reynal, Anna; Durrant, James R; Reisner, Erwin

    2014-01-08

    The generation of renewable H2 through an efficient photochemical route requires photoinduced electron transfer (ET) from a light harvester to an efficient electrocatalyst in water. Here, we report on a molecular H2 evolution catalyst (NiP) with a DuBois-type [Ni(P2(R')N2(R"))2](2+) core (P2(R')N2(R") = bis(1,5-R'-diphospha-3,7-R"-diazacyclooctane), which contains an outer coordination sphere with phosphonic acid groups. The latter functionality allows for good solubility in water and immobilization on metal oxide semiconductors. Electrochemical studies confirm that NiP is a highly active electrocatalyst in aqueous electrolyte solution (overpotential of approximately 200 mV at pH 4.5 with a Faradaic yield of 85 ± 4%). Photocatalytic experiments and investigations on the ET kinetics were carried out in combination with a phosphonated Ru(II) tris(bipyridine) dye (RuP) in homogeneous and heterogeneous environments. Time-resolved luminescence and transient absorption spectroscopy studies confirmed that directed ET from RuP to NiP occurs efficiently in all systems on the nano- to microsecond time scale, through three distinct routes: reductive quenching of RuP in solution or on the surface of ZrO2 ("on particle" system) or oxidative quenching of RuP when the compounds were immobilized on TiO2 ("through particle" system). Our studies show that NiP can be used in a purely aqueous solution and on a semiconductor surface with a high degree of versatility. A high TOF of 460 ± 60 h(-1) with a TON of 723 ± 171 for photocatalytic H2 generation with a molecular Ni catalyst in water and a photon-to-H2 quantum yield of approximately 10% were achieved for the homogeneous system.

  9. Versatile Photocatalytic Systems for H2 Generation in Water Based on an Efficient DuBois-Type Nickel Catalyst

    PubMed Central

    2013-01-01

    The generation of renewable H2 through an efficient photochemical route requires photoinduced electron transfer (ET) from a light harvester to an efficient electrocatalyst in water. Here, we report on a molecular H2 evolution catalyst (NiP) with a DuBois-type [Ni(P2R′N2R″)2]2+ core (P2R′N2R″ = bis(1,5-R′-diphospha-3,7-R″-diazacyclooctane), which contains an outer coordination sphere with phosphonic acid groups. The latter functionality allows for good solubility in water and immobilization on metal oxide semiconductors. Electrochemical studies confirm that NiP is a highly active electrocatalyst in aqueous electrolyte solution (overpotential of approximately 200 mV at pH 4.5 with a Faradaic yield of 85 ± 4%). Photocatalytic experiments and investigations on the ET kinetics were carried out in combination with a phosphonated Ru(II) tris(bipyridine) dye (RuP) in homogeneous and heterogeneous environments. Time-resolved luminescence and transient absorption spectroscopy studies confirmed that directed ET from RuP to NiP occurs efficiently in all systems on the nano- to microsecond time scale, through three distinct routes: reductive quenching of RuP in solution or on the surface of ZrO2 (“on particle” system) or oxidative quenching of RuP when the compounds were immobilized on TiO2 (“through particle” system). Our studies show that NiP can be used in a purely aqueous solution and on a semiconductor surface with a high degree of versatility. A high TOF of 460 ± 60 h–1 with a TON of 723 ± 171 for photocatalytic H2 generation with a molecular Ni catalyst in water and a photon-to-H2 quantum yield of approximately 10% were achieved for the homogeneous system. PMID:24320740

  10. Mixed Alcohol Synthesis Catalyst Screening

    SciTech Connect

    Gerber, Mark A.; White, James F.; Stevens, Don J.

    2007-09-03

    National Renewable Energy Laboratory (NREL) and Pacific Northwest National Laboratory (PNNL) are conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). PNNL is tasked with obtaining commercially available or preparing promising mixed-alcohol catalysts and screening them in a laboratory-scale reactor system. Commercially available catalysts and the most promising experimental catalysts are provided to NREL for testing using a slipstream from a pilot-scale biomass gasifier. From the standpoint of producing C2+ alcohols as the major product, it appears that the rhodium catalyst is the best choice in terms of both selectivity and space-time yield (STY). However, unless the rhodium catalyst can be improved to provide minimally acceptable STYs for commercial operation, mixed alcohol synthesis will involve significant production of other liquid coproducts. The modified Fischer-Tropsch catalyst shows the most promise for providing both an acceptable selectivity to C2+ alcohols and total liquid STY. However, further optimization of the Fischer-Tropsch catalysts to improve selectivity to higher alcohols is highly desired. Selection of a preferred catalyst will likely entail a decision on the preferred coproduct slate. No other catalysts tested appear amenable to the significant improvements needed for acceptable STYs.

  11. Reforming catalyst

    SciTech Connect

    Baird, W.C. Jr.; Swan, G.A.

    1991-11-19

    This patent describes a catalyst useful for reforming a naphtha feed at high severity reforming conditions. It comprises the metals, platinum, rhenium and iridium on a refractory porous inorganic oxide support, the support consisting essentially of alumina, wherein the concentration by weight of each of the metals platinum and rhenium is at least 0.1 percent and iridium at least 0.15 percent and at least one of the metals is present in a concentration of at least 0.3 percent, and the sum-total; concentration of the metals is greater than 0.9 percent, and wherein each catalyst particle contains all three of the metals platinum, rhenium and iridium. This patent also describes this composition wherein the catalyst contains from about 0.1 percent to about 3 percent of a halogen and from about 0.05 percent to about 0.02 percent sulfur.

  12. Brown algae hydrolysis in 1-n-butyl-3-methylimidazolium chloride with mineral acid catalyst system.

    PubMed

    Malihan, Lenny B; Nisola, Grace M; Chung, Wook-Jin

    2012-08-01

    The amenability of three brown algal species, Sargassum fulvellum, Laminaria japonica and Undaria pinnatifida, to hydrolysis were investigated using the ionic liquid (IL), 1-n-butyl-3-methylimidazolium chloride ([BMIM]Cl). Compositional analyses of the brown algae reveal that sufficient amounts of sugars (15.5-29.4 wt.%) can be recovered. Results from hydrolysis experiments show that careful selection of the type of mineral acid as catalyst and control of acid loading could maximize the recovery of sugars. Optimal reaction time and temperature were determined from the kinetic studies on the sequential reducing sugar (TRS) formation and degradation. Optimal reaction times were determined based on the extent of furfurals formation as TRS degradation products. X-ray diffraction and environmental scanning electron microscopy confirmed the suitability of [BMIM]Cl as solvent for the hydrolysis of the three brown algae. Overall results show the potential of brown algae as renewable energy resources for the production of valuable chemicals and biofuels.

  13. Responses of an immobilized-catalyst Belousov-Zabotinsky reaction system to electric fields

    NASA Astrophysics Data System (ADS)

    Miyakawa, Kenji; Mizoguchi, Michiko

    1998-11-01

    Effects of direct and alternating current electric fields on the chemical oscillator have been investigated. The chemical oscillator was realized by immersing the cation exchange bead loaded with the ferroin catalyst in the Belousov-Zabotinsky reaction solution. Various dynamic behaviors appeared depending on the direction, the frequency, and the strength of the electric field. Their time series were characterized in terms of power spectra. Observed behaviors were explained by assuming a field-induced transport of the inhibitor Br-. A phase diagram concerning dynamic behaviors was obtained as a function of the frequency and the strength of the electric field. The irregular oscillation was found to necessarily appear in the transition between 1/1 and 1/2 (or 2/1) entrainments. For further examination, a three-dimensional phase portrait was constructed using the time-delay method, and the largest Lyapunov exponent was calculated.

  14. Evaluation of the effects of a new combustion system and catalyst on engine emissions

    SciTech Connect

    Corbo, P.; Corcione, F.E.; Vaglieco, B.M.

    1990-01-01

    The paper reports the results of an experimental investigation carried out on a four-stroke single-cylinder D.I. diesel engine (100 {times} 95mm bore {times} stroke) with the aim to evaluate the effects of a four-lobe square combustion chamber on the gaseous and particulate emissions. Fluid-dynamic behaviour of the axisymmetric toroidal and four-lobe square chambers was investigated by Laser Doppler Anemometry. Engine tests at 2000 and 3000 rpm for different state of combustion (SOC) and A/F ratio are reported. Particulate, HC and NO{sub x} emission index measured under different operating conditions are given. In addition, the volatile content of the particulates produced from the two chambers at various engine operative conditions was measured by thermogravimetric analysis (TGA). Finally, the catalytic activity of a metal-oxide-based catalyst in the combustion of particulate was also evaluated by TGA.

  15. Nano-sized layered Mn oxides as promising and biomimetic water oxidizing catalysts for water splitting in artificial photosynthetic systems.

    PubMed

    Najafpour, Mohammad Mahdi; Heidari, Sima; Amini, Emad; Khatamian, Masoumeh; Carpentier, Robert; Allakhverdiev, Suleyman I

    2014-04-05

    One challenge in artificial photosynthetic systems is the development of artificial model compounds to oxidize water. The water-oxidizing complex of Photosystem II which is responsible for biological water oxidation contains a cluster of four Mn ions bridged by five oxygen atoms. Layered Mn oxides as efficient, stable, low cost, environmentally friendly and easy to use, synthesize, and manufacture compounds could be considered as functional and structural models for the site. Because of the related structure of these Mn oxides and the catalytic centre of the active site of the water oxidizing complex of Photosystem II, the study of layered Mn oxides may also help to understand more about the mechanism of water oxidation by the natural site. This review provides an overview of the current status of layered Mn oxides in artificial photosynthesis and discuss the sophisticated design strategies for Mn oxides as water oxidizing catalysts.

  16. Catalyst activator

    DOEpatents

    McAdon, Mark H.; Nickias, Peter N.; Marks, Tobin J.; Schwartz, David J.

    2001-01-01

    A catalyst activator particularly adapted for use in the activation of metal complexes of metals of Group 3-10 for polymerization of ethylenically unsaturated polymerizable monomers, especially olefins, comprising two Group 13 metal or metalloid atoms and a ligand structure including at least one bridging group connecting ligands on the two Group 13 metal or metalloid atoms.

  17. Hydrogen evolution reaction catalyst

    DOEpatents

    Subbaraman, Ram; Stamenkovic, Vojislav; Markovic, Nenad; Tripkovic, Dusan

    2016-02-09

    Systems and methods for a hydrogen evolution reaction catalyst are provided. Electrode material includes a plurality of clusters. The electrode exhibits bifunctionality with respect to the hydrogen evolution reaction. The electrode with clusters exhibits improved performance with respect to the intrinsic material of the electrode absent the clusters.

  18. Sabatier Catalyst Poisoning Investigation

    NASA Technical Reports Server (NTRS)

    Nallette, Tim; Perry, Jay; Abney, Morgan; Knox, Jim; Goldblatt, Loel

    2013-01-01

    The Carbon Dioxide Reduction Assembly (CRA) on the International Space Station (ISS) has been operational since 2010. The CRA uses a Sabatier reactor to produce water and methane by reaction of the metabolic CO2 scrubbed from the cabin air and the hydrogen byproduct from the water electrolysis system used for metabolic oxygen generation. Incorporating the CRA into the overall air revitalization system has facilitated life support system loop closure on the ISS reducing resupply logistics and thereby enhancing longer term missions. The CRA utilizes CO2 which has been adsorbed in a 5A molecular sieve within the Carbon Dioxide Removal Assembly, CDRA. There is a potential of compounds with molecular dimensions similar to, or less than CO2 to also be adsorbed. In this fashion trace contaminants may be concentrated within the CDRA and subsequently desorbed with the CO2 to the CRA. Currently, there is no provision to remove contaminants prior to entering the Sabatier catalyst bed. The risk associated with this is potential catalyst degradation due to trace organic contaminants in the CRA carbon dioxide feed acting as catalyst poisons. To better understand this risk, United Technologies Aerospace System (UTAS) has teamed with MSFC to investigate the impact of various trace contaminants on the CRA catalyst performance at relative ISS cabin air concentrations and at about 200/400 times of ISS concentrations, representative of the potential concentrating effect of the CDRA molecular sieve. This paper summarizes our initial assessment results.

  19. Method and system for the combination of non-thermal plasma and metal/metal oxide doped .gamma.-alumina catalysts for diesel engine exhaust aftertreatment system

    DOEpatents

    Aardahl, Christopher L.; Balmer-Miller, Mari Lou; Chanda, Ashok; Habeger, Craig F.; Koshkarian, Kent A.; Park, Paul W.

    2006-07-25

    The present disclosure pertains to a system and method for treatment of oxygen rich exhaust and more specifically to a method and system that combines non-thermal plasma with a metal doped .gamma.-alumina catalyst. Current catalyst systems for the treatment of oxygen rich exhaust are capable of achieving only approximately 7 to 12% NO.sub.x reduction as a passive system and only 25 40% reduction when a supplemental hydrocarbon reductant is injected into the exhaust stream. It has been found that treatment of an oxygen rich exhaust initially with a non-thermal plasma and followed by subsequent treatment with a metal doped .gamma.-alumina prepared by the sol gel method is capable of increasing the NO.sub.x reduction to a level of approximately 90% in the absence of SO.sub.2 and 80% in the presence of 20 ppm of SO.sub.2. Especially useful metals have been found to be indium, gallium, and tin.

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

    DOE PAGES

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

    2017-07-13

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

  1. Microstructure-strength relationships of heavily deformed Cu-based composites

    SciTech Connect

    Trybus, C.L.

    1988-01-01

    Heavily deformed Cu-based composites attain anomalous increases in strength upon mechanical deformation. The unique filamentary microstructures that evolve during processing (cold rolling, wire drawing or swaging) are the source of the strengthening. Composite strength is correlated to microstructural characteristics for arc-melted Cu-20 vol.% Nb cold rolled up to a true strain of 6.9. During rolling Nb elongates and becomes ribbon-like while the Cu matrix undergoes a cycle of deformation-dynamic recovery-recrystallization which allows for the further reduction of the Nb. Longitudinal and transverse specimens have equivalent mechanical properties. The ultimate tensile strength of the sheet showed a weak dependence on Nb filament spacing and its strength is controlled by a dislocation propagation mechanism. The feasibility of producing heavily deformed Cu-based composites via powder metallurgical processing techniques is explored because of the wider range of composite compositions which can be produced in contrast with ingot metallurgy.

  2. Continuous synthesis of methanol: heterogeneous hydrogenation of ethylene carbonate over Cu/HMS catalysts in a fixed bed reactor system.

    PubMed

    Chen, Xi; Cui, Yuanyuan; Wen, Chao; Wang, Bin; Dai, Wei-Lin

    2015-09-18

    Continuous fixed-bed catalytic hydrogenation of ethylene carbonate (EC) to methanol and ethylene glycol (EG), an emerging synthetic process of methanol via indirect conversion of CO2, was successfully performed over Cu/HMS catalysts prepared by the ammonia evaporation (AE) method. The catalysts possessed superb performance with a conversion of 100% and a selectivity to methanol of 74%.

  3. Manganese oxide supported on gold/iron as a water-oxidizing catalyst in artificial photosynthetic systems.

    PubMed

    Najafpour, Mohammad Mahdi; Hosseini, Seyedeh Maedeh; Zand, Zahra

    2016-05-31

    Herein, we reported that KMnO4 with iron nanoparticles coated with gold layers was a promising catalyst for water oxidation. The compound was characterized by scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, atomic absorption spectroscopy and electrochemistry. The new compound was a conductive, recyclable, highly dispersible, magnetically separable, environmentally friendly, and nano-sized catalyst for water oxidation via cerium(iv) ammonium nitrate or Ru(bpy)3(3+) and electrochemical water oxidation. The turnover frequency of Mn oxide/gold/iron for water oxidation via cerium(iv) ammonium nitrate is 0.4 mmol O2 per mol Mn per second, which shows that this catalyst is among the best Mn-based catalysts for water oxidation. We also showed a strategy for placing this catalyst on the surface of an electrode without adding any other compounds.

  4. A semiconductor gas sensor system for high throughput screening of heterogeneous catalysts for the production of benzene derivatives

    NASA Astrophysics Data System (ADS)

    Yamada, Yusuke; Ueda, Atsushi; Shioyama, Hiroshi; Maekawa, Toru; Kanda, Keisen; Suzuki, Kengo; Kobayashi, Tetsuhiko

    2005-01-01

    We used a semiconductor gas sensor system developed for odour discrimination for a rapid quantification of benzene derivatives which can be formed as the product of a catalytic reaction. Phenol can be obtained by the selective oxidation of benzene. The sensor system shows higher sensitivity to phenol than benzene. In particular, a SnO2 sensor sensitized with ZrO2 responds selectively to phenol. Aniline is provided as a reaction product between ammonia and benzene. The output signal of the gas sensor system increases when it is exposed to air containing aniline at the ppm level; on the other hand, the sensor output resulting from 1% ammonia in air does not increase so much. Cumene formation can be observed by the reaction of propane and benzene. The sensitivity of a SnO2 sensor sensitized with 12%SiO2-Al2O3 to cumene was about ten times higher than that to benzene. These results indicate that the semiconductor gas sensor system is useful for rapid screening of the catalyst for benzene functionalization.

  5. Corrosion behaviors of Al-Si-Cu-based filler metals and 6061-T6 brazements

    NASA Astrophysics Data System (ADS)

    Su, T. L.; Wang, S. S.; Tsao, L. C.; Chang, S. Y.; Chuang, T. H.; Yeh, M. S.

    2002-04-01

    The corrosion behaviors of a series of Al-Si-Cu-based filler metals and the 6061-T6 butt joints brazed with these filler metals are evaluated by polarization tests and immersion tests in a 3.5% NaCl aqueous solution. For comparison, a traditional Al-12Si filler metal is also employed. The results indicate that the Al-Si-Cu-based filler metals before brazing possess much higher corrosion current densities and pitting tendencies than the Al-12Si filler metal. However, brazing of the 6061-T6 alloy with an Al-12Si filler metal produces a wider butt joint, which, in this case, creates a more extensive corrosion region. Severe galvanic corrosion occurs at the 6061-T6 joints when brazed with Al-Si-Cu-based filler metals. However, in the case of the 6061-T6/Al-12Si brazements, selective corrosion of the Al-12Si eutectic phase can be observed. The bonding strengths of the 6061-T6 butt joints brazed with various filler metals are also measured before and after the immersion tests.

  6. Catalyst suppliers consolidate further, offer more catalysts

    SciTech Connect

    Rhodes, A.K.

    1995-10-02

    The list of suppliers of catalysts to the petroleum refining industry has decreased by five since Oil and Gas Journal`s survey of refining catalysts and catalytic additives was last published. Despite the consolidation, the list of catalyst designations has grown to about 950 in this latest survey, compared to 820 listed in 1993. The table divides the catalysts by use and gives data on their primary differentiating characteristics, feedstock, products, form, bulk density,catalyst support, active agents, availability, and manufactures.

  7. Synthesis and characterization of novel antibacterial polymers and clay delivery systems and polymeric phase transfer catalysts

    NASA Astrophysics Data System (ADS)

    Dizman, Bekir

    The research presented in this dissertation involves the syntheses of both novel antibacterial polymers and nanocomposites and polymeric phase transfer catalysts. The first section describes the synthesis, characterization, and antibacterial activities of new acrylate/methacrylate and acrylamide/methacrylamide polymers containing pendant quaternary ammonium compounds and norfloxacin. The first part of this section focuses on the syntheses and antibacterial activities of new water-soluble bis-quaternary ammonium methacrylate monomers and polymers (Chapter II). The monomers and polymers showed antibacterial activities against Staphylococcus aureus and Escherichia coli and the activity increased as the alkyl chain length in ammonium groups increased from 4 to 6 carbons. The results are very encouraging since polymers with quaternary ammonium compounds containing short alkyl chains are generally not active against bacteria. The second part of the first section involves the syntheses and antibacterial activities of various new monomers and polymers with amine and mono-quaternary ammonium groups on the side chain (Chapter III). The monomers were either the derivatives of 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) or based on acrylamide and methacrylamide derivatives. All monomers were homopolymerized and copolymerized with 2-hydroxyethylmethacrylate (HEMA). Amine monomers, their homopolymers and copolymers did not show any antibacterial activity against S. aureus and E. coli while the quaternized AHM-3-(aminomethyl) pyridine monomer, its homopolymer and copolymer with HEMA showed antibacterial activities against both bacteria. It was also found that the antibacterial activity of the quaternized methacrylamide-3-(aminomethyl) pyridine monomers and polymers increased as the alkyl chain length in ammonium groups increased. (Abstract shortened by UMI.)

  8. Hydrocracking catalyst

    SciTech Connect

    Arias, B.; Galiasso, R.; Kum, H.

    1985-02-12

    The invention relates to a particular method for the preparation of a hydrocracking catalyst, using a high iron content bauxite as a basis. This bauxite is ground and screened to a specific size and mixed with three types of additives: a promoter additive of the P, Mo, Co, Ni, W type. A hardener additive of the phosphoric acid type, ammonium phosphate. And a lubricant and pore-generating additive of the polyvinyl alcohol, polyethylene-glycol, starch type. The particularity consists in that the three additives are added simultaneously during the extrusion of the sample. That way, a particular surface composition is obtained which allows for the activity of the catalyst. Extruded products are obtained in sizes of 1/8, 1/16, and 1/32'' and submitted to drying and calcination programs for their activation. The obtained catalyst offers a good mechanical strength, a high content in macropores and a high activity, specifically for the hydrocracking of heavy Venezuelan crudes or residues.

  9. A Two-Component Alkyne Metathesis Catalyst System with an Improved Substrate Scope and Functional Group Tolerance: Development and Applications to Natural Product Synthesis.

    PubMed

    Schaubach, Sebastian; Gebauer, Konrad; Ungeheuer, Felix; Hoffmeister, Laura; Ilg, Marina K; Wirtz, Conny; Fürstner, Alois

    2016-06-13

    Although molybdenum alkylidyne complexes such as 1 endowed with triarylsilanolate ligands are excellent catalysts for alkyne metathesis, they can encounter limitations when (multiple) protic sites are present in a given substrate and/or when forcing conditions are necessary. In such cases, a catalyst formed in situ upon mixing of the trisamidomolybenum alkylidyne complex 3 and the readily available trisilanol derivatives 8 or 11 shows significantly better performance. This two-component system worked well for a series of model compounds comprising primary, secondary or phenolic -OH groups, as well as for a set of challenging (bis)propargylic substrates. Its remarkable efficiency is also evident from applications to the total syntheses of manshurolide, a highly strained sesquiterpene lactone with kinase inhibitory activity, and the structurally demanding immunosuppressive cyclodiyne ivorenolide A; in either case, the standard catalyst 1 largely failed to effect the critical macrocyclization, whereas the two-component system was fully operative. A study directed toward the quinolizidine alkaloid lythrancepine I features yet another instructive example, in that a triyne substrate was metathesized with the help of 3/11 such that two of the triple bonds participated in ring closure, while the third one passed uncompromised. As a spin-off of this project, a much improved ruthenium catalyst for the redox isomerization of propargyl alcohols to the corresponding enones was developed.

  10. Introducing a closed system approach for the investigation of chemical steps involving proton and electron transfer; as illustrated by a copper-based water oxidation catalyst.

    PubMed

    de Ruiter, Jessica M; Buda, Francesco

    2017-02-08

    The investigation of the catalytic mechanism of homogeneous water oxidation catalysts remains an active field of research. When examining catalytic steps theoretically, it is often difficult to account for the transfer of protons and electrons from step to step. To this end, a closed system approach is proposed which includes both proton and electron acceptors in the simulation box to allow for the description of proton-coupled electron transfer processes. Using Car-Parrinello Molecular Dynamics, a mononuclear copper water oxidation catalyst Cu(bpy)(OH)2 was used as a model system to explore this closed system approach. The exploration of this model system shows that, compared to traditional methods, this approach offers extra insight into proposed catalytic steps and allows for the clear identification of preferred reaction paths.

  11. Morphology Evolution on the Fracture Surface and Fracture Mechanisms of Multiphase Nanostructured ZrCu-Base Alloys.

    PubMed

    Qiu, Feng; Zhu, Lin; Zou, Qian; Wang, Lei; Han, Xue; Li, Qiang; Jiang, Qi-Chuan

    2017-03-13

    A multiphase nanostructured ZrCu-base bulk alloy which showed a unique microstructure consisting of sub-micrometer scale Zr₂Cu solid solution, nano-sized twinned plate-like ZrCu martensite (ZrCu (M)), and retained ZrCu (B2) austenite was fabricated by copper mold casting. The observation of periodic morphology evolution on the fracture surface of the multiphase nanostructured ZrCu-base alloys has been reported, which suggested a fluctuant local stress intensity along the crack propagation. It is necessary to investigate the compressive deformation behavior and the fracture mechanism of the multiphase alloy and the relation to the unique microstructures. The results obtained in this study provide a better understanding of the deformation and fracture mechanisms of multiphase hybrid nanostructured ZrCu-based alloys and give guidance on how to improve the ductility/toughness of bulk ZrCu-based alloys.

  12. Pd-catalysed decarboxylative Suzuki reactions and orthogonal Cu-based O-arylation of aromatic carboxylic acids.

    PubMed

    Dai, Jian-Jun; Liu, Jing-Hui; Luo, Dong-Fen; Liu, Lei

    2011-01-14

    Pd-catalysed decarboxylative Suzuki reactions and orthogonal Cu-based O-arylation reactions of aromatic carboxylic acids are reported. The new reactions may provide alternative routes for the synthesis of some biaryls and aromatic carboxylic esters.

  13. Structural and functional investigations of biological catalysts for optimization of solar-driven H II production systems

    NASA Astrophysics Data System (ADS)

    King, Paul W.; Svedruzic, Drazenka; Cohen, Jordi; Schulten, Klaus; Seibert, Michael; Ghirardi, Maria L.

    2006-08-01

    Research efforts to develop efficient systems for H II production encompass a variety of biological and chemical approaches. For solar-driven H II production we are investigating an approach that integrates biological catalysts, the [FeFe] hydrogenases, with a photoelectrochemical cell as a novel bio-hybrid system. Structurally the [FeFe] hydrogenases consist of an iron-sulfur catalytic site that in some instances is electronically wired to accessory iron-sulfur clusters proposed to function in electron transfer. The inherent structural complexity of most examples of these enzymes is compensated by characteristics desired for bio-hybrid systems (i.e., low activation energy, high catalytic activity and solubility) with the benefit of utilizing abundant, less costly non-precious metals. Redesign and modification of [FeFe] hydrogenases is being undertaken to reduce complexity and to optimize structural properties for various integration strategies. The least complex examples of [FeFe] hydrogenase are found in the species of photosynthetic green algae and are being studied as design models for investigating the effects of structural minimization on substrate transfer, catalytic activity and oxygen sensitivity. Redesigning hydrogenases for effective use in bio-hybrid systems requires a detailed understanding of the relationship between structure and catalysis. To achieve better mechanistic understanding of [FeFe] hydrogenases both structural and dynamic models are being used to identify potential substrate transfer mechanisms which are tested in an experimental system. Here we report on recent progress of our investigations in the areas of [FeFe] hydrogenase overexpression, minimization and biochemical characterization.

  14. In-line localized monitoring of catalyst activity in selective catalytic NO.sub.x reduction systems

    DOEpatents

    Muzio, Lawrence J.; Smith, Randall A.

    2009-12-22

    Localized catalyst activity in an SCR unit for controlling emissions from a boiler, power plant, or any facility that generates NO.sub.x-containing flue gases is monitored by one or more modules that operate on-line without disrupting the normal operation of the facility. Each module is positioned over a designated lateral area of one of the catalyst beds in the SCR unit, and supplies ammonia, urea, or other suitable reductant to the catalyst in the designated area at a rate that produces an excess of the reductant over NO.sub.x on a molar basis through the designated area. Sampling probes upstream and downstream of the designated area draw samples of the gas stream for NO.sub.x analysis, and the catalyst activity is determined from the difference in NO.sub.x levels between the two probes.

  15. Enhanced catalyst for conversion of syngas to liquid motor fuels

    DOEpatents

    Coughlin, P.K.; Rabo, J.A.

    1985-12-03

    Synthesis gas comprising carbon monoxide and hydrogen is converted to C[sub 5][sup +] hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising a SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

  16. Enhanced catalyst for conversion of syngas to liquid motor fuels

    DOEpatents

    Coughlin, Peter K.; Rabo, Jule A.

    1985-01-01

    Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

  17. Cationic ruthenium alkylidene catalysts bearing phosphine ligands.

    PubMed

    Endo, Koji; Grubbs, Robert H

    2016-02-28

    The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bearing bulky phosphine ligands. Simple ligand exchange using silver(i) salts of non-coordinating or weakly coordinating anions provided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported catalysts feature unique geometries caused by ligation of the bulky phosphine ligands. Their activities and selectivities in standard metathesis reactions were also investigated. These cationic ruthenium alkylidene catalysts reported here showed moderate activity and very similar stereoselectivity when compared to the second generation ruthenium dichloride catalyst in ring-closing metathesis, cross metathesis, and ring-opening metathesis polymerization assays.

  18. Autothermal reforming catalyst having perovskite structure

    DOEpatents

    Krumpel, Michael; Liu, Di-Jia

    2009-03-24

    The invention addressed two critical issues in fuel processing for fuel cell application, i.e. catalyst cost and operating stability. The existing state-of-the-art fuel reforming catalyst uses Rh and platinum supported over refractory oxide which add significant cost to the fuel cell system. Supported metals agglomerate under elevated temperature during reforming and decrease the catalyst activity. The catalyst is a perovskite oxide or a Ruddlesden-Popper type oxide containing rare-earth elements, catalytically active firs row transition metal elements, and stabilizing elements, such that the catalyst is a single phase in high temperature oxidizing conditions and maintains a primarily perovskite or Ruddlesden-Popper structure under high temperature reducing conditions. The catalyst can also contain alkaline earth dopants, which enhance the catalytic activity of the catalyst, but do not compromise the stability of the perovskite structure.

  19. Polyoxometalate (POM) catalyst systems : chemical principles and reactions with lignin and oxygen

    Treesearch

    I.A. Weinstock; R.H. Atalla; J.S. Bond; E.M.G. Barbuzzi; V.A. Grigoriev; Y. Gueletii; J.J. Cowan; D.M. Sonnen; R.S. Reiner; S.E. Reichel; R.A. Heintz; C.J. Houtman; A.J. Bailey; C.L. Hill

    2000-01-01

    Chemical data pertinent to most-recently developed POM delignification systems will be presented. These data will be used to demonstrate the fundamental basis for the stability, self-buffering properties, versatility and high selectivity of these systems when used in combination with oxygen to convert native or residual lignin in wood or wood-pulp fibers to CO2 and H2O...

  20. Case in Point: A Special Education Lawsuit: Catalyst for Positive Systemic Change? Maybe. Maybe Not.

    ERIC Educational Resources Information Center

    Amos, Gayle V.

    2003-01-01

    A special education lawsuit against the Baltimore City Public School System resulted in a consent decree that evolved into a systemwide management plan. By 1997, the system collapsed and a city-state partnership integrated special and regular education. The focus on outcomes for court disengagement instead of student outcomes is discussed. (CR)

  1. Development of a condenser for the dual catalyst water recovery system

    NASA Technical Reports Server (NTRS)

    Budinikas, P.; Rasouli, F.; Rabadi, N.

    1983-01-01

    Conceptual evaporation/condensation systems suitable for integration with the catalytic water recovery method were evaluated. The primary requirements for each concept were its capability to operate under zero-gravity conditions, condense recovered water from a vapor-noncondensable gas mixture, and integrate with the catalytic system. Specific energy requirements were estimated for concepts meeting the primary requirements, and the concept most suitable for integration with the catalytic system was proposed. A three-man rate condenser capable of integration with the proposed system, condensing water vapor in presence of noncondensables and transferring the heat of condensation to feed urine was designed, fabricated, and tested. It was treated with steam/air mixtures at atmospheric and elevated pressures and integrated with an actual catalytic water recovery system. The condenser has a condensation efficiency exceeding 90% and heat transfer rate of approximately 85% of theoretical value at coolant temperature ranging from 7 to 80 deg C.

  2. Cracking catalyst

    SciTech Connect

    Otterstedt, J. E. A.; Jaras, S. G.; Pudas, R.; Upson, L. L.

    1985-05-07

    A cracking catalyst having good resistance to metal poisoning has at least two particle fractions of different particle sizes, the cracking catalyzing zeolite material being concentrated to the coarser particle size fractions, and the finer particle size fractions being formed from material having relatively lower or no or insignificant cracking catalyzing activity. The particles of the finer particle size fractions have a matrix of kaolin and amorphous alumina--silica and may contain for example, an SO /SUB x/ eliminating additive such as Al/sub 2/O/sub 3/, CaO and/or MgO. The coarser particle size fractions having cracking catalyzing effect have a mean particle size of from 80 to 125 ..mu..m and the finer particle size fractions a mean particle size of from 30 to 75 ..mu..m. The coarser particle size fractions have a zeolite content of at least 20 weight % and may have a zeolite content of up to 100 weight %, the remainder consisting essentially of material which has relatively lower or no or insignificant cracking-catalyzing activity and which consists of kaolin and amorphous alumina-silica. The catalyst mass as a whole may have a zeolite content of up to 50 weight %.

  3. Ultrasound assisted free radical polymerization of glycidyl methacrylate by a new disite phase-transfer catalyst system: A kinetic study.

    PubMed

    Sankar, Kavitha; Rajendran, Venugopal

    2012-11-01

    The kinetics of multi-site phase-transfer catalyzed free radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxy disulphate (PDS) as water soluble initiator and newly synthesized 1,4-dihexadecylpyrazine-1,4-diium dibromide as multi-site phase-transfer catalyst (MPTC) has been investigated in ethyl acetate/water two phase system at constant temperature 65±1°C under nitrogen atmosphere and ultrasound irradiation conditions. The rate of polymerization increases with an increase in concentrations of GMA, PDS and MPTC. The order with respect to monomer, initiator and MPTC were found to be 1.0, 0.5 and 1.0, respectively. The comparative study reveals that the Rp of GMA determined in the presence of PTC combined with ultrasound has shown more enhancements in the activity than PTC alone. Based on the observed results a suitable mechanism has been proposed to account for the experimental observations and its significance was discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

  4. Electronic modification of Cu-based chalcopyrite semiconductors induced by lattice deformation and composition alchemy

    NASA Astrophysics Data System (ADS)

    Jiang, F. D.; Feng, J. Y.

    2008-02-01

    Using first principles calculation, we systematically investigate the electronic modification of Cu-based chalcopyrite semiconductors induced by lattice deformation and composition alchemy. It is shown that the optical band gap Eg is remarkably sensitive to the anion displacement μ, resulting from the opposite shifts of conduction band minimum and valence band maximum. Meanwhile, the dependence of structural parameters of alloyed compounds on alloy composition x is demonstrated for both cation and anion alloying. The d orbitals of group-III cations are found to be of great importance in the calculation. Abnormal changes in the optical band gap Eg induced by anion alloying are addressed.

  5. Development of brazing process for W-EUROFER joints using Cu-based fillers

    NASA Astrophysics Data System (ADS)

    de Prado, J.; Sánchez, M.; Ureña, A.

    2016-02-01

    A successful joint between W and EUROFER using high temperature brazing technique has been achieved for structural application in future fusion power plants. Cu-based powder alloy mixed with a polymeric binder has been used as filler. Microstructural analysis of the joints revealed that the joint consisted mainly of primary phases and acicular structures in a Cu matrix. Interaction between EUROFER and filler took place at the interface giving rise to several Cu-Ti-Fe rich layers. A loss of hardness at the EUROFER substrate close to the joint due to a diffusion phenomenon during brazing cycle was measured; however, the joints had an adequate shear strength value.

  6. Diagnostics for emission-control-system malfunction on three-way catalyst-equipped vehicles. Final report, November 1983-November 1985

    SciTech Connect

    Duleep, K.G.

    1985-11-01

    The report presents the results of a two part study. In Phase I, the contractor reviewed current manufacturer recommended diagnostic procedures for identifying vehicular emission control malfunctions on three-way catalyst-equipped gasoline-fueled automobiles and also surveyed diagnostic techniques used in the field. Diagnosis of malperformance was limited to the following systems: exhaust gas recirculating, secondary air, fuel, and catalyst. In Phase II, the contractor developed generalized diagnostic procedures for malfunctioning emission control systems and validated these procedures on 52 vehicles. Two mechanics alternatively disabled and repaired the vehicles using the diagnostic and repair procedures. The report also describes inspection procedures developed for the control of smoke emissions from light-duty diesel vehicles. Two types of procedures were developed, for component testing and for inspection/maintenance programs. These procedures were validated on six light-duty vehicles.

  7. Four-man rated dual catalyst system for the recovery of water from urine

    NASA Technical Reports Server (NTRS)

    Budininkas, P.

    1978-01-01

    The catalytic system was integrated with a 4-man rated urine wick evaporator. During operation, urine vapor produced by the wick-evaporator was treated in the catalytic system to remove ammonia and volatile hydrocarbons, and water was recovered by condensation in a water cooled condenser. The system operated completely automatically and required no manual adjustments, except periodic supply of urine and removal of the recovered water. Although the system was designed for treating 0.325 kg urine per hour, this rate could be achieved only with a fresh wick, then gradually decreased as the wick became saturated with urine solids. The average urine treatment rates achieved during each of the three endurance tests were 0.137, 0.217, and 0.235 kg/hr. The quality of the recovered water meets drinking water standards, with the exception of a generally low pH.

  8. Surface analysis of model systems: From a metal-graphite interface to an intermetallic catalyst

    SciTech Connect

    Kwolek, Emma J.

    2016-10-25

    This thesis summarizes research completed on two different model systems. In the first system, we investigate the deposition of the elemental metal dysprosium on highly-oriented pyrolytic graphite (HOPG) and its resulting nucleation and growth. The goal of this research is to better understand the metal-carbon interactions that occur on HOPG and to apply those to an array of other carbon surfaces. This insight may prove beneficial to developing and using new materials for electronic applications, magnetic applications and catalysis.

  9. A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

    PubMed

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

    2016-09-27

    Binary catalyst systems comprising a cationic Ru-CNC pincer complex and an alkali metal salt were developed for selective hydroboration of CO2 utilizing pinacolborane at r.t. and 1 atm CO2, with the combination of [Ru(CNCBn)(CO)2(H)][PF6] and KOCO2(t)Bu producing formoxyborane in 76% yield. A bicyclic catalytic mechanism was proposed and discussed.

  10. Integrated System in the Malaysian Education Paradigm: A Catalyst for a Holistic Personality Development

    ERIC Educational Resources Information Center

    Othman, Nooraini; Mohamad, Khairul Azmi

    2014-01-01

    This paper intends to describe and analyse the process of education reform that has taken place in Malaysia. Islamisation plays a major role in such reform. The approach is innovative and novel in nature. Historically, Malaysia was under the British colony and the British left a strong impact in the education system. Naturally the position of…

  11. Facilitation Skills: The Catalyst for Increased Effectiveness in Consultant Practice and Clinical Systems Leadership

    ERIC Educational Resources Information Center

    Manley, Kim; Titchen, Angie

    2017-01-01

    Consultant practitioner is the pinnacle of the clinical career ladder for all health care disciplines in the United Kingdom. Consultant nurse, midwife and health visitor roles build on the clinical credibility and expertise characteristic of advanced level practice, but also possess expertise in: clinical systems leadership and the facilitation of…

  12. The Systems Approach as a Catalyst for Creating an Effective Learning Environment.

    ERIC Educational Resources Information Center

    Biswalo, Peles

    2001-01-01

    An instructional systems design approach to distance education systematically applies instructional principles based on how people learn in order to create an effective learning environment. A performance-based philosophy and authentic performance assessments, including portfolios, are important elements. (Contains 16 references.) (SK)

  13. Charge transport properties of graphene: Effects of Cu-based gate electrode

    SciTech Connect

    Tang, Qide; Zhang, C. X. Tang, Chao Zhong, Jianxin; He, Chaoyu

    2016-07-21

    Using the first-principles nonequilibrium Green's function method, we study effects of Cu and Ni@Cu used as the Cu-based gate electrode on the charge transport of graphene in the field effect transistors (FET). We find that the transmission of graphene decreases with both Cu and Ni@Cu absorbed in the scatter region. Especially, noticeable transmission gaps are present around the Femi level. The transmission gaps are still effective, and considerable cut-off regions are found under the non-equilibrium environment. The Ni@Cu depresses the transmission of graphene more seriously than the Cu and enlarges the transmission gap in armchair direction. The effects on the charge transport are attributed to the redistribution of electronic states of graphene. Both Cu and Ni@Cu induce the localization of states, so as to block the electronic transport. The Ni@Cu transforms the interaction between graphene and gate electrode from the physisorption to the chemisorption, and then induces more localized states, so that the transmission decreases further. Our results suggest that besides being used to impose gate voltage, the Cu-based gate electrode itself will have a considerable effect on the charge transport of graphene and induces noticeable transmission gap in the FET.

  14. Theoretical investigation on thermoelectric properties of Cu-based chalcopyrite compounds

    NASA Astrophysics Data System (ADS)

    Wang, Biao; Xiang, Hongjun; Nakayama, Tsuneyoshi; Zhou, Jun; Li, Baowen

    2017-01-01

    Cu-based materials are potential candidates for commercial thermoelectric materials due to their abundance, nontoxicity, and high performance. We incorporate the multiband Boltzmann transport equations with first-principles calculations to theoretically investigate the thermoelectric properties of Cu-based chalcopyrite compounds. As a demonstration of our method, the thermoelectric properties of quaternary compounds Cu2ZnSnX4 (X = S, Se) and ternary compounds CuBTe2 (B = Ga, In) are studied. We systematically calculate the electrical conductivity, the Seebeck coefficient, and the power factor of the four materials above based on parameters obtained from first-principles calculations and using several other fitting parameters. For quaternary compounds, our results reveal that Cu2ZnSnSe4 is better than Cu2ZnSnS4 and its optimal hole concentration is around 5 ×1019cm-3 with the peak power factor 4.7 μ W/cm K 2 at 600 K. For ternary compounds, we find that their optimal hole concentrations are around 1 ×1020cm-3 with the peak power factors over 26 μ W/cm K 2 at 800 K.

  15. Facile heterogenization of a cobalt catalyst via graphene adsorption: robust and versatile dihydrogen production systems.

    PubMed

    Eady, Shawn C; Peczonczyk, Sabrina L; Maldonado, Stephen; Lehnert, Nicolai

    2014-07-28

    A heterogeneous dihydrogen (H2) production system has been attained by simply soaking electrodes made from electro-deposited graphene on FTO plated glass in solutions of a cobalt bis(dithiolate) compound. The resulting electrodes are active in weakly acidic aqueous solutions (pH > 3), have relatively low overpotentials (0.37 V versus platinum), show high catalytic rates (TOF > 1000 s(-1)), and are resistant to degradation by dioxygen.

  16. Highly active, thermally stable, ethylene-polymerisation pre-catalysts based on niobium/tantalum-imine systems.

    PubMed

    Redshaw, Carl; Walton, Mark; Clowes, Lucy; Hughes, David L; Fuller, Anna-Marie; Chao, Yimin; Walton, Alex; Sumerin, Victor; Elo, Pertti; Soshnikov, Igor; Zhao, Weizhen; Sun, Wen-Hua

    2013-07-01

    catalysts with, in the case of niobium, catalytic activities that were two orders of magnitude higher than those previously observed. The effects of steric hindrance and electronic configuration on the polymerisation activity of these tantalum and niobium pre-catalysts were investigated. Spectroscopic studies ((1)H NMR, (13)C NMR and (1)H-(1)H and (1)H-(13)C correlations) on the reactions of compounds 4a/4b with either MAO(50) or AlMe3/[CPh3](+)[B(C6F5)4](-) were consistent with the formation of a diamagnetic cation of the form [L(4)AlMe2](+) (MAO(50) is the product of the vacuum distillation of commercial MAO at +50 °C and contains only 1 mol% of Al in the form of free AlMe3). In the presence of MAO, this cationic aluminium complex was not capable of initiating the ROMP (ring opening metathesis polymerisation) of norbornene, whereas the 4a/4b systems with MAO(50) were active. A parallel pressure reactor (PPR)-based homogeneous polymerisation screening by using pre-catalysts 1b, 1c, 2a, 3a and 6a, in combination with MAO, revealed only moderate-to-good activities for the homo-polymerisation of ethylene and the co-polymerisation of ethylene/1-hexene. The molecular structures are reported for complexes 1a-1c, 2b, 5, 6a, 6b, 7a, 8a and 8c. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Modeling of the chemical-looping combustion of methane using a Cu-based oxygen-carrier

    SciTech Connect

    Abad, Alberto; Adanez, Juan; Garcia-Labiano, Francisco; de Diego, Luis F.; Gayan, Pilar

    2010-03-15

    A mathematical model for a bubbling fluidized bed has been developed to simulate the performance of the fuel-reactor in chemical-looping combustion (CLC) systems. This model considers both the fluid dynamic of the fluidized bed and freeboard and the kinetics of reduction of the oxygen-carrier, here CuO impregnated on alumina. The main outputs of the model are the conversion of the carrier and the gas composition at the reactor exit, the axial profiles of gas concentrations and the fluid dynamical structure of the reactor. The model was validated using measurements when burning CH{sub 4} in a 10 kW{sub th} prototype using a Cu-based oxygen-carrier. The influence of the circulation rate of solids, the load of fuel gas, the reactor temperature and size of the oxygen-carrier particles were analyzed. Combustion efficiencies predicted by the model showed a good agreement with measurements. Having validated the model, the implications for designing and optimizing a fuel-reactor were as follows. The inventory of solids for a high conversion of the fuel was sensitive to the reactor's temperature, the solids' circulation rate and the extent to which the solids entering to the reactor had been regenerated. The optimal ratio of oxygen-carrier to fuel was found to be 1.7-4 for the Cu-based oxygen-carrier used here. In this range, the inventory of solids to obtain a combustion efficiency of 99.9% at 1073 K was less than 130 kg/MW{sub th}. In addition, the model's results were very sensitive to the resistance to gas diffusing between the emulsion and bubble phases in the bed, to the decay of solids' concentration in the freeboard and to the efficiency contact between gas and solids in the freeboard. Thus, a simplified model, ignoring any restriction to gas and solids contacting each other, will under-predict the inventory of solids by a factor of 2-10. (author)

  18. Structure and characteristics of chitosan cobalt-containing hybrid systems, the catalysts of olefine oxidation

    NASA Astrophysics Data System (ADS)

    Mekhaev, A. V.; Pestov, A. V.; Molochnikov, L. S.; Kovaleva, E. G.; Pervova, M. G.; Yaltuk, Yu. G.; Grigor'ev, I. A.; Kirilyuk, I. A.

    2011-07-01

    Cobalt-containing hybrid organo-inorganic materials based on the chitosan-SiO2, chitosan-Al2O3, and chitosan-cellulose systems were obtained. The surface structure and processes that occur during the formation of metal-containing materials, the catalytic properties of which were studied in the oxidation reactions of alkene, were investigated by EPR spectroscopy using a stable pH-sensitive nitroxyl radical, 4-dimethylamino-2-ethyl-5,5-dimethyl-2-(pyridin-4-yl)-2,5-dihydro-1H-imidazole-1-oxyl, as the adsorbed probe molecules.

  19. Method of treating emissions of a hybrid vehicle with a hydrocarbon absorber and a catalyst bypass system

    DOEpatents

    Roos, Bryan Nathaniel; Gonze, Eugene V; Santoso, Halim G; Spohn, Brian L

    2014-01-14

    A method of treating emissions from an internal combustion engine of a hybrid vehicle includes directing a flow of air created by the internal combustion engine when the internal combustion engine is spinning but not being fueled through a hydrocarbon absorber to collect hydrocarbons within the flow of air. When the hydrocarbon absorber is full and unable to collect additional hydrocarbons, the flow of air is directed through an electrically heated catalyst to treat the flow of air and remove the hydrocarbons. When the hydrocarbon absorber is not full and able to collect additional hydrocarbons, the flow of air is directed through a bypass path that bypasses the electrically heated catalyst to conserve the thermal energy stored within the electrically heated catalyst.

  20. Characterisation of a PdCl 2/SnCl 2 electroless plating catalyst system adsorbed on barium titanate-based electroactive ceramics

    NASA Astrophysics Data System (ADS)

    Meenan, B. J.; Brown, N. M. D.; Wilson, J. W.

    1994-03-01

    A PdCl 2/SnCl 2 metallisation catalyst system, of the type used to activate non-conducting surfaces for electroless metal deposition, has been characterised by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The substrate is a barium titanate (BaTiO 3)-based electroactive ceramic of the type used in the fabrication of multilayer ceramic capacitors (MLCC). The treatment of the substrate surface with the PdCl 2/SnCl 2 "sensitiser" solution leads to the adsorption of catalytically inactive compounds of palladium and tin. Subsequent treatment of this surface with an "accelerator" solution removes excess oxides, hydroxides and salts of tin thereby leaving the active catalyst species, Pd xSn y, on the surface. Such sites, on exposure to the appropriete electroless plating bath, are then responsible for the metal deposition. In this study, the chemical state and relative quantities of the various surface species present after each of the processing stages have been determined by XPS. The surface roughness of the substrate results in less of the tin compounds present thereon being removed on washing the catalysed surface in the accelerator solution than normally reported for such systems, thereby affecting the measured Pd: Sn ratio. SEM studies show that the accelerator solution treatment generates crystalline areas, which may be a result of coagulation of the Pd xSn y particles present, in the otherwise amorphous catalyst coating.

  1. Wet air oxidation of pretreatment of pharmaceutical wastewater by Cu2+ and [PxWmOy]q- co-catalyst system.

    PubMed

    Wang, Guowen; Wang, Dong; Xu, Xiaochen; Liu, Lifen; Yang, Fenglin

    2012-05-30

    This study concentrates on the pretreatment of real wastewater using catalytic wet air oxidation (CWAO). WO(3-) and PO(4)(3-) contained in fosfomycin pharmaceutical wastewater (FPW) and Cu(2+) contained in berberine pharmaceutical wastewater (BPW) were studied as CWAO influent. Mixture of this two streams were reused to form Cu(2+) and [P(x)W(m)O(y)](q-), namely polyoxometalates (POMs) as co-catalyst system to treat themselves. Experiments were conducted to investigate the effects of the initial oxygen pressure and temperature on the COD (chemical oxygen demand), TOC (total organic carbon) removal and biodegradable enhancement, it was discovered that over 40% of COD and TOC removal can be easily realized in an hour of WAO oxidation at 523 K, 1.4 MPa. The BOD(5)/COD (BOD(5), biochemical oxygen demand in 5 days) of this two pharmaceutical mixture ascended from nonexistent to maximum 0.41 depends on the optimal FPW:BPW volume ratio 4:1, to compose POM co-catalyst system. Organic pollutants were incompletely oxidized to propionic acid and other intermediates. Some properties (e.g., TGA, IR, XRF) of POM catalyst separated from effluent, were obtained to provide additional information.

  2. Design, fabrication and testing of a dual catalyst ammonia removal system for a urine VCD unit

    NASA Technical Reports Server (NTRS)

    Budinikas, P.

    1980-01-01

    A three-man capacity catalytic system for the recovery of water from urine was designed, constructed, and tested, it was designed to operate with feed streams containing high concentrations of urine vapor and only 5 to 7% of oxygen for the oxidation of ammonia and volatile organic vapor.It can operate either in a flow-through or a recycle mode and is capable of accepting the urine vapor produced by a vapor compression distillation evaporator. Testing consisted of short preliminary and optimization test, an endurance test of 74 hours continuous operation, and recycle tests using both air and oxygen. The system was designed for a urine processing rate of 0.86 liters/hr; however, it was tested at rates up to 1.2 liter/hr. Untreated urine evaporated by an electrically heated evaporator was used. The quality of the recovered water meets the U.S. Drinking Water Standards, with the exception of a low pH. Accumulation of solids in the urine sludge is reduced to approximately 65% of the anticipated value.

  3. Near-edge band structures and band gaps of Cu-based semiconductors predicted by the modified Becke-Johnson potential plus an on-site Coulomb U

    SciTech Connect

    Zhang, Yubo; Zhang, Jiawei; Wang, Youwei; Gao, Weiwei; Abtew, Tesfaye A.; Zhang, Peihong E-mail: wqzhang@mail.sic.ac.cn; Zhang, Wenqing E-mail: wqzhang@mail.sic.ac.cn

    2013-11-14

    Diamond-like Cu-based multinary semiconductors are a rich family of materials that hold promise in a wide range of applications. Unfortunately, accurate theoretical understanding of the electronic properties of these materials is hindered by the involvement of Cu d electrons. Density functional theory (DFT) based calculations using the local density approximation or generalized gradient approximation often give qualitative wrong electronic properties of these materials, especially for narrow-gap systems. The modified Becke-Johnson (mBJ) method has been shown to be a promising alternative to more elaborate theory such as the GW approximation for fast materials screening and predictions. However, straightforward applications of the mBJ method to these materials still encounter significant difficulties because of the insufficient treatment of the localized d electrons. We show that combining the promise of mBJ potential and the spirit of the well-established DFT + U method leads to a much improved description of the electronic structures, including the most challenging narrow-gap systems. A survey of the band gaps of about 20 Cu-based semiconductors calculated using the mBJ + U method shows that the results agree with reliable values to within ±0.2 eV.

  4. Electrochemical catalyst recovery method

    DOEpatents

    Silva, Laura J.; Bray, Lane A.

    1995-01-01

    A method of recovering catalyst material from latent catalyst material solids includes: a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications.

  5. Electrochemical catalyst recovery method

    DOEpatents

    Silva, L.J.; Bray, L.A.

    1995-05-30

    A method of recovering catalyst material from latent catalyst material solids includes: (a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; (b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; (c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and (d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications. 3 figs.

  6. 2D-QSPR/DFT studies of aryl-substituted PNP-Cr-based catalyst systems for highly selective ethylene oligomerization.

    PubMed

    Tang, Siyang; Liu, Zhen; Zhan, Xingwen; Cheng, Ruihua; He, Xuelian; Liu, Boping

    2014-03-01

    1-Hexene and 1-octene are important comonomers for the synthesis of high performance polyolefins. Recently, various N-substituted Cr-bis(diphenylphosphino)amine (PNP-Cr) catalysts show the potential as excellent candidates for highly selective ethylene trimerization/tetramerization. In this work, a series of aryl-substituted PNP-Cr catalysts were studied by two-dimensional quantitative structure-property relationship (QSPR) method based on density functional theory (DFT) calculations. The heuristic method (HM) and best multi-linear regression (BMLR) were used to establish the best linear regression models to describe the relationship between selectivities and catalyst structures. Both Cr(I) and Cr(II) active site models for ethylene trimerization/tetramerization were considered. It was found that 1) the relativity and stability of the models were increased by using self-defined descriptors based on DFT calculations; 2) Cr(I)/Cr(III) centers were the most plausible active sites for ethylene trimerization, while Cr(II)/Cr(IV) active sites were most possibly responsible for ethylene tetramerization; and 3) the skeleton structures of the PNP-Cr system with good complanation and symmetry were crucial for achieving excellent catalytic selectivity of 1-octene, while the PNP-Cr backbone with a large steric effect on N atom would benefit ethylene trimerization. Six new PNP ligands with high selectivity toward ethylene trimerization/tetramerization were predicted based on descriptor analysis and the best linear regression models providing a good basis for further development of novel catalyst systems with better performance.

  7. Ceria nanoclusters on graphene/Ru(0001): A new model catalyst system

    SciTech Connect

    Novotny, Z.; Netzer, F. P.; Dohnalek, Z.

    2016-03-22

    In this study, the growth of ceria nanoclusters on single-layer graphene on Ru(0001) has been examined, with a view towards fabricating a stable system for model catalysis studies. The surface morphology and cluster distribution as a function of oxide coverage and substrate temperature has been monitored by scanning tunneling microscopy (STM), whereas the chemical composition of the cluster deposits has been determined by Auger electron spectroscopy (AES). The ceria nanoparticles are of the CeO2(111)-type and are anchored at the intrinsic defects of the graphene surface, resulting in a variation of the cluster densities across the macroscopic sample surface. The ceria clusters on graphene display a remarkable stability against reduction in ultrahigh vacuum up to 900 K, but some sintering of clusters is observed for temperatures > 450 K. The evolution of the cluster size distribution suggests that the sintering proceeds via a Smoluchowski ripening mechanism, i.e. diffusion and aggregation of entire clusters.

  8. Systems including catalysts in porous zeolite materials within a reactor for use in synthesizing hydrocarbons

    DOEpatents

    Rolllins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

    2012-07-24

    Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

  9. Ceria nanoclusters on graphene/Ru(0001): A new model catalyst system

    NASA Astrophysics Data System (ADS)

    Novotny, Z.; Netzer, F. P.; Dohnálek, Z.

    2016-10-01

    The growth of ceria nanoclusters on single-layer graphene on Ru(0001) has been examined, with a view towards fabricating a stable system for model catalysis studies. The surface morphology and cluster distribution as a function of oxide coverage and substrate temperature has been monitored by scanning tunneling microscopy (STM), whereas the chemical composition of the cluster deposits has been determined by Auger electron spectroscopy (AES). The ceria nanoparticles are of the CeO2(111)-type and are anchored at the intrinsic defects of the graphene surface, resulting in a variation of the cluster densities across the macroscopic sample surface. The ceria clusters on graphene display a remarkable stability against reduction in ultrahigh vacuum up to 900 K, but some sintering of clusters is observed for temperatures > 450 K. The evolution of the cluster size distribution suggests that the sintering proceeds via a Smoluchowski ripening mechanism, i.e. diffusion and aggregation of entire clusters.

  10. Rapid Syphilis Tests as Catalysts for Health Systems Strengthening: A Case Study from Peru

    PubMed Central

    García, Patricia J.; Cárcamo, César P.; Chiappe, Marina; Valderrama, Maria; La Rosa, Sayda; Holmes, King K.; Mabey, David C. W.; Peeling, Rosanna W.

    2013-01-01

    Objectives Untreated maternal syphilis leads to adverse pregnancy outcomes. The use of point of care tests (POCT) offers an opportunity to improve screening coverage for syphilis and other aspects of health systems. Our objective is to present the experience of the introduction of POCT for syphilis in Peru and describe how new technology can catalyze health system strengthening. Methods The study was implemented from September 2009–November 2010 to assess the feasibility of the use of a POCT for syphilis for screening pregnant women in Lima, Peru. Outcomes measured included access to syphilis screening, treatment coverage, partner treatment, effect on patient flow and service efficiency, acceptability among providers and patients, and sustainability. Results Before the introduction of POCT, a pregnant woman needed 6 visits to the health center in 27 days before she received her syphilis result. We trained 604 health providers and implemented the POCT for syphilis as the “two for one strategy”, offering with one finger stick both syphilis and HIV testing. Implementation of the POCT resulted in testing and treatment on the first visit. Screening and treatment coverages for syphilis improved significantly compared with the previous year. Implementation of POCT has been scaled up nationally since the study ended, and coverages for screening, treatment and partner treatment have remained over 92%. Conclusions Implementation of POCT for syphilis proved feasible and acceptable, and led to improvement in several aspects of health services. For the process to be effective we highlight the importance of: (1) engaging the authorities; (2) dissipating tensions between providers and identifying champions; (3) training according to the needs; (4) providing monitoring, supervision, support and recognition; (5) sharing results and discussing actions together; (6) consulting and obtaining feedback from users; and (7) integrating with other services such as with rapid HIV

  11. Long-Life Catalyst

    NASA Technical Reports Server (NTRS)

    1999-01-01

    STC Catalysts, Inc. (SCi) manufactures a noble metal reducible oxide catalyst consisting primarily of platinum and tin dioxide deposited on a ceramic substrate. It is an ambient temperature oxidation catalyst that was developed primarily for Carbon Dioxide Lasers.The catalyst was developed by the NASA Langley Research Center for the Laser Atmospheric Wind Sounder Program (LAWS) which was intended to measure wind velocity on a global basis. There are a number of NASA owned patents covering various aspects of the catalyst.

  12. System for continuously and catalytically removing arsenic from shale oil and regenerating the catalyst

    SciTech Connect

    Goyal, S.K.

    1989-04-25

    A system is described for producing and upgrading shale oil, comprising: (a) an oil shale retort for liberating a gaseous effluent stream containing hydrocarbons, residual amounts of arsenic and retort water vapor; (b) means connected to the retort for receiving the effluent stream, and recovering a liquid containing shale oil, arsenic and retort water; (c) separator means connected to the liquid recovery means for receiving the liquid and separating the shale oil arsenic from the retort water; (d) retort water purification means connected to the separator means for receiving and substantially purifying the retort water; (e) a first guard bed containing an arsenic-removing absorber; (f) a second guard bed containing an arsenic-removing absorber; (g) a first means interconnecting the separator means with each of the guard beds and having a first valve means for alternately directing a flow of the shale oil and arsenic through each of the guard beds; (h) a second means interconnecting the retort water purification means with each of the guard beds and having a second value means for alternately directing a flow of the purified retort water through each of the guard beds in opposite phase relationship to the flow of shade oil and arsenic through each of the guard beds.

  13. Ceria nanoclusters on graphene/Ru(0001): A new model catalyst system

    DOE PAGES

    Novotny, Z.; Netzer, F. P.; Dohnalek, Z.

    2016-03-22

    In this study, the growth of ceria nanoclusters on single-layer graphene on Ru(0001) has been examined, with a view towards fabricating a stable system for model catalysis studies. The surface morphology and cluster distribution as a function of oxide coverage and substrate temperature has been monitored by scanning tunneling microscopy (STM), whereas the chemical composition of the cluster deposits has been determined by Auger electron spectroscopy (AES). The ceria nanoparticles are of the CeO2(111)-type and are anchored at the intrinsic defects of the graphene surface, resulting in a variation of the cluster densities across the macroscopic sample surface. The ceriamore » clusters on graphene display a remarkable stability against reduction in ultrahigh vacuum up to 900 K, but some sintering of clusters is observed for temperatures > 450 K. The evolution of the cluster size distribution suggests that the sintering proceeds via a Smoluchowski ripening mechanism, i.e. diffusion and aggregation of entire clusters.« less

  14. Catalytic hydrodechlorination of trichloroethylene in a novel NaOH/2-propanol/methanol/water system on ceria-supported Pd and Rh catalysts.

    PubMed

    Cobo, Martha; Becerra, Jorge; Castelblanco, Miguel; Cifuentes, Bernay; Conesa, Juan A

    2015-08-01

    The catalytic hydrodechlorination (HDC) of high concentrations of trichloroethylene (TCE) (4.9 mol%, 11.6 vol%) was studied over 1%Pd, 1%Rh and 0.5%Pd-0.5%Rh catalysts supported on CeO2 under conditions of room temperature and pressure. For this, a one-phase system of NaOH/2-propanol/methanol/water was designed with molar percentages of 13.2/17.5/36.9/27.6, respectively. In this system, the alcohols delivered the hydrogen required for the reaction through in-situ dehydrogenation reactions. PdRh/CeO2 was the most active catalyst for the degradation of TCE among the evaluated materials, degrading 85% of the trichloroethylene, with alcohol dehydrogenation rates of 89% for 2-propanol and 83% for methanol after 1 h of reaction. Fresh and used catalysts were characterized by Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), and Thermogravimetric analysis (TGA). These results showed important differences of the active phase in each catalyst sample. Rh/CeO2 had particle sizes smaller than 1 nm and the active metal was partially oxidized (Rh(0)/Rh(+δ) ratio of 0.43). This configuration showed to be suitable for alcohols dehydrogenation. On the contrary, Pd/CeO2 showed a Pd completed oxidized and with a mean particle size of 1.7 nm, which seemed to be unfavorable for both, alcohols dehydrogenation and TCE HDC. On PdRh/CeO2, active metals presented a mean particle size of 2.7 nm and more reduced metallic species, with ratios of Rh(0)/Rh(+δ) = 0.67 and Pd(0)/Pd(+δ) = 0.28, which showed to be suitable features for the TCE HDC. On the other hand, TGA results suggested some deposition of NaCl residues over the catalyst surfaces. Thus, the new reaction system using PdRh/CeO2 allowed for the degradation of high concentrations of the chlorinated compound by using in situ hydrogen liquid donors in a reaction at room temperature and pressure.

  15. Low-temperature catalytic oxidative coupling of methane in an electric field over a Ce-W-O catalyst system

    NASA Astrophysics Data System (ADS)

    Sugiura, Kei; Ogo, Shuhei; Iwasaki, Kousei; Yabe, Tomohiro; Sekine, Yasushi

    2016-04-01

    We examined oxidative coupling of methane (OCM) over various Ce-W-O catalysts at 423 K in an electric field. Ce2(WO4)3/CeO2 catalyst showed high OCM activity. In a periodic operation test over Ce2(WO4)3/CeO2 catalyst, C2 selectivity exceeded 60% during three redox cycles. However, Ce2(WO4)3/CeO2 catalyst without the electric field showed low activity, even at 1073 K: CH4 Conv., 6.0%; C2 Sel., 2.1%. A synergetic effect between the Ce2(WO4)3 structure and electric field created the reactive oxygen species for selective oxidation of methane. Results of XAFS, in-situ Raman and periodic operation tests demonstrated that OCM occurred as the lattice oxygen in Ce2(WO4)3 (short W-O bonds in distorted WO4 unit) was consumed. The consumed oxygen was reproduced by a redox mechanism in the electric field.

  16. Low-temperature catalytic oxidative coupling of methane in an electric field over a Ce–W–O catalyst system

    PubMed Central

    Sugiura, Kei; Ogo, Shuhei; Iwasaki, Kousei; Yabe, Tomohiro; Sekine, Yasushi

    2016-01-01

    We examined oxidative coupling of methane (OCM) over various Ce–W–O catalysts at 423 K in an electric field. Ce2(WO4)3/CeO2 catalyst showed high OCM activity. In a periodic operation test over Ce2(WO4)3/CeO2 catalyst, C2 selectivity exceeded 60% during three redox cycles. However, Ce2(WO4)3/CeO2 catalyst without the electric field showed low activity, even at 1073 K: CH4 Conv., 6.0%; C2 Sel., 2.1%. A synergetic effect between the Ce2(WO4)3 structure and electric field created the reactive oxygen species for selective oxidation of methane. Results of XAFS, in-situ Raman and periodic operation tests demonstrated that OCM occurred as the lattice oxygen in Ce2(WO4)3 (short W–O bonds in distorted WO4 unit) was consumed. The consumed oxygen was reproduced by a redox mechanism in the electric field. PMID:27118726

  17. Low-temperature catalytic oxidative coupling of methane in an electric field over a Ce-W-O catalyst system.

    PubMed

    Sugiura, Kei; Ogo, Shuhei; Iwasaki, Kousei; Yabe, Tomohiro; Sekine, Yasushi

    2016-04-27

    We examined oxidative coupling of methane (OCM) over various Ce-W-O catalysts at 423 K in an electric field. Ce2(WO4)3/CeO2 catalyst showed high OCM activity. In a periodic operation test over Ce2(WO4)3/CeO2 catalyst, C2 selectivity exceeded 60% during three redox cycles. However, Ce2(WO4)3/CeO2 catalyst without the electric field showed low activity, even at 1073 K: CH4 Conv., 6.0%; C2 Sel., 2.1%. A synergetic effect between the Ce2(WO4)3 structure and electric field created the reactive oxygen species for selective oxidation of methane. Results of XAFS, in-situ Raman and periodic operation tests demonstrated that OCM occurred as the lattice oxygen in Ce2(WO4)3 (short W-O bonds in distorted WO4 unit) was consumed. The consumed oxygen was reproduced by a redox mechanism in the electric field.

  18. Method for reactivating catalysts and a method for recycling supercritical fluids used to reactivate the catalysts

    SciTech Connect

    Ginosar, Daniel M.; Thompson, David N.; Anderson, Raymond P.

    2008-08-05

    A method of reactivating a catalyst, such as a solid catalyst or a liquid catalyst. The method comprises providing a catalyst that is at least partially deactivated by fouling agents. The catalyst is contacted with a fluid reactivating agent that is at or above a critical point of the fluid reactivating agent and is of sufficient density to dissolve impurities. The fluid reactivating agent reacts with at least one fouling agent, releasing the at least one fouling agent from the catalyst. The at least one fouling agent becomes dissolved in the fluid reactivating agent and is subsequently separated or removed from the fluid reactivating agent so that the fluid reactivating agent may be reused. A system for reactivating a catalyst is also disclosed.

  19. A comparison study of toluene removal by two-stage DBD-catalyst systems loading with MnO(x), CeMnO(x), and CoMnO(x).

    PubMed

    Huang, Yifan; Dai, Shaolong; Feng, Fada; Zhang, Xuming; Liu, Zhen; Yan, Keping

    2015-12-01

    This paper studies the toluene removal by a two-stage dielectric barrier discharge (DBD)-catalyst system with three catalysts: MnO(x)/ZSM-5, CoMnO(x)/ZSM-5, and CeMnO(x)/ZSM-5. V-Q Lissajous method, Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), and X-ray photoelectron (XPS) are used to characterize the DBD and catalysts. The DBD processing partially oxidizes the toluene, and the removal efficiency has a linear relationship with ozone generation. Three DBD-catalyst systems are compared in terms of their toluene removal efficiency, Fourier transform infrared (FTIR) spectra, carbon balance, CO selectivity, CO2 selectivity, and ozone residual. The results show that the DBD-catalyst system with CoMnO(x)/ZSM-5 performs better than the other two systems. It has the highest removal efficiency of about 93.7%, and the corresponding energy yield is 4.22 g/kWh. The carbon balance and CO2 selectivity of CoMnO(x)/ZSM-5 is also better than the other two catalysts. The measurements of two important byproducts including aerosols and ozone are also presented.

  20. Combinatorial methods in catalyst development

    NASA Astrophysics Data System (ADS)

    Lauterbach, Jochen

    2002-03-01

    The discovery of novel catalytic materials has traditionally followed a hypothesize-and-test methodology with limited systematic guidance. In the past few years, a high-throughput approach to catalysis has emerged, which includes efficient sample preparation, parallel processing, and rapid sequential or parallel testing of large diversities of different catalytic materials. A short review of high-throughput screening techniques will be presented. We combine computer-aided materials design techniques with high-throughput screening methodologies for automating and systematizing the catalyst design process. Rapid-scan Fourier transform infrared hyperspectral imaging is used as the main tool for the parallel investigation of multiple member supported catalyst systems. It combines the chemical specificity of infrared spectroscopy with the ability to rapidly analyze multiple samples simultaneously. Using CO oxidation, propylene oxidation, and NO decomposition as model systems, it will be demonstrated that FTIR imaging is well suited to high throughput parallel analysis of reaction products from supported catalyst libraries. A novel, systems-oriented, integrated knowledge architecture that enables the use of high-throughput data for catalyst design will be presented. This new approach involves solving the forward problem of performance prediction using hybrid first principles, rule-based and statistical models and then using that solution to solve the inverse problem: the determination of the optimal catalyst descriptors that meet the target performance.

  1. Highly cube textured Cu-based substrates for YBCO-coated conductors

    NASA Astrophysics Data System (ADS)

    Nast, R.; Obst, B.; Goldacker, W.; Holzapfel, B.

    2006-06-01

    Cube textured Cu/Cu-based tapes are shown to be an alternative to Ni/Ni alloy substrates widely used in high current capability YBCO-coated conductors. Copper, other than nickel, is non-magnetic and has a larger thermal and electrical conductivity, keeping up thermal stabilization of the superconductor at cryogenic temperatures. Jointly with the cube texture of exceptional strength that develops after rolling and recrystallization, Cu is, therefore, a candidate material for coated conductor architecture. In this work, we report on the texturing of pure copper and different copper alloys, such as Cu- Mn and a dispersion hardened Cu-B4C tape. For Cu and Cu-B4C, the maximum found in the cube texture histograms are 3.8° and 4.4°, respectively.

  2. Dealloying of Cu-Based Metallic Glasses in Acidic Solutions: Products and Energy Storage Applications

    PubMed Central

    Wang, Zhifeng; Liu, Jiangyun; Qin, Chunling; Yu, Hui; Xia, Xingchuan; Wang, Chaoyang; Zhang, Yanshan; Hu, Qingfeng; Zhao, Weimin

    2015-01-01

    Dealloying, a famous ancient etching technique, was used to produce nanoporous metals decades ago. With the development of dealloying techniques and theories, various interesting dealloying products including nanoporous metals/alloys, metal oxides and composites, which exhibit excellent catalytic, optical and sensing performance, have been developed in recent years. As a result, the research on dealloying products is of great importance for developing new materials with superior physical and chemical properties. In this paper, typical dealloying products from Cu-based metallic glasses after dealloying in hydrofluoric acid and hydrochloric acid solutions are summarized. Several potential application fields of these dealloying products are discussed. A promising application of nanoporous Cu (NPC) and NPC-contained composites related to the energy storage field is introduced. It is expected that more promising dealloying products could be developed for practical energy storage applications. PMID:28347030

  3. Effect of graphene addition on properties of Cu-based composites for electrical contacts

    NASA Astrophysics Data System (ADS)

    Liu, Huanchao; Teng, Xinying; Wu, Weibing; Wu, Xiangwei; Leng, Jinfeng; Geng, Haoran

    2017-06-01

    In this paper, graphene was used as an additive in Cu-based composites employed as electrical contacts. In order to solve the problem of interface bonding between graphene and copper matrix, electroless silver coating on graphene and copper powder were investigated. The Gr/Cu composites were prepared by ball milling and cold compacting sintering process. The mechanical and physicochemical properties including hardness, relative density, conductivity and oxidation resistance were tested. Based on the comprehensive analysis of the microstructure and properties of the materials, the optimum additive amount of graphene was 0.2 wt.%. The relative density, hardness, oxidation weight gain and IACS of the materials obtained by the optimum process parameters were 90.0%, 53.4HB, 1.6 mg cm-2 and 76.2%, respectively.

  4. From Homogeneous to Heterogenized Solar Fuels Assemblies: Observation of Electron Transfer Events in Systems Containing Dye-Sensitized Semiconductors and Molecular Catalysts

    NASA Astrophysics Data System (ADS)

    Kamire, Rebecca Joy

    The conversion of solar energy into chemical energy by simultaneously oxidizing water and reducing protons to hydrogen could provide a much-needed fuel source within a more sustainable energy economy. Dye-sensitized photoelectrochemical cells (DSPECs) are capable of forming fuels using sunlight if photoexcited chromophores transfer charges to semiconductor electrodes and catalysts, and catalysis occurs, at rates exceeding those of charge recombination. The rational design of efficient DSPECs will require an understanding of the catalytic mechanisms and rate-limiting steps of the oxidative and reductive reactions. Here, we focus on how molecular and electrode design can be used to favor the desired charge transfer events from photoexcited perylene-3,4-dicarboximide (PMI) chromophores into semiconductor films and to molecular catalysts. Previous efforts with related chromophores have focused on charge transfer between dyes and catalysts in homogeneous covalent systems without the presence of a supporting electrode. In this work, femtosecond to millisecond transient absorption spectroscopies are utilized to identify a PMI derivative capable of injecting electrons into nanostructured semiconductor films with favorable rates and yields. The identified derivative is further used to oxidize covalently attached homogeneous water oxidation catalyst (WOC) precursor Cp*Ir III(ppy)Cl, where ppy = 2-phenylpyridine, on TiO2 and then incorporated into several photoelectrodes for photodriven water oxidation and hydrogen production. Atomic layer deposition of Al2O3 following chromophore adsorption is employed to improve the chemical stability of the chromophores and to prevent rapid electron-hole recombination. The TiO2-based photoanodes contain a coadsorbed WOC [(Ir IV(pyalc)(H2O)R)2(micro-O)] +2, where pyalc = 2-(2'pyridyl)-2-propanolate, or its mononuclear precursor functionalized with a siloxane binding group. NiO-based photocathodes include molecular cobaloxime- or [Ni(P2N2) 2

  5. Microstructure-strength relationships of heavily deformed Cu-based composites

    SciTech Connect

    Trybus, C.L.

    1988-07-01

    Heavily deformed Cu-based composites attain anomalous increases in strength upon mechanical deformation. The unique filamentary microstructures that evolve during processing (cold rolling, wire drawing or swaging) are the source of the strengthening. Composite strength is correlated to microstructural characteristics for arc melted Cu-20 vol.% Nb cold rolled up to a true strain of 6.9. During rolling Nb elongates and becomes ribbon-like while the Cu matrix undergoes a cycle of deformation-dynamic recovery-recrystallization which allows for the further reduction of the Nb. Longitudinal and transverse specimens have equivalent mechanical properties. The ultimate tensile strength of the sheet showed a weak dependence on Nb filament spacing and its strength is controlled by a dislocation propagation mechanism. TEM analysis of the composite sheet substructure revealed dislocation densities of 1-2 /times/ 10/sup 10//cm/sup 2/. TEM sample preparation of Cu by ion-thinning was found to increase the dislocation density of annealed Cu by more than 400% but had a relatively small effect on heavily worked Cu. The orientations and textures of Cu and Nb in the composite are evaluated by TEM. The feasibility of producing heavily deformed Cu-based composites via powder metallurgical processing techniques is explored because of the wider range of composite compositions which can be produced in contrast with ingot metallurgy. Specifically, the mechanical and microstructural characteristics of hot extruded elemental Cu and Nb powders and Cu-Nb powders pre-alloyed by the rotating electrode process are examined. 103 refs., 54 figs., 8 tabs.

  6. Formation of alumina-nickel-molybdenum catalysts

    SciTech Connect

    Erofeev, V.I.; Basov, V.G.; Vagin, A.I.; Kalechits, I.V.

    1982-06-01

    On the basis of the results obtained in physical and chemical studies of alumina-nickel-molybdenum oxide catalysts as well as binary system and the individual oxides, the conclusions show that the commercial catalyst consists mainly of nickel and aluminium molybdates, aluminium molybdates, molybdenum oxide, and the alumina support. 4 figures.

  7. Nanostructured catalysts for organic transformations.

    PubMed

    Chng, Leng Leng; Erathodiyil, Nandanan; Ying, Jackie Y

    2013-08-20

    and/or recyclability of the nanostructured catalysts via control of the structure, composition of the catalytically active NPs, and/or nature of the support. These principles will aid researchers in the rational design and engineering of new types of multifunctional nanocatalysts for the achievement of green and sustainable chemical processes. Although the past decade has brought many advances, there are still challenges in the area of nanocatalysis that need to be addressed. These include loss of catalytic activity during operation due to sintering, leaching of soluble species from the nanocatalysts under harsh reaction conditions, loss of control over well-defined morphologies during the scale-up synthesis of the nanocomposites, and limited examples of enantioselective nanocatalytic systems. The future of nanocatalyst research lies in the judicious design and development of nanocomposite catalysts that are stable and resistant to sintering and leaching, and yet are highly active and enantioselective for the desired catalytic organic transformations, even after multiple runs. The successful generation of such multifunctional nanocatalysts especially in tandem, domino, or cascade reactions would provide a powerful tool for the establishment of green and sustainable technologies.

  8. Microreactor for efficient catalyst evaluation

    NASA Astrophysics Data System (ADS)

    Besser, Ronald S.; Ouyang, Sean; Surangalikar, Harshal; Prevot, Michelle

    2001-09-01

    This paper describes ongoing work in the development of microreactor-based systems for applications in the chemical process industry. The microreactors discussed here are formed from silicon using robust micromachining processes to produce devices with micrometer-scale fluidic structures including passageways for the introduction and removal of gases, and a reaction zone with a thin-film catalyst. We describe experiments done to characterize these reactors for use as development tools for industrial catalytic processes in terms of catalyst screening, acquisition of rate laws, and determination of optimal process conditions. The system studied here, the reaction of a cyclic olefin (cyclohexene) with hydrogen in the presence of platinum catalyst, is a model for industrially important catalytic hydrogenation and dehydrogenation reactions.

  9. Nanolayered manganese oxide/C(60) composite: a good water-oxidizing catalyst for artificial photosynthetic systems.

    PubMed

    Najafpour, Mohammad Mahdi; Abasi, Mahnaz; Tomo, Tatsuya; Allakhverdiev, Suleyman I

    2014-08-21

    For the first time, we considered Mn oxide/C60 composites as water-oxidizing catalysts. The composites were synthesized by easy and simple procedures, and characterized by some methods. The water-oxidizing activities of these composites were also measured in the presence of cerium(iv) ammonium nitrate. We found that the nanolayered Mn oxide/C60 composites show promising activity toward water oxidation.

  10. Direct Synthesis of Renewable Dodecanol and Dodecane with Methyl Isobutyl Ketone over Dual-Bed Catalyst Systems.

    PubMed

    Sheng, Xueru; Li, Ning; Li, Guangyi; Wang, Wentao; Wang, Aiqin; Cong, Yu; Wang, Xiaodong; Zhang, Tao

    2017-03-09

    For the first time, we demonstrated two integrated processes for the direct synthesis of dodecanol or 2,4,8-trimethylnonane (a jet fuel range C12 -branched alkane) using methyl isobutyl ketone (MIBK) that can be derived from lignocellulose. The reactions were carried out in dual-bed continuous flow reactors. In the first bed, MIBK was selectively converted to a mixture of C12 alcohol and ketone. Over the Pd-modified magnesium- aluminium hydrotalcite (Pd-MgAl-HT) catalyst, a high total carbon yield (73.0 %) of C12 oxygenates can be achieved under mild conditions. In the second bed, the C12 oxygenates generated in the first bed were hydrogenated to dodecanol over a Ru/C catalyst or hydrodeoxygenated to 2,4,8-trimethylnonane over a Cu/SiO2 catalyst. The as-obtained dodecanol can be used as feedstock in the production of sodium dodecylsulfate (SDS) and sodium dodecyl benzene sulfonate (SDBS), which are widely used as surfactants or detergents. The asobtained 2,4,8-trimethylnonane can be blended into conventional jet fuel without hydroisomerization.

  11. Investigation of Methane Oxidation Reactions Over a Dual-Bed Catalyst System using (18) O Labelled DRIFTS coupling.

    PubMed

    Richard, Melissandre; Duprez, Daniel; Bion, Nicolas; Can, Fabien

    2017-01-10

    Low loading Pd-supported (0.2 wt % Pd) Y-stabilized zirconia (YSZ) and LaMnO3 (LM) perovskite were associated to study the partial oxidation of methane using labelled (18) O2 in the gas phase. Synthesis gas production was demonstrated to occur through an indirect reaction in which oxygen is first consumed in the total methane combustion. A Mars-van Krevelen mechanism was observed over Pd/YSZ at 425 °C to yield C(16) O2 and C(16) O. A significant enhancement of the Pd/YSZ catalyst activity was achieved by the association of LM-Pd/YSZ in a dual catalyst bed, resulting in a significant increase of the oxidation rate. Vibration bands of adsorbed formate species, assumed to be intermediates to the gas production, were observed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) coupling experiments. It was proposed that LM enables the generation of highly active singlet O2 , which is activated on the YSZ oxygen vacancies to assist a rapid recovery of surface PdO and increase formate decomposition into CO and H2 in Pd-supported catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Lewis Base Catalysts 6: Carbene Catalysts

    PubMed Central

    Moore, Jennifer L.

    2013-01-01

    The use of N-heterocyclic carbenes as catalysts for organic transformations has received increased attention in the past 10 years. A discussion of catalyst development and nucleophilic characteristics precedes a description of recent advancements and new reactions using N-heterocyclic carbenes in catalysis. PMID:21494949

  13. Facile synthesis of a Cu-based MOF confined in macroporous carbon hybrid material with enhanced electrocatalytic ability.

    PubMed

    Zhang, Yufan; Bo, Xiangjie; Luhana, Charles; Wang, Huan; Li, Mian; Guo, Liping

    2013-08-07

    The Cu-based MOF loaded on macroporous carbon (MPC) creates novel Cu-MOF-MPC hybrids for the first time. The obtained Cu-MOF-MPC composites are used as electrocatalysts for the oxidation of NADH and reduction of H2O2 in neutral solution.

  14. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts

    SciTech Connect

    Klier, K.; Herman, R.G.; Richards-Babb, M.

    1992-06-01

    During this quarter, the high pressure (up to 100 atm), high temperature (up to 350{degrees}C) catalyst testing system was rebuilt with clean tubing, etc. A new preparation of MoS{sub 2} catalyst was carried out, and this catalyst will be doped with alkali and tested during the next quarter of research.

  15. Deactivation of Oxidation Catalysts

    DTIC Science & Technology

    1991-05-01

    the fresh catalyst . The loss in chromium may be related to the formation of volatile chromium oxychlorde which vaporizes from the catalyst . It is...CeO2 only marginally improved the thtrmal stability. The addition of 2% water vapor inhibited the oxidation of ethanol for all three copper catalysts ...original activity. Field tests of a copper chromite catalyst on process gas containing H2S, methyl mercaptan, n-aldehydes, and furfural showed

  16. Syngas Conversion to Gasoline-Range Hydrocarbons over Pd/ZnO/Al2O3 and ZSM-5 Composite Catalyst System

    SciTech Connect

    Dagle, Robert A.; Lizarazo Adarme, Jair A.; Lebarbier, Vanessa MC; Gray, Michel J.; White, James F.; King, David L.; Palo, Daniel R.

    2014-07-01

    A composite Pd/ZnO/Al2O3-HZSM-5 (Si/Al=40) catalytic system was evaluated for the synthesis of gasoline-range hydrocarbons directly from synthesis gas. Bifunctional catalyst comprising PdZn metal and acid sites present the required catalytically active sites necessary for the methanol synthesis, methanol dehydration, and methanol-to-gasoline reactions. This system provides a unique catalytic pathway for the production of liquid hydrocarbons directly from syngas. However, selectivity control is difficult and poses many challenges. The composite catalytic system was evaluated under various process conditions. Investigated were the effects of temperature (310-375oC), pressure (300-1000 psig), time-on-stream (50 hrs), and gas-hour space velocity (740-2970 hr-1), using a H2/CO molar syngas ratio of 2.0. By operating at the lower end of the temperature range investigated, liquid hydrocarbon formation was favored, as was decreased amounts of undesirable light hydrocarbons. However, lower operating temperatures also facilitated undesirable CO2 formation via the water-gas shift reaction. Higher operating pressures slightly favored liquid synthesis. Operating at relatively low pressures (e.g. 300 psig) was made possible, whereas for methanol synthesis alone higher pressure are usually required to achieve similar conversion levels (e.g. 1000 psig). Thermodynamic constraints on methanol synthesis are eased by pushing the equilibrium through hydrocarbon formation. Catalytic performance was also evaluated by altering Pd and Zn composition of the Pd/ZnO/Al2O3 catalyst. Of the catalysts and conditions tested, selectivity toward liquid hydrocarbon was highest when using a 5% Pd metal loading and Pd/Zn molar ratio of 0.25 and mixed with HZMS-5, operating at 310oC and 300 psig, CO conversion was 43 % and selectivity (carbon weight basis) to hydrocarbons was 49 wt. %. Of the hydrocarbon fraction, 44wt. % was in the C5-C12 liquid product range and consisted primarily of aromatic

  17. Tethered catalysts for the hydration of carbon dioxide

    SciTech Connect

    Valdez, Carlos A; Satcher, Jr., Joe H; Aines, Roger D; Wong, Sergio E; Baker, Sarah E; Lightstone, Felice C; Stolaroff, Joshuah K

    2014-11-04

    A system is provided that substantially increases the efficiency of CO.sub.2 capture and removal by positioning a catalyst within an optimal distance from the air-liquid interface. The catalyst is positioned within the layer determined to be the highest concentration of carbon dioxide. A hydrophobic tether is attached to the catalyst and the hydrophobic tether modulates the position of the catalyst within the liquid layer containing the highest concentration of carbon dioxide.

  18. Characterization of three-way automotive catalysts

    SciTech Connect

    Kenik, E.A.; More, K.L.; LaBarge, W.

    1995-05-01

    This has been the second year of a CRADA between General Motors - AC Delco Systems (GM-ACDS) and Martin Marietta Energy Systems (MMES) aimed at improved performance/lifetime of platinum-rhodium based three-way-catalysts (TWC) for automotive emission control systems. While current formulations meet existing emission standards, higher than optimum Pt-Rh loadings are often required. In additionk, more stringent emission standards have been imposed for the near future, demanding improved performance and service life from these catalysts. Understanding the changes of TWC conversion efficiency with ageing is a critical need in improving these catalysts.

  19. Integrated control of wood destroying basidiomycetes combining Cu-based wood preservatives and Trichoderma spp.

    PubMed

    Ribera, Javier; Fink, Siegfried; Bas, Maria Del Carmen; Schwarze, Francis W M R

    2017-01-01

    The production of new generation of wood preservatives (without addition of a co-biocide) in combination with an exchange of wood poles on identical sites with high fungal inoculum, has resulted in an increase of premature failures of wood utility poles in the last decades. Wood destroying basidiomycetes inhabiting sites where poles have been installed, have developed resistance against wood preservatives. The objective of the in vitro studies was to identify a Trichoderma spp. with a highly antagonistic potential against wood destroying basidiomycetes that is capable of colonizing Cu-rich environments. For this purpose, the activity of five Trichoderma spp. on Cu-rich medium was evaluated according to its growth and sporulation rates. The influence of the selected Trichoderma spp. on wood colonization and degradation by five wood destroying basidiomycetes was quantitatively analyzed by means of dry weight loss of wood specimens. Furthermore, the preventative effect of the selected Trichoderma spp. in combination with four Cu-based preservatives was also examined by mass loss and histological changes in the wood specimens. Trichoderma harzianum (T-720) was considered the biocontrol agent with higher antagonistic potential to colonize Cu-rich environments (up to 0.1% CuSO4 amended medium). T. harzianum demonstrated significant preventative effect on wood specimens against four wood destroying basidiomycetes. The combined effect of T. harzianum and Cu-based wood preservatives demonstrated that after 9 months incubation with two wood destroying basidiomycetes, wood specimens treated with 3.8 kg m-3 copper-chromium had weight losses between 55-65%, whereas containers previously treated with T. harzianum had significantly lower weight losses (0-25%). Histological studies on one of the wood destroying basidiomycetes revealed typical decomposition of wood cells by brown-rot fungi in Cu-impregnated samples, that were notably absent in wood specimens previously exposed to T

  20. Integrated control of wood destroying basidiomycetes combining Cu-based wood preservatives and Trichoderma spp.

    PubMed Central

    2017-01-01

    The production of new generation of wood preservatives (without addition of a co-biocide) in combination with an exchange of wood poles on identical sites with high fungal inoculum, has resulted in an increase of premature failures of wood utility poles in the last decades. Wood destroying basidiomycetes inhabiting sites where poles have been installed, have developed resistance against wood preservatives. The objective of the in vitro studies was to identify a Trichoderma spp. with a highly antagonistic potential against wood destroying basidiomycetes that is capable of colonizing Cu-rich environments. For this purpose, the activity of five Trichoderma spp. on Cu-rich medium was evaluated according to its growth and sporulation rates. The influence of the selected Trichoderma spp. on wood colonization and degradation by five wood destroying basidiomycetes was quantitatively analyzed by means of dry weight loss of wood specimens. Furthermore, the preventative effect of the selected Trichoderma spp. in combination with four Cu-based preservatives was also examined by mass loss and histological changes in the wood specimens. Trichoderma harzianum (T-720) was considered the biocontrol agent with higher antagonistic potential to colonize Cu-rich environments (up to 0.1% CuSO4 amended medium). T. harzianum demonstrated significant preventative effect on wood specimens against four wood destroying basidiomycetes. The combined effect of T. harzianum and Cu-based wood preservatives demonstrated that after 9 months incubation with two wood destroying basidiomycetes, wood specimens treated with 3.8 kg m-3 copper-chromium had weight losses between 55–65%, whereas containers previously treated with T. harzianum had significantly lower weight losses (0–25%). Histological studies on one of the wood destroying basidiomycetes revealed typical decomposition of wood cells by brown-rot fungi in Cu-impregnated samples, that were notably absent in wood specimens previously exposed

  1. Development of industrial catalysts for sustainable chlorine production.

    PubMed

    Mondelli, Cecilia; Amrute, Amol P; Moser, Maximilian; Schmidt, Timm; Pérez-Ramírez, Javier

    2012-01-01

    The heterogeneously catalyzed gas-phase oxidation of HCl to Cl(2) offers an energy-efficient and eco- friendly route to recover chlorine from HCl-containing byproduct streams in the chemical industry. This process has attracted renewed interest in the last decade due to an increased chlorine demand and the growing excess of byproduct HCl from chlorination processes. Since its introduction (by Deacon in 1868) and till recent times, the industrialization of this reaction has been hindered by the lack of sufficiently active and durable materials. Recently, RuO(2)-based catalysts with outstanding activity and stability have been designed and they are being implemented for large-scale Cl(2) recycling. Herein, we review the main limiting features of traditional Cu-based catalysts and survey the key steps in the development of the new generation of industrial RuO(2)-based materials. As the expansion of this technology would benefit from cheaper, but comparably robust, alternatives to RuO(2)-based catalysts, a nov el CeO(2)-based catalyst which offers promising perspectives for application in this field has been introduced.

  2. CO-induced inversion of the layer sequence of a model CoCu catalyst

    NASA Astrophysics Data System (ADS)

    Collinge, Greg; Xiang, Yizhi; Barbosa, Roland; McEwen, Jean-Sabin; Kruse, Norbert

    2016-06-01

    Experimental X-ray photoelectron spectroscopy (XPS) and theoretical density functional theory (DFT) calculations reveal the electronic and structural properties of CoCu catalysts before and after CO adsorption. DFT calculations show that, prior to CO adsorption, CoCu has a high tendency to self-assemble into a Co@Cu core-shell structure, which is in accordance with previous atom probe tomography (APT) results for CoCu-based systems and the known mutually low miscibility of Co and Cu. We demonstrate that Co and Cu are electronically immiscible using a density of states (DOS) analysis wherein neither metal's electronic structure is greatly perturbed by the other in ;mixed; CoCu. However, CO adsorption on Co is in fact weakened in CoCu compared to CO adsorption on pure Co despite being electronically unchanged in the alloy. Differential charge density analysis suggests that this is likely due to a lower electron density made available to Co by Cu. CO adsorption at coverages up to 1.00 ML are then investigated on a Cu/Co(0001) model slab to demonstrate CO-induced segregation effects in CoCu. Accordingly, a large driving force for a Co surface enrichment is found. At high coverages, CO can completely invert the layer sequence of Co and Cu. This result is echoed by XPS evidence, which shows that the surface Co/Cu ratio of CoCu is much larger in the presence of CO than in H2.

  3. Chemical transformations of glucose to value added products using Cu-based catalytic systems.

    PubMed

    Yepez, Alfonso; Pineda, Antonio; Garcia, Angel; Romero, Antonio A; Luque, Rafael

    2013-08-07

    Cu nanoparticles have been supported by two types of aluminosilicate materials with and without Zn in their composition in view of their application in the microwave-assisted conversion of glucose to valuable products via tandem formic acid-promoted dehydration (to 5-hydroxymethylfurfural--HMF) and further selective hydrogenation to 5-methylfurfuryl alcohol (MFA). Results show that interesting selectivities (up to 60% to MFA or HMF) could be achieved after short times of reaction (typically 2-30 min) using Cu-containing nanomaterials. Zn was found to play an interesting role in the selectivity to reduced products, even if present in very small quantities (0.2 wt%).

  4. Electrochemical Behavior of TiO(x)C(y) as Catalyst Support for Direct Ethanol Fuel Cells at Intermediate Temperature: From Planar Systems to Powders.

    PubMed

    Calvillo, Laura; García, Gonzalo; Paduano, Andrea; Guillen-Villafuerte, Olmedo; Valero-Vidal, Carlos; Vittadini, Andrea; Bellini, Marco; Lavacchi, Alessandro; Agnoli, Stefano; Martucci, Alessandro; Kunze-Liebhäuser, Julia; Pastor, Elena; Granozzi, Gaetano

    2016-01-13

    To achieve complete oxidation of ethanol (EOR) to CO2, higher operating temperatures (often called intermediate-T, 150-200 °C) and appropriate catalysts are required. We examine here titanium oxycarbide (hereafter TiOxCy) as a possible alternative to standard carbon-based supports to enhance the stability of the catalyst/support assembly at intermediate-T. To test this material as electrocatalyst support, a systematic study of its behavior under electrochemical conditions was carried out. To have a clear description of the chemical changes of TiOxCy induced by electrochemical polarization of the material, a special setup that allows the combination of X-ray photoelectron spectroscopy and electrochemical measurements was used. Subsequently, an electrochemical study was carried out on TiOxCy powders, both at room temperature and at 150 °C. The present study has revealed that TiOxCy is a sufficiently conductive material whose surface is passivated by a TiO2 film under working conditions, which prevents the full oxidation of the TiOxCy and can thus be considered a stable electrode material for EOR working conditions. This result has also been confirmed through density functional theory (DFT) calculations on a simplified model system. Furthermore, it has been experimentally observed that ethanol molecules adsorb on the TiOxCy surface, inhibiting its oxidation. This result has been confirmed by using in situ Fourier transform infrared spectroscopy (FTIRS). The adsorption of ethanol is expected to favor the EOR in the presence of suitable catalyst nanoparticles supported on TiOxCy.

  5. Monopropellant engine investigation for space shuttle reaction control system. Volume 3: Improvement of metal foam for catalyst retention

    NASA Technical Reports Server (NTRS)

    1975-01-01

    The retention of granular catalyst in a metal foam matrix was demonstrated to greatly increase the life capability of hydrazine monopropellant reactors. Since nickel foam used in previous tests was found to become degraded after long-term exposure the cause of degradation was examined and metal foams of improved durability were developed. The most durable foam developed was a rhodium-coated nickel foam. An all-platinum foam was found to be incompatible in a hot ammonia (hydrazine) environment. It is recommended to scale up the manufacturing process for the improved foam to produce samples sufficiently large for space shuttle APU gas generator testing.

  6. Performance of vegetative and fruits Zn/Cu based electrochemical cell

    NASA Astrophysics Data System (ADS)

    Khan, Md. Kamrul Alam, Prof. _., Dr.

    2017-01-01

    We have studied the performance of PKL, Aloe Vera, Tomato and Lemon juice electrochemical Cells without load condition for 1:1 Zn/Cu based electrodes. It was studied the variation of Open circuit voltage (Voc), Short current (Isc) and Maximum Power (Pmax) with the variation of time for PKL, Aloe Vera, Tomato and Lemon juice electrochemical Cells. It was seen from the research observation that the discharge characteristic of the PKL electrochemical cell was more efficient than the other three Aloe Vera, Tomato and Lemon juice electrochemical Cells. Because the Open circuit voltage (Voc), Short current (Isc) and Maximum Power (Pmax) are more stable and steady than the others three Aloe Vera, Tomato and Lemon juice electrochemical Cells. Furthermore, to enhance the performance we have also studied the secondary salt effect by using the NaCl as an electrolyte with the PKL, Aloe Vera and Lemon juice electrochemical Cells. Most of the results have been tabulated and graphically discussed. I am grateful to the authority of the Science and technology ministry,Bangladesh for financial support during the research work.

  7. Field and temperature dependence of magnetization in FeCu-based amorphous alloys

    NASA Astrophysics Data System (ADS)

    Crespo, P.; Multigner, M.; Castaño, F. J.; Casero, R.; Hernando, A.; García Escorial, A.; Schultz, L.; Kaul, S. N.

    2000-06-01

    In this paper, the production of FeCu-based FeCuZr amorphous alloys by ball milling is reported. The thermal dependence of magnetization for the (Fe0.5Cu0.5)85Zr15 (at. %) amorphous alloy has been found to show a dramatic field dependence of the kink point of the magnetization. This kink corresponds to a temperature different from the Curie temperature, above 400 K, of the ferromagnetic phase, which, according to spin waves fitting, can be induced by applying external fields. Just above 235 K, the thermoremanence increases sharply, and this feature strongly suggests an increase of the ferromagnetic ordering under zero field heating. Neutron diffraction experiments seem to confirm the enhancement of spin alignment. The thermal expansion above the compensation temperature is proposed to be the origin of the thermoremanence enhancement through the anti-Invar effect as might be explained within the framework of recent ab initio calculations [M. van Schilfgaarde et al., Nature (London) 400, 46 (1999)].

  8. Process for magnetic beneficiating petroleum cracking catalyst

    DOEpatents

    Doctor, R.D.

    1993-10-05

    A process is described for beneficiating a particulate zeolite petroleum cracking catalyst having metal values in excess of 1000 ppm nickel equivalents. The particulate catalyst is passed through a magnetic field in the range of from about 2 Tesla to about 5 Tesla generated by a superconducting quadrupole open-gradient magnetic system for a time sufficient to effect separation of said catalyst into a plurality of zones having different nickel equivalent concentrations. A first zone has nickel equivalents of about 6,000 ppm and greater, a second zone has nickel equivalents in the range of from about 2000 ppm to about 6000 ppm, and a third zone has nickel equivalents of about 2000 ppm and less. The zones of catalyst are separated and the second zone material is recycled to a fluidized bed of zeolite petroleum cracking catalyst. The low nickel equivalent zone is treated while the high nickel equivalent zone is discarded. 1 figures.

  9. Process for magnetic beneficiating petroleum cracking catalyst

    DOEpatents

    Doctor, Richard D.

    1993-01-01

    A process for beneficiating a particulate zeolite petroleum cracking catalyst having metal values in excess of 1000 ppm nickel equivalents. The particulate catalyst is passed through a magnetic field in the range of from about 2 Tesla to about 5 Tesla generated by a superconducting quadrupole open-gradient magnetic system for a time sufficient to effect separation of said catalyst into a plurality of zones having different nickel equivalent concentrations. A first zone has nickel equivalents of about 6,000 ppm and greater, a second zone has nickel equivalents in the range of from about 2000 ppm to about 6000 ppm, and a third zone has nickel equivalents of about 2000 ppm and less. The zones of catalyst are separated and the second zone material is recycled to a fluidized bed of zeolite petroleum cracking catalyst. The low nickel equivalent zone is treated while the high nickel equivalent zone is discarded.

  10. Metal/metal oxide doped oxide catalysts having high deNOx selectivity for lean NOx exhaust aftertreatment systems

    DOEpatents

    Park, Paul W.

    2004-03-16

    A lean NOx catalyst and method of preparing the same is disclosed. The lean NOx catalyst includes a ceramic substrate, an oxide support material, preferably .gamma.-alumina, deposited on the substrate and a metal promoter or dopant introduced into the oxide support material. The metal promoters or dopants are selected from the group consisting of indium, gallium, tin, silver, germanium, gold, nickel, cobalt, copper, iron, manganese, molybdenum, chromium, cerium, vanadium, oxides thereof, and combinations thereof. The .gamma.-alumina preferably has a pore volume of from about 0.5 to about 2.0 cc/g; a surface area of between about 80 to 350 m.sup.2 /g; an average pore size diameter of between about 3 to 30 nm; and an impurity level of less than or equal to 0.2 weight percent. In a preferred embodiment the .gamma.-alumina is prepared by a sol-gel method, with the metal doping of the .gamma.-alumina preferably accomplished using an incipient wetness impregnation technique.

  11. Prelife catalysts and replicators

    PubMed Central

    Ohtsuki, Hisashi; Nowak, Martin A.

    2009-01-01

    Life is based on replication and evolution. But replication cannot be taken for granted. We must ask what there was prior to replication and evolution. How does evolution begin? We have proposed prelife as a generative system that produces information and diversity in the absence of replication. We model prelife as a binary soup of active monomers that form random polymers. ‘Prevolutionary’ dynamics can have mutation and selection prior to replication. Some sequences might have catalytic activity, thereby enhancing the rates of certain prelife reactions. We study the selection criteria for these prelife catalysts. Their catalytic efficiency must be above certain critical values. We find a maintenance threshold and an initiation threshold. The former is a linear function of sequence length, and the latter is an exponential function of sequence length. Therefore, it is extremely hard to select for prelife catalysts that have long sequences. We compare prelife catalysis with a simple model for replication. Assuming fast template-based elongation reactions, we can show that replicators have selection thresholds that are independent of their sequence length. Our calculation demonstrates the efficiency of replication and provides an explanation of why replication was selected over other forms of prelife catalysis. PMID:19692408

  12. Catalyst patterning for nanowire devices

    NASA Technical Reports Server (NTRS)

    Li, Jun (Inventor); Cassell, Alan M. (Inventor); Han, Jie (Inventor)

    2004-01-01

    Nanowire devices may be provided that are based on carbon nanotubes or single-crystal semiconductor nanowires. The nanowire devices may be formed on a substrate. Catalyst sites may be formed on the substrate. The catalyst sites may be formed using lithography, thin metal layers that form individual catalyst sites when heated, collapsible porous catalyst-filled microscopic spheres, microscopic spheres that serve as masks for catalyst deposition, electrochemical deposition techniques, and catalyst inks. Nanowires may be grown from the catalyst sites.

  13. Ruthenium-based olefin metathesis catalysts bearing pH-responsive ligands: External control of catalyst solubility and activity

    NASA Astrophysics Data System (ADS)

    Balof, Shawna Lynn

    2011-12-01

    Sixteen novel, Ru-based olefin metathesis catalysts bearing pH responsive ligands were synthesized. The pH-responsive groups employed with these catalysts included dimethylamino (NMe2) modified NHC ligands as well as N-donor dimethylaminopyridine (DMAP) and 3-(o-pyridyl)propylidene ligands. These pH-responsive ligands provided the means by which the solubility and/or activity profiles of the catalysts produced could be controlled via acid addition. The main goal of this dissertation was to design catalyst systems capable of performing ring opening metathesis (ROMP) and ring closing metathesis (RCM) reactions in both organic and aqueous media. In an effort to quickly gain access to new catalyst structures, a template synthesis for functionalized NHC ligand precursors was designed, in addition to other strategies, to obtain ligand precursors with ancillary NMe2 groups. Kinetic studies for the catalysts produced from these precursors showed external control of catalyst solubility was afforded via protonation of the NMe2 groups of their NHC ligands. Additionally, this protonation afforded external control of catalyst propagation rates for several catalysts. This is the first known independent external control for the propagation rates of ROMP catalysts. The incorporation of pH-responsive N-donor ligands into catalyst structures also provided the means for the external control of metathesis activity, as the protonation of these ligands resulted in an increased initiation rate based on their fast and irreversible dissociation from the metal center. The enhanced external control makes these catalysts applicable to a wide range of applications, some of which have been explored by us and/or through collaboration. Three of the catalysts designed showed remarkable metathesis activity in aqueous media. These catalysts displayed comparable RCM activity in aqueous media to a class of water-soluble catalysts reported by Grubbs et al., considered to be the most active catalyst for

  14. Engineering design and testing of a ground water remediation system using electrolytically generated hydrogen with a palladium catalyst for dehalogenation of chlorinated hydrogen

    SciTech Connect

    Ruiz, R.

    1997-12-01

    Recent studies have shown that dissolved hydrogen causes rapid dehalogenation of chlorinated hydrocarbons in the presence of a palladium catalyst. The speed and completeness of these reactions offer advantages in designing remediation technologies for certain ground water contamination problems. However, a practical design challenge arises in the need to saturate the aqueous phase with hydrogen in an expeditious manner. To address this issue, a two-stage treatment reactor has been developed. The first stage consists of an electrolytic cell that generates hydrogen by applying a voltage potential across the influent water stream. The second stage consists of a catalyst column of palladium metal supported on alumina beads. A bench-scale reactor has been used to test this design for treating ground water contaminated with trichloroethene and other chlorinated hydrocarbons. In influent streams containing contaminant concentrations up to 4 ppm, initial results confirm that destruction efficiencies greater than 95% may be achieved with residence times short enough to allow practical implementation in specially designed flow-through treatment wells. Results from the bench-scale tests are being used to design a pilot ground water treatment system.

  15. A fully integrated continuous-flow system for asymmetric catalysis: enantioselective hydrogenation with supported ionic liquid phase catalysts using supercritical CO(2) as the mobile phase.

    PubMed

    Hintermair, Ulrich; Franciò, Giancarlo; Leitner, Walter

    2013-04-02

    A continuous-flow process based on a chiral transition-metal complex in a supported ionic liquid phase (SILP) with supercritical carbon dioxide (scCO(2)) as the mobile phase is presented for asymmetric catalytic transformations of low-volatility organic substrates at mild reaction temperatures. Enantioselectivity of >99% ee and quantitative conversion were achieved in the hydrogenation of dimethylitaconate for up to 30 h, reaching turnover numbers beyond 100000 for the chiral QUINAPHOS-rhodium complex. By using an automated high-pressure continuous-flow setup, the product was isolated in analytically pure form without the use of any organic co-solvent and with no detectable catalyst leaching. Phase-behaviour studies and high-pressure NMR spectroscopy assisted the localisation of optimum process parameters by quantification of substrate partitioning between the IL and scCO(2). Fundamental insight into the molecular interactions of the metal complex, ionic liquid and the surface of the support in working SILP catalyst materials was gained by means of systematic variations, spectroscopic studies and labelling experiments. In concert, the obtained results provided a rationale for avoiding progressive long-term deactivation. The optimised system reached stable selectivities and productivities that correspond to 0.7 kgL(-1)h(-1) space-time yield and at least 100 kg product per gram of rhodium, thus making such processes attractive for larger-scale application.

  16. Textured catalysts and methods of making textured catalysts

    DOEpatents

    Werpy, Todd; Frye, Jr., John G.; Wang, Yong; Zacher, Alan H.

    2007-03-06

    A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

  17. Enhanced Oxidation Catalysts for Water Reclamation

    NASA Technical Reports Server (NTRS)

    Jolly, Clifford D.

    1999-01-01

    This effort seeks to develop and test high-performance, long operating life, physically stable catalysts for use in spacecraft water reclamation systems. The primary goals are to a) reduce the quantity of expendable water filters used to purify water aboard spacecraft, b) to extend the life of the oxidation catalysts used for eliminating organic contaminants in the water reclamation systems, and c) reduce the weight/volume of the catalytic oxidation systems (e.g. VRA) used. This effort is targeted toward later space station utilization and will consist of developing flight-qualifiable catalysts and long-term ground tests of the catalyst prior to their utilization in flight. Fixed -bed catalytic reactors containing 5% platinum on granular activated carbon have been subjected to long-term dynamic column tests to measure catalyst stability vs throughput. The data generated so far indicate that an order of magnitude improvement can be obtained with the treated catalysts vs the control catalyst, at only a minor loss (approx 10%) in the initial catalytic activity.

  18. Integrated lipase production and in situ biodiesel synthesis in a recombinant Pichia pastoris yeast: an efficient dual biocatalytic system composed of cell free enzymes and whole cell catalysts

    PubMed Central

    2014-01-01

    Background Lipase-catalyzed biotransformation of acylglycerides or fatty acids into biodiesel via immobilized enzymes or whole cell catalysts has been considered as one of the most promising methods to produce renewable and environmentally friendly alternative liquid fuels, thus being extensively studied so far. In all previously pursued approaches, however, lipase enzymes are prepared in an independent process separated from enzymatic biodiesel production, which would unavoidably increase the cost and energy consumption during industrial manufacture of this cost-sensitive energy product. Therefore, there is an urgent need to develop novel cost-effective biocatalysts and biocatalytic processes with genuine industrial feasibility. Result Inspired by the consolidated bioprocessing of lignocellulose to generate bioethanol, an integrated process with coupled lipase production and in situ biodiesel synthesis in a recombinant P. pastoris yeast was developed in this study. The novel and efficient dual biocatalytic system based on Thermomyces lanuginosus lipase took advantage of both cell free enzymes and whole cell catalysts. The extracellular and intracellular lipases of growing yeast cells were simultaneously utilized to produce biodiesel from waste cooking oils in situ and in one pot. This integrated system effectively achieved 58% and 72% biodiesel yield via concurrent esterified-transesterified methanolysis and stepwise hydrolysis-esterification at 3:1 molar ratio between methanol and waste cooking oils, respectively. Further increasing the molar ratio of methanol to waste cooking oils to 6:1 led to an 87% biodiesel yield using the stepwise strategy. Both water tolerance and methanol tolerance of this novel system were found to be significantly improved compared to previous non-integrated biodiesel production processes using separately prepared immobilized enzymes or whole cell catalysts. Conclusion We have proposed a new concept of integrated biodiesel production

  19. Unraveling a Single-Step Simultaneous Two-Electron Transfer Process from Semiconductor to Molecular Catalyst in a CoPy/CdS Hybrid System for Photocatalytic H2 Evolution under Strong Alkaline Conditions.

    PubMed

    Xu, Yuxing; Ye, Yun; Liu, Taifeng; Wang, Xiuli; Zhang, Bingqing; Wang, Mei; Han, Hongxian; Li, Can

    2016-08-31

    Electron transfer processes from semiconductor to molecular catalysts was studied in a model hybrid photocatalytic hydrogen evolution system composed of [Co((III))(dmgH)2PyCl] (CoPy) and CdS under different pH conditions. Thermodynamic and kinetic studies revealed that photocatalytic H2 evolution under high pH conditions (pH 13.5) can only account for the thermodynamically more favorable single-step simultaneous two-electron transfer from photoirradiated CdS to Co(III)Py to produce unavoidable intermediate Co(I)Py, rather than a two-step successive one-electron transfer process. This finding not only provides new insight into the charge transfer processes between semiconductors and molecular catalysts but also opens up a new avenue for the assembly and optimization of semiconductor-molecular catalyst hybrid systems processed through multielectron transfer processes.

  20. Light alkane conversion processes - Suprabiotic catalyst systems for selective oxidation of light alkane gases to fuel oxygenates.

    SciTech Connect

    Lyons, J.E.

    1992-07-01

    The objective of the work presented in this paper is to develop new, efficient catalysts for the selective transformation of the light alkanes in natural gas to alcohols for use as liquid transportation fuels, fuel precursors and chemical products. There currently exists no DIRECT one-step catalytic air-oxidation process to convert these substrates to alcohols. Such a one-step route would represent superior useful technology for the utilization of natural gas and similar refinery-derived light hydrocarbon streams. Processes for converting natural gas or its components (methane, ethane, propane, and the butanes) to alcohols for use as motor fuels, fuel additives or fuel precursors will not only add a valuable alternative to crude oil but will produce a clean-burning, high octane alternative to conventional gasoline.

  1. Light alkane conversion processes - Suprabiotic catalyst systems for selective oxidation of light alkane gases to fuel oxygenates

    SciTech Connect

    Lyons, J.E.

    1992-01-01

    The objective of the work presented in this paper is to develop new, efficient catalysts for the selective transformation of the light alkanes in natural gas to alcohols for use as liquid transportation fuels, fuel precursors and chemical products. There currently exists no DIRECT one-step catalytic air-oxidation process to convert these substrates to alcohols. Such a one-step route would represent superior useful technology for the utilization of natural gas and similar refinery-derived light hydrocarbon streams. Processes for converting natural gas or its components (methane, ethane, propane, and the butanes) to alcohols for use as motor fuels, fuel additives or fuel precursors will not only add a valuable alternative to crude oil but will produce a clean-burning, high octane alternative to conventional gasoline.

  2. Facile synthesis and characterization of trimesic acid-Cu based metal organic frameworks

    NASA Astrophysics Data System (ADS)

    Sahiner, Nurettin; Sel, Kivanc; Ozturk, Omer Faruk; Demirci, Sahin; Terzi, Gozde

    2014-09-01

    Metal-organic frameworks based on trimesic acid (TMA) as organic linker and Cu (II) as metal ions from different metal salts such as CuCl2, Cu(NO3)2, CuSO4 and Cu(CH3COOH)2 were prepared in relatively environmentally friendly media e.g., at room temperature in DI water and at the boiling point of ethanol. The prepared TMA-Cu MOFs showed very interesting porosity and optical coloring based on the source of the used metal salts and preparation medium. The prepared MOFs were characterized in terms of their porosity with BET measurements and it was found that about 850 m2/g for the MOF prepared from Cu(NO3)2 salt in ethanol. The amounts of metal ions connected to TMA were determined by atomic absorption spectroscopy measurements (AAS) after dissolution of TMA-Cu MOFs by concentrated HCl treatments. From AAS measurements the mole ratio of Cu(II) to TMA was found to vary between 1.5 and 2, depending on the source of metal ions and the solvent used during preparation. The structural analysis and thermal characterization of the prepared MOFs were done by using FT-IR and TGA analysis, respectively. Additionally, TMA-Cu based MOF disks were prepared and their conductivities were determined by I-V measurements. The conductivity of TMA-Cu MOFs was calculated to be between 8.26E-08 and 5.29E-11 S/cm.

  3. Methods of making textured catalysts

    DOEpatents

    Werpy, Todd [West Richland, WA; Frye, Jr., John G.; Wang, Yong [Richland, WA; Zacher, Alan H [Kennewick, WA

    2010-08-17

    A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

  4. Catalyst Alloys Processing

    NASA Astrophysics Data System (ADS)

    Tan, Xincai

    2014-10-01

    Catalysts are one of the key materials used for diamond formation at high pressures. Several such catalyst products have been developed and applied in China and around the world. The catalyst alloy most widely used in China is Ni70Mn25Co5 developed at Changsha Research Institute of Mining and Metallurgy. In this article, detailed techniques for manufacturing such a typical catalyst alloy will be reviewed. The characteristics of the alloy will be described. Detailed processing of the alloy will be presented, including remelting and casting, hot rolling, annealing, surface treatment, cold rolling, blanking, finishing, packaging, and waste treatment. An example use of the catalyst alloy will also be given. Industrial experience shows that for the catalyst alloy products, a vacuum induction remelt furnace can be used for remelting, a metal mold can be used for casting, hot and cold rolling can be used for forming, and acid pickling can be used for metal surface cleaning.

  5. Microstructural evolution and surface properties of nanostructured Cu-based alloy by ultrasonic nanocrystalline surface modification technique

    NASA Astrophysics Data System (ADS)

    Amanov, Auezhan; Cho, In-Sik; Pyun, Young-Sik

    2016-12-01

    A nanostructured surface layer with a thickness of about 180 μm was successfully produced in Cu-based alloy using an ultrasonic nanocrystalline surface modification (UNSM) technique. Cu-based alloy was sintered onto low carbon steel using a powder metallurgy (P/M) method. Transmission electron microscope (TEM) characterization revealed that the severe plastic deformation introduced by UNSM technique resulted in nano-sized grains in the topmost surface layer and deformation twins. It was also found by atomic force microscope (AFM) observations that the UNSM technique provides a significant reduction in number of interconnected pores. The effectiveness of nanostructured surface layer on the tribological and micro-scratch properties of Cu-based alloy specimens was investigated using a ball-on-disk tribometer and micro-scratch tester, respectively. Results exhibited that the UNSM-treated specimen led to an improvement in tribological and micro-scratch properties compared to that of the sintered specimen, which may be attributed to the presence of nanostructured surface layer having an increase in surface hardness and reduction in surface roughness. The findings from this study are expected to be implemented to the automotive industry, in particular connected rod bearings and bushings in order to increase the efficiency and performance of internal combustion engines (ICEs).

  6. Stereospecific olefin polymerization catalysts

    DOEpatents

    Bercaw, John E.; Herzog, Timothy A.

    1998-01-01

    A metallocene catalyst system for the polymerization of .alpha.-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula ##STR1## wherein: R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; R.sup.4 and R.sup.6 are substituents both having van der Waals radii larger than the van der Waals radii of groups R.sup.1 and R.sup.3 ; R.sup.5 is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E.sup.1, E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; and the ligand may have C.sub.S or C.sub.1 -symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from .alpha.-olefin monomers.

  7. Stereospecific olefin polymerization catalysts

    DOEpatents

    Bercaw, J.E.; Herzog, T.A.

    1998-01-13

    A metallocene catalyst system is described for the polymerization of {alpha}-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula shown wherein: R{sup 1}, R{sup 2}, and R{sup 3} are independently selected from the group consisting of hydrogen, C{sub 1} to C{sub 10} alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C{sub 1} to C{sub 10} alkyls as a substituent, C{sub 6} to C{sub 15} aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R{sup 8}){sub 3} where R{sup 8} is selected from the group consisting of C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; R{sup 4} and R{sup 6} are substituents both having van der Waals radii larger than the van der Waals radii of groups R{sup 1} and R{sup 3}; R{sup 5} is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E{sup 1}, E{sup 2} are independently selected from the group consisting of Si(R{sup 9}){sub 2}, Si(R{sup 9}){sub 2}--Si(R{sup 9}){sub 2}, Ge(R{sup 9}){sub 2}, Sn(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}--C(R{sup 9}){sub 2}, where R{sup 9} is C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; and the ligand may have C{sub S} or C{sub 1}-symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from {alpha}-olefin monomers.

  8. METHOD OF PURIFYING CATALYSTS

    DOEpatents

    Joris, G.G.

    1958-09-01

    It has been fuund that the presence of chlorine as an impurity adversely affects the performance of finely divided platinum catalysts such as are used in the isotopic exchange process for the production of beavy water. This chlorine impurity may be removed from these catalysts by treating the catalyst at an elevated temperature with dry hydrogen and then with wet hydrogen, having a hydrogen-water vapor volume of about 8: 1. This alternate treatment by dry hydrogen and wet hydrogen is continued until the chlorine is largely removed from the catalyst.

  9. Polyolefin catalyst manufacturing

    SciTech Connect

    Inkrott, K.E.; Scinta, J.; Smith, P.D. )

    1989-10-16

    Statistical process control (SPC) procedures are absolutely essential for making new-generation polyolefin catalysts with the consistent high quality required by modern polyolefin processes. Stringent quality assurance is critical to the production of today's high-performance catalysts. Research and development efforts during the last 20 years have led to major technological improvements in the polyolefin industry. New generation catalysts, which once were laboratory curiosities, must now be produced commercially on a regular and consistent basis to meet the increasing requirements of the plastics manufacturing industry. To illustrate the more stringent requirements for producing the new generation polyolefin catalysts, the authors compare the relatively simple, first-generation polypropylene catalyst production requirements with some of the basic requirements of manufacturing a more complex new-generation catalyst, such as Catalyst Resources Inc.'s LYNX 900. The principles which hold true for the new-generation catalysts such as LYNX 900 are shown to apply equally to the scale-up of other advanced technology polyolefin catalysts.

  10. Liquefaction with microencapsulated catalysts

    DOEpatents

    Weller, Sol W.

    1985-01-01

    A method of dispersing a liquefaction catalyst within coal or other carbonaceous solids involves providing a suspension in oil of microcapsules containing the catalyst. An aqueous solution of a catalytic metal salt is emulsified in the water-immiscible oil and the resulting minute droplets microencapsulated in polymeric shells by interfacial polycondensation. The catalyst is subsequently blended and dispersed throughout the powdered carbonaceous material to be liquefied. At liquefaction temperatures the polymeric microcapsules are destroyed and the catalyst converted to minute crystallites in intimate contact with the carbonaceous material.

  11. OsO(4) in ionic liquid [Bmim]PF(6): a recyclable and reusable catalyst system for olefin dihydroxylation. remarkable effect of DMAP.

    PubMed

    Yao, Qingwei

    2002-06-27

    [reaction: see text] The combination of the ionic liquid [bmim]PF(6) and DMAP provides a most simple and practical approach to the immobilization of OsO(4) as catalyst for olefin dihydroxylation. Both the catalyst and the ionic liquid can be repeatedly recycled and reused in the dihydroxylation of a variety of olefins with only a very slight drop in catalyst activity.

  12. Cooperation of catalysts and templates

    NASA Technical Reports Server (NTRS)

    White, D. H.; Kanavarioti, A.; Nibley, C. W.; Macklin, J. W.

    1986-01-01

    In order to understand how self-reproducing molecules could have originated on the primitive Earth or extraterrestrial bodies, it would be useful to find laboratory models of simple molecules which are able to carry out processes of catalysis and templating. Furthermore, it may be anticipated that systems in which several components are acting cooperatively to catalyze each other's synthesis will have different behavior with respect to natural selection than those of purely replicating systems. As the major focus of this work, laboratory models are devised to study the influence of short peptide catalysts on template reactions which produce oligonucleotides or additional peptides. Such catalysts could have been the earliest protoenzymes of selective advantage produced by replicating oligonucleotides. Since this is a complex problem, simpler systems are also studied which embody only one aspect at a time, such as peptide formation with and without a template, peptide catalysis of nontemplated peptide synthesis, and model reactions for replication of the type pioneered by Orgel.

  13. Cooperation of catalysts and templates

    NASA Technical Reports Server (NTRS)

    White, D. H.; Kanavarioti, A.; Nibley, C. W.; Macklin, J. W.

    1986-01-01

    In order to understand how self-reproducing molecules could have originated on the primitive Earth or extraterrestrial bodies, it would be useful to find laboratory models of simple molecules which are able to carry out processes of catalysis and templating. Furthermore, it may be anticipated that systems in which several components are acting cooperatively to catalyze each other's synthesis will have different behavior with respect to natural selection than those of purely replicating systems. As the major focus of this work, laboratory models are devised to study the influence of short peptide catalysts on template reactions which produce oligonucleotides or additional peptides. Such catalysts could have been the earliest protoenzymes of selective advantage produced by replicating oligonucleotides. Since this is a complex problem, simpler systems are also studied which embody only one aspect at a time, such as peptide formation with and without a template, peptide catalysis of nontemplated peptide synthesis, and model reactions for replication of the type pioneered by Orgel.

  14. Elucidating the interaction between Ni and CeOx in ethanol steam reforming catalysts: A perspective of recent studies over model and powder systems

    SciTech Connect

    Liu, Zongyuan; Senanayake, Sanjaya D.; Rodriguez, Jose A.

    2016-11-15

    Bulk metallic nickel is a poor catalyst for the reforming of oxygenates being deactivated by the deposition of coke. In contrast, Ni-ceria is an active system for the catalytic extraction of H2 from the ethanol steam reforming reaction (ESR, C2H5OH + 3H2O ↔ 2CO2 + 6H2). Numerous studies, with model (well-defined crystal surfaces) and technical (high surface area powders) catalysts, have been devoted to understand the fundamental role of each catalyst component, the performance of adjacent sites in the metal-oxide interface, and the complex mechanistic steps that convert two oxygenated reactants (ethanol and H2O) into H2. The size and low loading of Ni on ceria facilitate metal-oxide support interactions that probably enhance the reactivity of the system. To establish the precise role of both Ni and Ce is challenging. However it is clear that both Ni and Ce are associated with the dissociation of H2O (OH + H), while ceria readily adsorbs and partially dissociates ethanol (i.e. ethoxy formation). The most difficult step of Csingle bondC bond dissociation likely occurs only on Ni or at the Ni-Ce interface. H2O and OH remain as important agents for the prevention of excess C build up during the C—H/C—C dissociation process. Often, deactivation upon C build up, is a direct result of Ni sintering and decoupling of the Ni-Ce interactions. One strategy to maintain good activity and stability is to protect the Ni-Ce interaction, and this can be achieved through the use of solid solutions (Ce1–xNixO2–y) or by employing stabilizing agents such as W (NixWyCezO2). In this study, we present and discuss the most recent work for the ESR reaction and show the important role of ceria which participates directly in the reaction and also enhances catalytic activity through metal-support interactions.

  15. Elucidating the interaction between Ni and CeOx in ethanol steam reforming catalysts: A perspective of recent studies over model and powder systems

    SciTech Connect

    Liu, Zongyuan; Senanayake, Sanjaya D.; Rodriguez, Jose A.

    2016-11-15

    Bulk metallic nickel is a poor catalyst for the reforming of oxygenates being deactivated by the deposition of coke. In contrast, Ni-ceria is an active system for the catalytic extraction of H2 from the ethanol steam reforming reaction (ESR, C2H5OH + 3H2O ↔ 2CO2 + 6H2). Numerous studies, with model (well-defined crystal surfaces) and technical (high surface area powders) catalysts, have been devoted to understand the fundamental role of each catalyst component, the performance of adjacent sites in the metal-oxide interface, and the complex mechanistic steps that convert two oxygenated reactants (ethanol and H2O) into H2. The size and low loading of Ni on ceria facilitate metal-oxide support interactions that probably enhance the reactivity of the system. To establish the precise role of both Ni and Ce is challenging. However it is clear that both Ni and Ce are associated with the dissociation of H2O (OH + H), while ceria readily adsorbs and partially dissociates ethanol (i.e. ethoxy formation). The most difficult step of Csingle bondC bond dissociation likely occurs only on Ni or at the Ni-Ce interface. H2O and OH remain as important agents for the prevention of excess C build up during the Csingle bondH/Csingle bondC dissociation process. Often, deactivation upon C build up, is a direct result of Ni sintering and decoupling of the Ni-Ce interactions. One strategy to maintain good activity and stability is to protect the Ni-Ce interaction, and this can be achieved through the use of solid solutions (Ce1–xNixO2–y) or by employing stabilizing agents such as W (NixWyCezO2). In this paper, we present and discuss the most recent work for the ESR reaction and show the important role of ceria which participates directly in the reaction and also enhances catalytic activity through

  16. Elucidating the interaction between Ni and CeOx in ethanol steam reforming catalysts: A perspective of recent studies over model and powder systems

    DOE PAGES

    Liu, Zongyuan; Senanayake, Sanjaya D.; Rodriguez, Jose A.

    2016-11-15

    Bulk metallic nickel is a poor catalyst for the reforming of oxygenates being deactivated by the deposition of coke. In contrast, Ni-ceria is an active system for the catalytic extraction of H2 from the ethanol steam reforming reaction (ESR, C2H5OH + 3H2O ↔ 2CO2 + 6H2). Numerous studies, with model (well-defined crystal surfaces) and technical (high surface area powders) catalysts, have been devoted to understand the fundamental role of each catalyst component, the performance of adjacent sites in the metal-oxide interface, and the complex mechanistic steps that convert two oxygenated reactants (ethanol and H2O) into H2. The size and lowmore » loading of Ni on ceria facilitate metal-oxide support interactions that probably enhance the reactivity of the system. To establish the precise role of both Ni and Ce is challenging. However it is clear that both Ni and Ce are associated with the dissociation of H2O (OH + H), while ceria readily adsorbs and partially dissociates ethanol (i.e. ethoxy formation). The most difficult step of Csingle bondC bond dissociation likely occurs only on Ni or at the Ni-Ce interface. H2O and OH remain as important agents for the prevention of excess C build up during the Csingle bondH/Csingle bondC dissociation process. Often, deactivation upon C build up, is a direct result of Ni sintering and decoupling of the Ni-Ce interactions. One strategy to maintain good activity and stability is to protect the Ni-Ce interaction, and this can be achieved through the use of solid solutions (Ce1–xNixO2–y) or by employing stabilizing agents such as W (NixWyCezO2). In this paper, we present and discuss the most recent work for the ESR reaction and show the important role of ceria which participates directly in the reaction and also enhances catalytic activity through metal-support interactions.« less

  17. Elucidating the interaction between Ni and CeOx in ethanol steam reforming catalysts: A perspective of recent studies over model and powder systems

    DOE PAGES

    Liu, Zongyuan; Senanayake, Sanjaya D.; Rodriguez, Jose A.

    2016-11-15

    Bulk metallic nickel is a poor catalyst for the reforming of oxygenates being deactivated by the deposition of coke. In contrast, Ni-ceria is an active system for the catalytic extraction of H2 from the ethanol steam reforming reaction (ESR, C2H5OH + 3H2O ↔ 2CO2 + 6H2). Numerous studies, with model (well-defined crystal surfaces) and technical (high surface area powders) catalysts, have been devoted to understand the fundamental role of each catalyst component, the performance of adjacent sites in the metal-oxide interface, and the complex mechanistic steps that convert two oxygenated reactants (ethanol and H2O) into H2. The size and lowmore » loading of Ni on ceria facilitate metal-oxide support interactions that probably enhance the reactivity of the system. To establish the precise role of both Ni and Ce is challenging. However it is clear that both Ni and Ce are associated with the dissociation of H2O (OH + H), while ceria readily adsorbs and partially dissociates ethanol (i.e. ethoxy formation). The most difficult step of Csingle bondC bond dissociation likely occurs only on Ni or at the Ni-Ce interface. H2O and OH remain as important agents for the prevention of excess C build up during the C—H/C—C dissociation process. Often, deactivation upon C build up, is a direct result of Ni sintering and decoupling of the Ni-Ce interactions. One strategy to maintain good activity and stability is to protect the Ni-Ce interaction, and this can be achieved through the use of solid solutions (Ce1–xNixO2–y) or by employing stabilizing agents such as W (NixWyCezO2). In this study, we present and discuss the most recent work for the ESR reaction and show the important role of ceria which participates directly in the reaction and also enhances catalytic activity through metal-support interactions.« less

  18. Polypropylene reinvented: Costs of using metallocene catalysts

    SciTech Connect

    Brockmeier, N.F.

    1996-05-01

    This study develops scoping estimates of the required capital investment and manufacturing costs to make a zirconocene catalyst/cocatalyst system [(F{sub 6}-acen)Zr(CH{sub 2}CMe{sub 3})(NMe{sub 2}Ph)][B(C{sub 6}F{sub 5}){sub 4}] immobilized on a silica support. Costs for this fluorine-based system are compared with estimates for two other metallocene catalysts using methylaluminoxane (MAO)-based cocatalysts. Including wt of support and cocatalyst, each of the production facilities for making the 3 zirconocene catalyst systems is sized at 364--484 tonnes/year. Cost to make the F-based catalyst system is estimated to be $10780/kg, assuming 20% return on capital invested. Costs for the two MAO-based catalyst system fall in the range of $10950--12160/kg, assuming same return. Within the {plus_minus}50% accuracy of these estimates, these differences are not significant. Given a catalyst productivity of 250 kg resin/gram zirconocene, the cost contribution in the finished ethylene-propylene copolymer resin is 4.4 cents/kg, excluding selling, administrative, research costs.

  19. Aqueous Biphasic Systems for the Synthesis of Formates by Catalytic CO2 Hydrogenation: Integrated Reaction and Catalyst Separation for CO2 -Scrubbing Solutions.

    PubMed

    Scott, Martin; Blas Molinos, Beatriz; Westhues, Christian; Franciò, Giancarlo; Leitner, Walter

    2017-03-22

    Aqueous biphasic systems were investigated for the production of formate-amine adducts by metal-catalyzed CO2 hydrogenation, including typical scrubbing solutions as feedstocks. Different hydrophobic organic solvents and ionic liquids could be employed as the stationary phase for cis-[Ru(dppm)2 Cl2 ] (dppm=bis-diphenylphosphinomethane) as prototypical catalyst without any modification or tagging of the complex. The amines were found to partition between the two phases depending on their structure, whereas the formate-amine adducts were nearly quantitatively extracted into the aqueous phase, providing a favorable phase behavior for the envisaged integrated reaction/separation sequence. The solvent pair of methyl isobutyl carbinol (MIBC) and water led to the most practical and productive system and repeated use of the catalyst phase was demonstrated. The highest single batch activity with a TOFav of approximately 35 000 h(-1) and an initial TOF of approximately 180 000 h(-1) was achieved in the presence of NEt3 . Owing to higher stability, the highest productivities were obtained with methyl diethanolamine (Aminosol CST 115) and monoethanolamine (MEA), which are used in commercial scale CO2 -scrubbing processes. Saturated aqueous solutions (CO2 overpressure 5-10 bar) of MEA could be converted into the corresponding formate adducts with average turnover frequencies up to 14×10(3)  h(-1) with an overall yield of 70 % based on the amine, corresponding to a total turnover number of 150 000 over eleven recycling experiments. This opens the possibility for integrated approaches to carbon capture and utilization.

  20. Hydroxide catalysts for lignin depolymerization

    DOEpatents

    Beckham, Gregg T.; Biddy, Mary J.; Chmely, Stephen C.; Sturgeon, Matthew

    2017-04-25

    Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

  1. Self-organization of Cu-based immiscible alloys under irradiation: An atom-probe tomography study

    NASA Astrophysics Data System (ADS)

    Stumphy, Brad D.

    The stability of materials subjected to prolonged irradiation has been a topic of renewed interest in recent years due to the projected growth of nuclear power as an alternative energy source. The irradiating particles impart energy into the material, thereby causing atomic displacements to occur. These displacements result in the creation of point defects and the random ballistic mixing of the atoms. Consequently, the material is driven away from its equilibrium structure. The supersaturation of defects can lead to the degradation of mechanical properties, but a high density of internal interfaces, which act as defect sinks, will suppress the supersaturation and long-range transport of defects. The microstructural evolution of the material is controlled by the ballistic mixing as well as the mobility of the point defects. In immiscible alloys, these two processes compete against one another, as the ballistic mixing acts to solutionize the alloy components, and the thermal diffusion of the large number of defects acts to phase separate the components. The work presented in this dissertation examines the effect of heavy-ion irradiation on immiscible, binary Cu-based alloys. Dilute alloys of Cu-Fe, Cu-V, and V-Cu have been subjected to irradiation, and atom-probe tomography has been utilized in order to better understand the complex nature of the response of these simple model systems to an irradiation environment. The results show that a steady-state, nano-scale patterning structure, with a high density of unsaturable defect sinks, can be maintained under prolonged irradiation. Additionally, precipitation from a supersaturated solid solution is shown to be a function of both the thermal diffusion and the ballistic mixing. Solvent-rich secondary precipitates, termed "cherry-pits," are observed inside of the solute-rich primary precipitates. Through a combination of simulation work and analyzing multiple alloys experimentally, it was determined that this cherry

  2. Advanced Petroleum-Based Fuels - Diesel Emissions Project (APBF-DEC): 2,000-Hour Performance of a NOx Adsorber Catalyst and Diesel Particle Filter System for a Medium-Duty, Pick-Up Diesel Engine Platform; Final Report

    SciTech Connect

    Not Available

    2007-03-01

    Presents the results of a 2,000-hour test of an emissions control system consisting of a nitrogen oxides adsorber catalyst in combination with a diesel particle filter, advanced fuels, and advanced engine controls in an SUV/pick-up truck vehicle platform.

  3. Development and performance of Cu-based oxygen carriers for chemical-looping combustion

    SciTech Connect

    Chuang, S.Y.; Dennis, J.S.; Hayhurst, A.N.; Scott, S.A.

    2008-07-15

    Chemical-looping combustion (CLC) has the inherent property of separating the product CO{sub 2} from flue gases. Instead of air, it uses an oxygen carrier, usually in the form of a metal oxide, to provide oxygen for combustion. This paper focuses on the development and performance of a suitable Cu-based oxygen carrier for burning solid fuels using CLC. Carriers were made from CuO and Al{sub 2}O{sub 3} (as a support) in three different ways: mechanical mixing, wet impregnation, and co-precipitation. The reactivity of these solids was assessed by measuring their ability to oxidize CO, when in a hot bed of sand fluidized by a mixture of CO and N{sub 2}. After that, the Cu in the carrier was oxidized back to CuO by fluidizing the hot bed with air. These oxygen carriers were tested over many such cycles of reduction and oxidation. This work confirms that supporting CuO on Al{sub 2}O{sub 3} enhances the ability of the resulting particles to withstand mechanical and thermal stresses in a fluidized bed. Also, only co-precipitation produces particles that have a high loading of copper and do not agglomerate at 800-900 C. The performance of co-precipitated particles of CuO/Al{sub 2}O{sub 3} at oxidizing CO to CO{sub 2} was significantly affected by the pH of the solution in which precipitation occurred: a high pH (9.7) gave particles that reacted completely and rapidly. After 18 cycles, such a co-precipitated carrier with 82.5 wt% CuO yielded all its oxygen when oxidizing CO. X-ray analysis showed that when heated, CuO reacted with Al{sub 2}O{sub 3} to form CuAl{sub 2}O{sub 4}, which was fully reducible, so CuO experienced no loss in extent of reaction after forming this mixed oxide. An increase in operating temperature from 800 to 900 C led to the CuO providing slightly less oxygen; this was because a little of the CuO decomposed to Cu{sub 2}O between its reduction and oxidation, when the bed was fluidized by pure N{sub 2}. (author)

  4. Nano-catalysts: Bridging the gap between homogeneous and heterogeneous catalysis

    EPA Science Inventory

    Functionalized nanoparticles have emerged as sustainable alternatives to conventional materials, as robust, high-surface-area heterogeneous catalyst supports. We envisioned a catalyst system, which can bridge the homogenous and heterogeneous system. Postsynthetic surface modifica...

  5. Recombination Catalysts for Hypersonic Fuels

    NASA Technical Reports Server (NTRS)

    Chinitz, W.

    1998-01-01

    The goal of commercially-viable access to space will require technologies that reduce propulsion system weight and complexity, while extracting maximum energy from the products of combustion. This work is directed toward developing effective nozzle recombination catalysts for the supersonic and hypersonic aeropropulsion engines used to provide such access to space. Effective nozzle recombination will significantly reduce rk=le length (hence, propulsion system weight) and reduce fuel requirements, further decreasing the vehicle's gross lift-off weight. Two such catalysts have been identified in this work, barium and antimony compounds, by developing chemical kinetic reaction mechanisms for these materials and determining the engine performance enhancement for a typical flight trajectory. Significant performance improvements are indicated, using only 2% (mole or mass) of these compounds in the combustor product gas.

  6. Nanostructured catalyst supports

    DOEpatents

    Zhu, Yimin; Goldman, Jay L.; Qian, Baixin; Stefan, Ionel C.

    2012-10-02

    The present invention relates to SiC nanostructures, including SiC nanopowder, SiC nanowires, and composites of SiC nanopowder and nanowires, which can be used as catalyst supports in membrane electrode assemblies and in fuel cells. The present invention also relates to composite catalyst supports comprising nanopowder and one or more inorganic nanowires for a membrane electrode assembly.

  7. Nanostructured catalyst supports

    DOEpatents

    Zhu, Yimin; Goldman, Jay L.; Qian, Baixin; Stefan, Ionel C.

    2015-09-29

    The present invention relates to SiC nanostructures, including SiC nanopowder, SiC nanowires, and composites of SiC nanopowder and nanowires, which can be used as catalyst supports in membrane electrode assemblies and in fuel cells. The present invention also relates to composite catalyst supports comprising nanopowder and one or more inorganic nanowires for a membrane electrode assembly.

  8. Reducible oxide based catalysts

    DOEpatents

    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.

  9. Fischer-Tropsch Catalysts

    NASA Technical Reports Server (NTRS)

    White, James H. (Inventor); Taylor, Jesse W. (Inventor)

    2008-01-01

    Catalyst compositions and methods for F-T synthesis which exhibit high CO conversion with minor levels (preferably less than 35% and more preferably less than 5%) or no measurable carbon dioxide generation. F-T active catalysts are prepared by reduction of certain oxygen deficient mixed metal oxides.

  10. Catalysts and process for liquid hydrocarbon fuel production

    DOEpatents

    White, Mark G.; Ranaweera, Samantha A.; Henry, William P.

    2016-08-02

    The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality distillates, gasoline components, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel supported bimetallic ion complex catalyst for conversion, and provides methods of preparing such novel catalysts and use of the novel catalysts in the process and system of the invention.

  11. High-temperature catalyst for catalytic combustion and decomposition

    NASA Technical Reports Server (NTRS)

    Mays, Jeffrey A. (Inventor); Lohner, Kevin A. (Inventor); Sevener, Kathleen M. (Inventor); Jensen, Jeff J. (Inventor)

    2005-01-01

    A robust, high temperature mixed metal oxide catalyst for propellant composition, including high concentration hydrogen peroxide, and catalytic combustion, including methane air mixtures. The uses include target, space, and on-orbit propulsion systems and low-emission terrestrial power and gas generation. The catalyst system requires no special preheat apparatus or special sequencing to meet start-up requirements, enabling a fast overall response time. Start-up transients of less than 1 second have been demonstrated with catalyst bed and propellant temperatures as low as 50 degrees Fahrenheit. The catalyst system has consistently demonstrated high decomposition effeciency, extremely low decomposition roughness, and long operating life on multiple test particles.

  12. Hydroliquefaction of coal with supported catalysts: 1980 status review

    SciTech Connect

    Polinski, Leon M.; Stiegel, Gary J.; Tischer, Richard E.

    1981-06-01

    The objectives of the program have been to determine catalyst deactivation kinetic models and catalyst deactivation modes for supported Co-Mo and Ni-Mo catalysts used primarily in coal liquefaction via the H-COAL process. Emphasis has been on developing methods to increase catalyst usage by determining how to decrease catalyst replacement rates in the process and how to decrease catalyst poisoning. An important conclusion reached via model analysis and verified by experiment is that larger diameter (1/16 in.) catalysts resist poisoning deactivation much more than smaller (1/32 in.) catalysts over extended periods (60 to 110 hours) of time. If this trend can be verified, it gives a powerful tool for reducing catalyst replacement rate in the H-COAL ebullated bed system by factors of 2 or more. A second conclusion is that poisoning of catalysts occurs by several possible mechanisms or modes. Indirect or direct evidence of all these modes can be presented, though the relative importance of each mechanism has not been established. The modes include (a) poisoning by coking - with gradual increase in C/H ratio (more refractory coke) with time, (b) poisoning by metallization (selective/non-selective adsorption of inorganics such as Ti and Fe on the catalyst), (c) sintering - increase in larger pores/decrease in surface area, and (d) parallel poisoning by irreversible nitrogen compound adsorption.

  13. Organometallic polymerization catalysts

    SciTech Connect

    Waymouth, R.M.

    1993-12-31

    Well-defined transition metal catalysts have resulted in exciting new opportunities in polymer synthesis. The stereochemistry of vinyl polymers can be rationally controlled with choice of the appropriate catalysts. Studies with optically active catalyst precursors have revealed considerable information on the absolute stereochemistry of olefin polymerization and have led to the synthesis of novel chiral polyolefins. The development of homogeneous olefin metathesis catalysts has also led to a variety of well-defined new polymer structures with controlled molecular weight and molecular weight distribution. Recent advances in understanding the mechanisms and stereochemistry of homogeneous transition metal catalyzed polymerization will be discussed. The ability to control polymer structure through catalyst design presents exciting opportunities in the synthesis of {open_quotes}tailor-made{close_quotes} macromolecules.

  14. Surface Al leached Ti3AlC2 as a substitute for carbon for use as a catalyst support in a harsh corrosive electrochemical system.

    PubMed

    Xie, Xiaohong; Xue, Yun; Li, Li; Chen, Siguo; Nie, Yao; Ding, Wei; Wei, Zidong

    2014-10-07

    Surface Al leached Ti3AlC2 particles (e-TAC) with high corrosion resistance and excellent electrical conductivity were developed as an advanced support material for Pt catalysts. Electrochemical measurements confirm that the supported Pt/e-TAC electrocatalyst shows much improved activity and enhanced durability toward the oxygen reduction reaction when compared with the commercial Pt/C catalyst.

  15. Protic acid immobilized on solid support as an extremely efficient recyclable catalyst system for a direct and atom economical esterification of carboxylic acids with alcohols.

    PubMed

    Chakraborti, Asit K; Singh, Bavneet; Chankeshwara, Sunay V; Patel, Alpesh R

    2009-08-21

    A convenient and clean procedure of esterification is reported by direct condensation of equimolar amounts of carboxylic acids with alcohols catalyzed by an easy to prepare catalyst system of perchloric acid immobilized on silica gel (HClO(4)-SiO(2)). The direct condensation of aryl, heteroaryl, styryl, aryl alkyl, alkyl, cycloalkyl, and long-chain aliphatic carboxylic acids with primary/secondary alkyl/cycloalkyl, allyl, propargyl, and long-chain aliphatic alcohols has been achieved to afford the corresponding esters in excellent yields. Chiral alcohol and N-t-Boc protected chiral amino acid also resulted in ester formation with the representative carboxylic acid or alcohol without competitive N-t-Boc deprotection and detrimental effect on the optical purity of the product demonstrating the mildness and chemoselectivity of the procedure. The esters of long-chain (>C(10)) acids and alcohols are obtained in high yields. The catalyst is recovered and recycled without significant loss of activity. The industrial application of the esterification process is demonstrated by the synthesis of prodrugs of ibuprofen and a few commercial flavoring agents. Other protic acids such as H(2)SO(4), HBr, TfOH, HBF(4), and TFA that were adsorbed on silica gel were less effective compared to HClO(4)-SiO(2) following the order HClO(4)-SiO(2) > H(2)SO(4)-SiO(2) > HBr-SiO(2) > TfOH-SiO(2) > HBF(4)-SiO(2) approximately TFA-SiO(2). When HClO(4) was immobilized on other solid supports the catalytic efficiency followed the order HClO(4)-SiO(2) > HClO(4)-K10 > HClO(4)-Al(2)O(3) (neutral) > HClO(4)-Al(2)O(3) (acidic) > HClO(4)-Al(2)O(3) (basic).

  16. Cu-based carbene involved in a radical process: a new crossover reaction to construct γ-peroxy esters and 1,4-dicarbonyl compounds.

    PubMed

    Jiang, Jiewen; Liu, Jiajun; Yang, Ling; Shao, Ying; Cheng, Jiang; Bao, Xiaoguang; Wan, Xiaobing

    2015-10-11

    Through merging Cu-based carbenes in a radical process, a novel crossover reaction has been successfully established, leading to the facile and efficient syntheses of various γ-peroxy esters and 1,4-dicarbonyl compounds. Considering that both Cu-based carbene complexes and radicals are extremely reactive, and therefore exist only in extraordinarily low concentrations, the high selectivity of this coupling reaction is unusual.

  17. Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process

    DOEpatents

    Peng, Xiang-Dong; Parris, Gene E.; Toseland, Bernard A.; Battavio, Paula J.

    1998-01-01

    The present invention pertains to a process for the coproduction of methanol and dimethyl ether (DME) directly from a synthesis gas in a single step (hereafter, the "single step DME process"). In this process, the synthesis gas comprising hydrogen and carbon oxides is contacted with a dual catalyst system comprising a physical mixture of a methanol synthesis catalyst and a methanol dehydration catalyst. The present invention is an improvement to this process for providing an active and stable catalyst system. The improvement comprises the use of an aluminum phosphate based catalyst as the methanol dehydration catalyst. Due to its moderate acidity, such a catalyst avoids the coke formation and catalyst interaction problems associated with the conventional dual catalyst systems taught for the single step DME process.

  18. Synthesis and Understanding of Novel Catalysts

    SciTech Connect

    Stair, Peter C.

    2013-07-09

    The research took advantage of our capabilities to perform in-situ and operando Raman spectroscopy on complex systems along with our developing expertise in the synthesis of uniform, supported metal oxide materials to investigate relationships between the catalytically active oxide composition, atomic structure, and support and the corresponding chemical and catalytic properties. The project was organized into two efforts: 1) Synthesis of novel catalyst materials by atomic layer deposition (ALD). 2) Spectroscopic and chemical investigations of coke formation and catalyst deactivation. ALD synthesis was combined with conventional physical characterization, Raman spectroscopy, and probe molecule chemisorption to study the effect of supported metal oxide composition and atomic structure on acid-base and catalytic properties. Operando Raman spectroscopy studies of olefin polymerization leading to coke formation and catalyst deactivation clarified the mechanism of coke formation by acid catalysts.

  19. Fundamental studies of supported bimetallic catalysts by NMR spectroscopy

    SciTech Connect

    Savargaonkar, Nilesh

    1996-10-17

    Various hydrogenation reactions on transition metals are important commercially whereas certain hydrogenolysis reactions are useful from fundamental point of view. Understanding the hydrogen mobility and kinetics of adsorption-desorption of hydrogen is important in understanding the mechanisms of such reactions involving hydrogen. The kinetics of hydrogen chemisorption was studied by means of selective excitation NMR on silica supported Pt, Rh and Pt-Rh catalysts. The activation energy of hydrogen desorption was found to be lower on silica supported Pt catalysts as compared to Rh and Pt-Rh catalysts. It was found that the rates of hydrogen adsorption and desorption on Pt-Rh catalyst were similar to those on Rh catalyst and much higher as compared to Pt catalyst. The Ru-Ag bimetallic system is much simpler to study than the Pt-Rh system and serves as a model system to characterize more complicated systems such as the K/Ru system. Ag was found to decrease the amounts of adsorbed hydrogen and the hydrogen-to-ruthenium stoichiometry. Ag reduced the populations of states with low and intermediate binding energies of hydrogen on silica supported Ru catalyst. The rates of hydrogen adsorption and desorption were also lower on silica supported Ru-Ag catalyst as compared to Ru catalyst. This report contains introductory information, the literature review, general conclusions, and four appendices. An additional four chapters and one appendix have been processed separately for inclusion on the data base.

  20. Photoreduction of CO2 using [Ru(bpy)2(CO)L]n+ catalysts in biphasic solution/supercritical CO2 systems.

    PubMed

    Voyame, Patrick; Toghill, Kathryn E; Méndez, Manuel A; Girault, Hubert H

    2013-10-07

    The reduction of CO2 in a biphasic liquid-condensed gas system was investigated as a function of the CO2 pressure. Using 1-benzyl-1,4-dihydronicotinamide (BNAH) as sacrificial electron donor dissolved in a dimethylformamide-water mixture and [Ru(bpy)2(CO)L](n+) as a catalyst and [Ru(bpy)3](2+) as a photosensitizer, the reaction was found to produce a mixture of CO and formate, in total about 250 μmol after just 2 h. As CO2 pressure increases, CO formation is greatly favored, being four times greater than that of formate in aqueous systems. In contrast, formate production was independent of CO2 pressure, present at about 50 μmol. Using TEOA as a solvent instead of water created a single-phase supercritical system and greatly favored formate synthesis, but similarly increasing CO2 concentration favored the CO catalytic cycle. Under optimum conditions, a turnover number (TON) of 125 was obtained. Further investigations of the component limits led to an unprecedented TON of over 1000, and an initial turnover frequency (TOF) of 1600 h(-1).

  1. Polymerization catalyst, production and use

    SciTech Connect

    Best, S.A.

    1987-01-06

    A process is described for the polymerization of ethylene and alpha-olefins having from 1 to 2 carbon atoms of mixtures of ethylene, alpha-olefins or diolefins. The process comprises polymerizing one or more olefins in the presence of the catalyst system comprising (A) an organo aluminum cocatalyst, and (B) a vanadium-containing catalyst component obtained by sequentially treating an inert solid support material in an inert solvent with (i) a dihydrocarbyl magnesium compound, (ii) optionally an oxygen-containing compound which is an alcohol, ketone or aldehyde, (iii) a vanadium compound, and (iv) a Group IIIa metal halide. The process as above is described wherein the inert solid support material is an inorganic oxide or mixtures of inorganic oxides.

  2. Polymerization catalyst, production and use

    SciTech Connect

    Best, S.A.

    1987-04-14

    A process is described for the polymerization of ethylene and alphaolefins having from 1 to 20 carbon atoms or mixtures of ethylene, alpha-olefins or diolefins. The process comprises polymerizing one or more olefins in the presence of the catalyst system comprising (A) an organo aluminum cocatalyst, and (B) a vanadium-containing catalyst component obtained by treating an inert support material in an inert solvent with (i) a dihydrocarbyl magnesium compound or a complex or mixture of an organic dihydrocarbyl magnesium compound and an aluminum compound, (ii) optionally an oxygen-containing compound which is an alcohol, ketone or aldehyde, (iii) a Group IIIa metal halide, (iv) at least one vanadium compound, and as the last step a second treatment with a Group IIIa metal halide.

  3. Catalysts and process for liquid hydrocarbon fuel production

    DOEpatents

    White, Mark G; Liu, Shetian

    2014-12-09

    The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality gasoline components, aromatic compounds, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel molybdenum-zeolite catalyst in high pressure hydrogen for conversion, as well as a novel rhenium-zeolite catalyst in place of the molybdenum-zeolite catalyst, and provides for use of the novel catalysts in the process and system of the invention.

  4. Catalyst for Carbon Monoxide Oxidation

    NASA Technical Reports Server (NTRS)

    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

  5. Cross-coupling of diarylborinic acids and anhydrides with arylhalides catalyzed by a phosphite/N-heterocyclic carbene co-supported palladium catalyst system.

    PubMed

    Chen, Xiaofeng; Ke, Haihua; Chen, Yao; Guan, Changwei; Zou, Gang

    2012-09-07

    A highly efficient cross-coupling of diarylborinic acids and anhydrides with aryl chlorides and bromides has been effected by using a palladium catalyst system co-supported by a strong σ-donor N-heterocyclic carbene (NHC), N,N'-bis(2,6-diisopropylphenyl) imidazol-2-ylidene, and a strong π-acceptor phosphite, triphenylphosphite, in tert-BuOH in the present of K(3)PO(4)·3H(2)O. Unsymmetrical biaryls with a variety of functional groups could be obtained in good to excellent yields using as low as 0.01, 0.2-0.5, and 1 mol % palladium loadings for aryl bromides and activated and deactivated aryl chlorides, respectively, under mild conditions. A ligand synergy between the σ-donor NHC and the π-acceptor phosphite in the Pd/NHC/P(OPh)(3) catalytic system has been proposed to be responsible for the high efficacy to arylchlorides in the cross-coupling. A scalable and economical process has therefore been developed for synthesis of Sartan biphenyl from the Pd/NHC/P(OPh)(3) catalyzed cross-coupling of di(4-methylphenyl)borinic acid with 2-chlorobenzonitrile.

  6. Catalysts and method

    DOEpatents

    Taylor, Charles E.; Noceti, Richard P.

    1991-01-01

    An improved catlayst and method for the oxyhydrochlorination of methane is disclosed. The catalyst includes a pyrogenic porous support on which is layered as active material, cobalt chloride in major proportion, and minor proportions of an alkali metal chloride and of a rare earth chloride. On contact of the catalyst with a gas flow of methane, HC1 and oxygen, more than 60% of the methane is converted and of that converted more than 40% occurs as monochloromethane. Advantageously, the monochloromethane can be used to produce gasoline boiling range hydrocarbons with the recycle of HCl for further reaction. This catalyst is also of value for the production of formic acid as are analogous catalysts with lead, silver or nickel chlorides substituted for the cobalt chloride.

  7. Epoxidation catalyst and process

    DOEpatents

    Linic, Suljo; Christopher, Phillip

    2010-10-26

    Disclosed herein is a catalytic method of converting alkenes to epoxides. This method generally includes reacting alkenes with oxygen in the presence of a specific silver catalyst under conditions suitable to produce a yield of the epoxides. The specific silver catalyst is a silver nanocrystal having a plurality of surface planes, a substantial portion of which is defined by Miller indices of (100). The reaction is performed by charging a suitable reactor with this silver catalyst and then feeding the reactants to the reactor under conditions to carry out the reaction. The reaction may be performed in batch, or as a continuous process that employs a recycle of any unreacted alkenes. The specific silver catalyst has unexpectedly high selectivity for epoxide products. Consequently, this general method (and its various embodiments) will result in extraordinarily high epoxide yields heretofore unattainable.

  8. Reclaim spent catalysts properly

    SciTech Connect

    Lassner, J.A.; Lasher, L.B.; Koppel, R.L.; Hamilton, J.N.

    1994-08-01

    Treatment of spent catalysts and metallic by products has become increasingly more complex over the last couple of years, due to tightening environmental concerns. Three options are available: (1) Reclaiming the metals and either reusing them to make new catalyst or recycling them for other uses. This is now the preferred option. A reclaiming firm is generally employed to handle the task. (2) Regeneration and reuse. While this generally is the preferred option, few commercial catalysts can be regenerated effectively and economically. (3) Landfilling. This has been the traditional route. However, stricter environmental regulations have made landfilling unattractive. To maximize the reclamation both economically and environmentally, five factors should be addressed: (1) proper planning and physical handling; (2) transportation of materials; (3) environmental concerns; (4) end uses of the catalyst; and (5) choosing the proper reclamation partner. These factors are discussed.

  9. Innovative PCDD/F-containing gas stream generating system applied in catalytic decomposition of gaseous dioxins over V2O5-WO3/TiO2-based catalysts.

    PubMed

    Yang, Chia Cheng; Chang, Shu Hao; Hong, Bao Zhen; Chi, Kai Hsien; Chang, Moo Been

    2008-10-01

    Development of effective PCDD/F (polychlorinated dibenzo-p-dioxin and dibenzofuran) control technologies is essential for environmental engineers and researchers. In this study, a PCDD/F-containing gas stream generating system was developed to investigate the efficiency and effectiveness of innovative PCDD/F control technologies. The system designed and constructed can stably generate the gas stream with the PCDD/F concentration ranging from 1.0 to 100ng TEQ Nm(-3) while reproducibility test indicates that the PCDD/F recovery efficiencies are between 93% and 112%. This new PCDD/F-containing gas stream generating device is first applied in the investigation of the catalytic PCDD/F control technology. The catalytic decomposition of PCDD/Fs was evaluated with two types of commercial V(2)O(5)-WO(3)/TiO(2)-based catalysts (catalyst A and catalyst B) at controlled temperature, water vapor content, and space velocity. 84% and 91% PCDD/F destruction efficiencies are achieved with catalysts A and B, respectively, at 280 degrees C with the space velocity of 5000h(-1). The results also indicate that the presence of water vapor inhibits PCDD/F decomposition due to its competition with PCDD/F molecules for adsorption on the active vanadia sites for both catalysts. In addition, this study combined integral reaction and Mars-Van Krevelen model to calculate the activation energies of OCDD and OCDF decomposition. The activation energies of OCDD and OCDF decomposition via catalysis are calculated as 24.8kJmol(-1) and 25.2kJmol(-1), respectively.

  10. Solar-Driven Reduction of Aqueous Protons Coupled to Selective Alcohol Oxidation with a Carbon Nitride-Molecular Ni Catalyst System.

    PubMed

    Kasap, Hatice; Caputo, Christine A; Martindale, Benjamin C M; Godin, Robert; Lau, Vincent Wing-Hei; Lotsch, Bettina V; Durrant, James R; Reisner, Erwin

    2016-07-27

    Solar water-splitting represents an important strategy toward production of the storable and renewable fuel hydrogen. The water oxidation half-reaction typically proceeds with poor efficiency and produces the unprofitable and often damaging product, O2. Herein, we demonstrate an alternative approach and couple solar H2 generation with value-added organic substrate oxidation. Solar irradiation of a cyanamide surface-functionalized melon-type carbon nitride ((NCN)CNx) and a molecular nickel(II) bis(diphosphine) H2-evolution catalyst (NiP) enabled the production of H2 with concomitant selective oxidation of benzylic alcohols to aldehydes in high yield under purely aqueous conditions, at room temperature and ambient pressure. This one-pot system maintained its activity over 24 h, generating products in 1:1 stoichiometry, separated in the gas and solution phases. The (NCN)CNx-NiP system showed an activity of 763 μmol (g CNx)(-1) h(-1) toward H2 and aldehyde production, a Ni-based turnover frequency of 76 h(-1), and an external quantum efficiency of 15% (λ = 360 ± 10 nm). This precious metal-free and nontoxic photocatalytic system displays better performance than an analogous system containing platinum instead of NiP. Transient absorption spectroscopy revealed that the photoactivity of (NCN)CNx is due to efficient substrate oxidation of the material, which outweighs possible charge recombination compared to the nonfunctionalized melon-type carbon nitride. Photoexcited (NCN)CNx in the presence of an organic substrate can accumulate ultralong-lived "trapped electrons", which allow for fuel generation in the dark. The artificial photosynthetic system thereby catalyzes a closed redox cycle showing 100% atom economy and generates two value-added products, a solar chemical, and solar fuel.

  11. Solar-Driven Reduction of Aqueous Protons Coupled to Selective Alcohol Oxidation with a Carbon Nitride–Molecular Ni Catalyst System

    PubMed Central

    2016-01-01

    Solar water-splitting represents an important strategy toward production of the storable and renewable fuel hydrogen. The water oxidation half-reaction typically proceeds with poor efficiency and produces the unprofitable and often damaging product, O2. Herein, we demonstrate an alternative approach and couple solar H2 generation with value-added organic substrate oxidation. Solar irradiation of a cyanamide surface-functionalized melon-type carbon nitride (NCNCNx) and a molecular nickel(II) bis(diphosphine) H2-evolution catalyst (NiP) enabled the production of H2 with concomitant selective oxidation of benzylic alcohols to aldehydes in high yield under purely aqueous conditions, at room temperature and ambient pressure. This one-pot system maintained its activity over 24 h, generating products in 1:1 stoichiometry, separated in the gas and solution phases. The NCNCNx–NiP system showed an activity of 763 μmol (g CNx)−1 h–1 toward H2 and aldehyde production, a Ni-based turnover frequency of 76 h–1, and an external quantum efficiency of 15% (λ = 360 ± 10 nm). This precious metal-free and nontoxic photocatalytic system displays better performance than an analogous system containing platinum instead of NiP. Transient absorption spectroscopy revealed that the photoactivity of NCNCNx is due to efficient substrate oxidation of the material, which outweighs possible charge recombination compared to the nonfunctionalized melon-type carbon nitride. Photoexcited NCNCNx in the presence of an organic substrate can accumulate ultralong-lived “trapped electrons”, which allow for fuel generation in the dark. The artificial photosynthetic system thereby catalyzes a closed redox cycle showing 100% atom economy and generates two value-added products, a solar chemical, and solar fuel. PMID:27337491

  12. Crystalline titanate catalyst supports

    DOEpatents

    Anthony, Rayford G.; Dosch, Robert G.

    1993-01-01

    A series of new crystalline titanates (CT) are shown to have considerable potential as catalyst supports. For Pd supported catalyst, the catalytic activity for pyrene hydrogenation was substantially different depending on the type of CT, and one was substantially more active than Pd on hydrous titanium oxide (HTO). For 1-hexene hydrogenation the activities of the new CTs were approximately the same as for the hydrous metal oxide supports.

  13. Crystalline titanate catalyst supports

    DOEpatents

    Anthony, R.G.; Dosch, R.G.

    1993-01-05

    A series of new crystalline titanates (CT) are shown to have considerable potential as catalyst supports. For Pd supported catalyst, the catalytic activity for pyrene hydrogenation was substantially different depending on the type of CT, and one was substantially more active than Pd on hydrous titanium oxide (HTO). For 1-hexene hydrogenation the activities of the new CTs were approximately the same as for the hydrous metal oxide supports.

  14. Catalytic reforming catalyst

    SciTech Connect

    Buss, W.C.; Kluksdahl, H.E.

    1980-12-09

    An improved catalyst, having a reduced fouling rate when used in a catalytic reforming process, said catalyst comprising platinum disposed on an alumina support wherein the alumina support is obtained by removing water from aluminum hydroxide produced as a by-product from a ziegler higher alcohol synthesis reaction, and wherein the alumina is calcined at a temperature of 1100-1400/sup 0/F so as to have a surface area of 165 to 215 square meters per gram.

  15. Catalysts from synthetic genetic polymers

    PubMed Central

    Taylor, Alexander I.; Pinheiro, Vitor B.; Smola, Matthew J.; Morgunov, Alexey S.; Peak-Chew, Sew; Cozens, Christopher; Weeks, Kevin M.; Herdewijn, Piet; Holliger, Philipp

    2014-01-01

    The emergence of catalysis in early genetic polymers like RNA is considered a key transition in the origin of life1, predating the appearance of protein enzymes. DNA also demonstrates the capacity to fold into three-dimensional structures and form catalysts in vitro2. However, to what degree these natural biopolymers comprise functionally privileged chemical scaffolds3 for folding or the evolution of catalysis is not known. The ability of synthetic genetic polymers (XNAs) with alternative backbone chemistries not found in nature to fold into defined structures and bind ligands4 raises the possibility that these too might be capable of forming catalysts (XNAzymes). Here we report the discovery of such XNAzymes, elaborated in four different chemistries (ANA (arabino nucleic acids)5, FANA (2′-fluoroarabino nucleic acids)6, HNA (hexitol nucleic acids) and CeNA (cyclohexene nucleic acids)7 directly from random XNA oligomer pools, exhibiting in trans RNA endonuclease and ligase activities. We also describe an XNA-XNA ligase metalloenzyme in the FANA framework, establishing catalysis in an entirely synthetic system and enabling the synthesis of FANA oligomers and an active RNA endonuclease FANAzyme from its constituent parts. These results extend catalysis beyond biopolymers and establish technologies for the discovery of catalysts in a wide range of polymer scaffolds not found in nature8. Evolution of catalysis independent of any natural polymer has implications for the definition of chemical boundary conditions for the emergence of life on earth and elsewhere in the universe9. PMID:25470036

  16. Catalysts from synthetic genetic polymers.

    PubMed

    Taylor, Alexander I; Pinheiro, Vitor B; Smola, Matthew J; Morgunov, Alexey S; Peak-Chew, Sew; Cozens, Christopher; Weeks, Kevin M; Herdewijn, Piet; Holliger, Philipp

    2015-02-19

    The emergence of catalysis in early genetic polymers such as RNA is considered a key transition in the origin of life, pre-dating the appearance of protein enzymes. DNA also demonstrates the capacity to fold into three-dimensional structures and form catalysts in vitro. However, to what degree these natural biopolymers comprise functionally privileged chemical scaffolds for folding or the evolution of catalysis is not known. The ability of synthetic genetic polymers (XNAs) with alternative backbone chemistries not found in nature to fold into defined structures and bind ligands raises the possibility that these too might be capable of forming catalysts (XNAzymes). Here we report the discovery of such XNAzymes, elaborated in four different chemistries (arabino nucleic acids, ANA; 2'-fluoroarabino nucleic acids, FANA; hexitol nucleic acids, HNA; and cyclohexene nucleic acids, CeNA) directly from random XNA oligomer pools, exhibiting in trans RNA endonuclease and ligase activities. We also describe an XNA-XNA ligase metalloenzyme in the FANA framework, establishing catalysis in an entirely synthetic system and enabling the synthesis of FANA oligomers and an active RNA endonuclease FANAzyme from its constituent parts. These results extend catalysis beyond biopolymers and establish technologies for the discovery of catalysts in a wide range of polymer scaffolds not found in nature. Evolution of catalysis independent of any natural polymer has implications for the definition of chemical boundary conditions for the emergence of life on Earth and elsewhere in the Universe.

  17. Two-beam Laser Brazing of Thin Sheet Steel for Automotive Industry Using Cu-base Filler Material

    NASA Astrophysics Data System (ADS)

    Mittelstädt, C.; Seefeld, T.; Reitemeyer, D.; Vollertsen, F.

    This work shows the potential of two-beam laser brazing for joining both Zn-coated steel and 22MnB5. Brazing of Zn-coated steel sheets using Cu-Si filler wire is already state of the art in car manufacturing. New press-hardened steels like 22MnB5 are more and more used in automotive industry, offering high potential to save costs and improve structural properties (reduced weight / higher stiffness). However, for joining of these ultra-high strength steels investigations are mandatory. In this paper, a novel approach using a two-beam laser brazing process and Cu-base filler material is presented. The use of Cu-base filler material leads to a reduced heat input, compared to currently applied welding processes, which may result in benefits concerning distortion, post processing and tensile strength of the joint. Reliable processing at desired high speeds is attained by means of laser-preheating. High feed rates prevent significant diffusion of copper into the base material.

  18. Colloidal chemically fabricated ZnO : Cu-based photodetector with extended UV-visible detection waveband

    NASA Astrophysics Data System (ADS)

    Hu, Liang; Zhu, Liping; He, Haiping; Guo, Yanming; Pan, Guoyao; Jiang, Jie; Jin, Yizheng; Sun, Luwei; Ye, Zhizhen

    2013-09-01

    Polycrystalline ZnO : Cu-based film photodetectors with extended detection waveband (UV and visible light) were fabricated using facile colloidal chemistry and a post-annealing process. The obtained detectors are highly sensitive to visible light and can realize the response switch between UV and visible light. A native and extrinsic trap cooperatively controlled space charge limited (SCL) transport mechanism is proposed to understand this complex photoconduction behaviour.Polycrystalline ZnO : Cu-based film photodetectors with extended detection waveband (UV and visible light) were fabricated using facile colloidal chemistry and a post-annealing process. The obtained detectors are highly sensitive to visible light and can realize the response switch between UV and visible light. A native and extrinsic trap cooperatively controlled space charge limited (SCL) transport mechanism is proposed to understand this complex photoconduction behaviour. Electronic supplementary information (ESI) available: TEM image of Cu-doped ZnO nanocrystals, dark current comparison of all doped samples including pure ZnO, and I-V characteristics of pure ZnO film. See DOI: 10.1039/c3nr01979a

  19. Characterization of three-way automotive catalysts

    SciTech Connect

    Kenik, E.A.; More, K.L.; LaBarge, W.

    1997-04-01

    The CRADA between Delphi Automotive Systems (Delphi; formerly General Motors - AC Delco, Systems) and Lockheed Martin Energy Research (LMER) on automotive catalysts was completed at the end of FY96, after a ten month, no-cost extension. The CRADA was aimed at improved performance and lifetime of noble metal based three-way-catalysts (TWC), which are the primary catalytic system for automotive emission control systems. While these TWC can meet the currently required emission standards, higher than optimum noble metal loadings are often required to meet lifetime requirements. In addition, more stringent emission standards will be imposed in the near future, demanding improved performance and service life from these catalysts. Understanding the changes of TWC conversion efficiency with ageing is a critical need in improving these catalysts. Initially in a fresh catalyst, the active material is often distributed on a very fine scale, approaching single atoms or small atomic clusters. As such, a wide range of analytical techniques have been employed to provide high spatial resolution characterization of the evolving state of the catalytic material.

  20. Process and catalyst for carbonylating olefins

    DOEpatents

    Zoeller, J.R.

    1998-06-02

    Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

  1. Process and catalyst for carbonylating olefins

    DOEpatents

    Zoeller, Joseph Robert

    1998-06-02

    Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

  2. Preferential Carbon Monoxide Oxidation over Copper-Based Catalysts under In Situ Ball Milling.

    PubMed

    Eckert, Rene; Felderhoff, Michael; Schüth, Ferdi

    2017-02-20

    In situ ball milling of solid catalysts is a promising yet almost unexplored concept for boosting catalytic performance. The continuous preferential oxidation of CO (CO-PROX) under in situ ball milling of Cu-based catalysts such as Cu/Cr2 O3 is presented. At temperatures as low as -40 °C, considerable activity and more than 95 % selectivity were achieved. A negative apparent activation energy was observed, which is attributed to the mechanically induced generation and subsequent thermal healing of short-lived surface defects. In situ ball milling at sub-zero temperatures resulted in an increase of the CO oxidation rate by roughly 4 orders of magnitude. This drastic and highly selective enhancement of CO oxidation showcases the potential of in situ ball milling in heterogeneous catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    PubMed Central

    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

  4. Transforming the Fight Against Tuberculosis: Targeting Catalysts of Transmission

    PubMed Central

    Dowdy, David W.; Azman, Andrew S.; Kendall, Emily A.; Mathema, Barun

    2014-01-01

    The global tuberculosis control community has committed itself to ambitious 10-year targets. To meet these targets, biomedical advances alone will be insufficient; a more targeted public health tuberculosis strategy is also needed. We highlight the role of “tuberculosis transmission catalysts,” defined as variabilities in human behavior, bacillary properties, and host physiology that fuel the propagation of active tuberculosis at the local level. These catalysts can be categorized as factors that increase contact rates, infectiousness, or host susceptibility. Different catalysts predominate in different epidemiological and sociopolitical settings, and public health approaches are likely to succeed only if they are tailored to target the major catalysts driving transmission in the corresponding community. We argue that global tuberculosis policy should move from a country-level focus to a strategy that prioritizes collection of data on key transmission catalysts at the local level followed by deployment of “catalyst-targeted” interventions, supported by strengthened health systems. PMID:24982034

  5. Catalyst Additives to Enhance Mercury Oxidation and Capture

    SciTech Connect

    Thomas K. Gale

    2005-12-31

    Preliminary research has shown that SCR catalysts employed for nitrogen-oxide reduction can effectively oxidize mercury. Three different SCR catalysts are currently being studied in this project--honeycomb-type, plate-type, and a hybrid-type catalyst. The catalysts were manufactured and supplied by Cormetech Inc., Hitachi America Ltd., and Haldor-Topsoe Inc., respectively. Parametric testing was performed to investigate the contribution of flue-gas chemistry on mercury oxidation via SCR catalysts. Future work to characterize flue gas simulations typically derived from low and high sulfur bituminous coal are being performed in a stepwise manner, to avoid the constant interruptions in testing that occur when leaks in the system are generated during temperature transitions. Specifically, chlorine concentration vs. mercury oxidation correlations will be developed for each catalyst. The contributions of temperature are also being investigated. SO2 oxidation is also being investigated for each test condition.

  6. High-quality bio-oil from one-pot catalytic hydrocracking of kraft lignin over supported noble metal catalysts in isopropanol system.

    PubMed

    Yang, Jing; Zhao, Liang; Liu, Shaotong; Wang, Yuanyuan; Dai, Liyi

    2016-07-01

    Catalytic hydrocracking of kraft lignin was carried out in isopropanol system and an orthogonal array design (OAD) was employed to optimize the experimental conditions. GC-MS/FID, elemental analysis, GPC and (1)H-(13)C HSQC NMR were carried out for entire investigation of the liquid products. The results indicated that the hydrocracking process was thermally controlled and catalysts showed significant influences on the product distributions. Comparing with Pd/C, Pt/C and Ru/C, Rh/C inhibited the self-condensation of isopropanol and reduced the formation of oxygenic-chain compounds. The excellent catalytic activity for phenols conversion was obtained over Rh/C. The routes of oxygenic-chain compounds formation and phenol conversion were proposed in detail. The least oxygenic-chain compounds formation, the highest phenols conversion (93.4%), the lowest O/C ratio (0.094) and the highest HHV (37.969MJ/kg) provided the possibility of the high quality bio-oil obtained over Rh/C in isopropanol medium. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Magnetic and dendritic catalysts.

    PubMed

    Wang, Dong; Deraedt, Christophe; Ruiz, Jaime; Astruc, Didier

    2015-07-21

    The recovery and reuse of catalysts is a major challenge in the development of sustainable chemical processes. Two methods at the frontier between homogeneous and heterogeneous catalysis have recently emerged for addressing this problem: loading the catalyst onto a dendrimer or onto a magnetic nanoparticle. In this Account, we describe representative examples of these two methods, primarily from our research group, and compare them. We then describe new chemistry that combines the benefits of these two methods of catalysis. Classic dendritic catalysis has involved either attaching the catalyst covalently at the branch termini or within the dendrimer core. We have used chelating pyridyltriazole ligands to insolubilize catalysts at the termini of dendrimers, providing an efficient, recyclable heterogeneous catalysts. With the addition of dendritic unimolecular micelles olefin metathesis reactions catalyzed by commercial Grubbs-type ruthenium-benzylidene complexes in water required unusually low amounts of catalyst. When such dendritic micelles include intradendritic ligands, both the micellar effect and ligand acceleration promote faster catalysis in water. With these types of catalysts, we could carry out azide alkyne cycloaddition ("click") chemistry with only ppm amounts of CuSO4·5H2O and sodium ascorbate under ambient conditions. Alternatively we can attach catalysts to the surface of superparamagnetic iron oxide nanoparticles (SPIONs), essentially magnetite (Fe3O4) or maghemite (γ-Fe2O3), offering the opportunity to recover the catalysts using magnets. Taking advantage of the merits of both of these strategies, we and others have developed a new generation of recyclable catalysts: dendritic magnetically recoverable catalysts. In particular, some of our catalysts with a γ-Fe2O3@SiO2 core and 1,2,3-triazole tethers and loaded with Pd nanoparticles generate strong positive dendritic effects with respect to ligand loading, catalyst loading, catalytic activity and

  8. Revisiting the behaviour of BiVO4 as a carbon dioxide reduction photo-catalyst.

    PubMed

    Sommers, Jacob M; Alderman, Nicholas P; Viasus, Camilo J; Gambarotta, Sandro

    2017-05-16

    Bismuth vanadate is a widely known photocatalyst for the hydro-reduction of CO2. In spite of the great appeal of such a catalytic system, problems arise due to deactivation of the catalyst with consequent low reaction yield. We have investigated the catalyst behavior during methanol production and have found that the catalyst irreversibly loses vanadium from the structure whilst depositing bismuth oxides on the surface of the catalyst. While catalyst activity can be restored upon heating, leaching of vanadium, leading in long term to catalyst decomposition, is unavoidable and irreversible.

  9. Characterisation of gold catalysts.

    PubMed

    Villa, Alberto; Dimitratos, Nikolaos; Chan-Thaw, Carine E; Hammond, Ceri; Veith, Gabriel M; Wang, Di; Manzoli, Maela; Prati, Laura; Hutchings, Graham J

    2016-09-21

    Au-based catalysts have established a new important field of catalysis, revealing specific properties in terms of both high activity and selectivity for many reactions. However, the correlation between the morphology and the activity of the catalyst is not always clear although much effort has been addressed to this task. To some extent the problem relates to the complexity of the characterisation techniques that can be applied to Au catalyst and the broad range of ways in which they can be prepared. Indeed, in many reports only a few characterization techniques have been used to investigate the potential nature of the active sites. The aim of this review is to provide a critical description of the techniques that are most commonly used as well as the more advanced characterization techniques available for this task. The techniques that we discuss are (i) transmission electron microscopy methods, (ii) X-ray spectroscopy techniques, (iii) vibrational spectroscopy techniques and (iv) chemisorption methods. The description is coupled with developing an understanding of a number of preparation methods. In the final section the example of the supported AuPd alloy catalyst is discussed to show how the techniques can gain an understanding of an active oxidation catalyst.

  10. Cobalt Fischer-Tropsch catalysts having improved selectivity

    DOEpatents

    Miller, James G.; Rabo, Jule A.

    1989-01-01

    A cobalt Fischer-Tropsch catalyst having an improved steam treated, acid extracted LZ-210 support is taught. The new catalyst system demonstrates improved product selectivity at Fischer-Tropsch reaction conditions evidenced by lower methane production, higher C.sub.5.sup.+ yield and increased olefin production.

  11. The Information Ecology of Personal Health Record Systems: Secure Messaging as Catalyst and Its Evolving Impact on Use and Consequences

    ERIC Educational Resources Information Center

    Nazi, Kim M.

    2012-01-01

    Personal Health Records (PHRs) and PHR systems have been designed as consumer-oriented tools to empower patients and improve health care. Despite significant consumer interest and anticipated benefits, adoption remains low. Understanding the consumer perspective is necessary, but insufficient by itself. Consumer PHR use also has broad implications…

  12. The Information Ecology of Personal Health Record Systems: Secure Messaging as Catalyst and Its Evolving Impact on Use and Consequences

    ERIC Educational Resources Information Center

    Nazi, Kim M.

    2012-01-01

    Personal Health Records (PHRs) and PHR systems have been designed as consumer-oriented tools to empower patients and improve health care. Despite significant consumer interest and anticipated benefits, adoption remains low. Understanding the consumer perspective is necessary, but insufficient by itself. Consumer PHR use also has broad implications…

  13. CERES AuTomAted job Loading SYSTem (CATALYST): An automated workflow manager for satellite data production

    NASA Astrophysics Data System (ADS)

    Gleason, J. L.; Hillyer, T. N.; Wilkins, J.

    2012-12-01

    The CERES Science Team integrates data from 5 CERES instruments onboard the Terra, Aqua and NPP missions. The processing chain fuses CERES observations with data from 19 other unique sources. The addition of CERES Flight Model 5 (FM5) onboard NPP, coupled with ground processing system upgrades further emphasizes the need for an automated job-submission utility to manage multiple processing streams concurrently. The operator-driven, legacy-processing approach relied on manually staging data from magnetic tape to limited spinning disk attached to a shared memory architecture system. The migration of CERES production code to a distributed, cluster computing environment with approximately one petabyte of spinning disk containing all precursor input data products facilitates the development of a CERES-specific, automated workflow manager. In the cluster environment, I/O is the primary system resource in contention across jobs. Therefore, system load can be maximized with a throttling workload manager. This poster discusses a Java and Perl implementation of an automated job management tool tailored for CERES processing.

  14. Chemical interactions in multimetal/zeolite catalysts

    SciTech Connect

    Sachtler, W.M.H.

    1992-12-21

    Research is proposed on two groups of zeolite based catalysts that contain two transition elements. In one group both metals are fully reduced, in the other group one element is left as a positive ion; it can act as a chemical anchor'', or as a catalyst promoter for the reduced metal. The objective is to explore the potential of such materials for designing superior catalysts for synthesis and conversion of hydrocarbons and other energy carriers. ENDOR, EXAFS, CO-FTIR and TPD will be used to identify the interaction of Mn[sup 2+] ions with Rh[sub n] particles in the same zeolite cage. EXAFS at the Kedge of Fe and Pd, FTIR and Moessbauer spectroscopy will be used to characterize Fe ions and alloyed Fe atoms in PdFe/NaHY. The catalysts will be probed with CO hydrogenation and conversion of hydrocarbons. Methods Which proved successful in our study of Y supported bimetal systems will be applied to identify the state of Pt and Cu in ZSM-5, a catalyst system holding large promise for NO abatement, even in the presence of oxygen.

  15. From surface-inspired oxovanadium silsesquioxane models to active catalysts for the oxidation of alcohols with O(2)-the cinnamic acid/metavanadate system.

    PubMed

    Ohde, Christian; Limberg, Christian

    2010-06-18

    Silsesquioxane dioxovanadate(V) complexes were investigated with respect to their potential as a catalyst for the oxidative dehydrogenation of alcohols with O(2) as an oxidant. The turnover frequencies determined were comparatively low, but during the oxidation of cinnamic alcohol an increase in activity was observed in the course of the process, which was inspected more closely. It turned out that during the oxidation of cinnamic alcohol, not only was the aldehyde formed but also cinnamic acid, which in turn reacts with the silsesquioxane complex employed to give NBu(4)[O(2)V(O(2)CC(2)H(2)Ph)(2)], which can also be obtained from NBu(4)VO(3) and cinnamic acid and represents a far more active catalyst, not only for cinnamic alcohol but also for other activated alcohols and hydrocarbons. The rate-determining step of the conversion corresponds to an hydrogen-atom abstraction from the C-H units, as shown by the determination of the kinetic isotope effect in case of 9-hydroxyfluorene, and the reoxidation of the reduced catalyst proceeds via a peroxo intermediate, which is also capable of oxidizing one alcohol equivalent. Furthermore the influence of the organic residues at the carboxylate ligands on the catalyst performance was investigated, which showed that the activity increases with decreasing pK(s) value. Moreover, it was found that during the oxidation the catalyst slowly decomposes, but can be regenerated by addition of excessive carboxylic acid.

  16. Supported organoiridium catalysts for alkane dehydrogenation

    SciTech Connect

    Baker, R. Thomas; Sattelberger, Alfred P.; Li, Hongbo

    2013-09-03

    Solid supported organoiridium catalysts, a process for preparing such solid supported organoiridium catalysts, and the use of such solid supported organoiridium catalysts in dehydrogenation reactions of alkanes is provided. The catalysts can be easily recovered and recycled.

  17. In –Situ Spectroscopic Investigation of Immobilized Organometallic Catalysts

    SciTech Connect

    Davis, Robert, J.

    2007-11-14

    Immobilized organometallic catalysts, in principle, can give high rates and selectivities like homogeneous catalysts with the ease of separation enjoyed by heterogeneous catalysts. However, the science of immobilized organometallics has not been developed because the field lies at the interface between the homogeneous and heterogeneous catalysis communities. By assembling an interdisciplinary research team that can probe all aspects of immobilized organometallic catalyst design, the entire reacting system can be considered, where the transition metal complex, the complex-support interface and the properties of the support can all be considered simultaneously from both experimental and theoretical points of view. Researchers at Georgia Tech and the University of Virginia are studying the fundamental principles that can be used to understand and design future classes of immobilized organometallic catalysts. In the framework of the overall collaborative project with Georgia Tech, our work focused on (a) the X-ray absorption spectroscopy of an immobilized Pd-SCS-O complex (b) the mode of metal leaching from supported Pd catalysts during Heck catalysis and (c) the mode of deactivation of Jacobsen’s Co-salen catalysts during the hydrolytic kinetic resolution of terminal epoxides. Catalysts containing supported Pd pincer complexes, functionalized supports containing mercapto and amine groups, and oligomeric Co-salen catalysts were synthesized at Georgia Tech and sent to the University of Virginia. Incorporation of Pd onto several different kinds of supports (silica, mercapto-functionalized silica, zeolite Y) was performed at the University of Virginia.

  18. A catalyst for system change: a case study of child health network formation, evolution and sustainability in Canada.

    PubMed

    McPherson, Charmaine; Ploeg, Jenny; Edwards, Nancy; Ciliska, Donna; Sword, Wendy

    2017-02-01

    The purpose of this study was to examine key processes and supportive and inhibiting factors involved in the development, evolution, and sustainability of a child health network in rural Canada. This study contributes to a relatively new research agenda aimed at understanding inter-organizational and cross-sectoral health networks. These networks encourage collaboration focusing on complex issues impacting health - issues that individual agencies cannot effectively address alone. This paper presents an overview of the study findings. An explanatory qualitative case study approach examined the Network's 13-year lifespan. Data sources were documents and Network members, including regional and 71 provincial senior managers from 11 child and youth service sectors. Data were collected through 34 individual interviews and a review of 127 documents. Interview data were analyzed using framework analysis methods; Prior's approach guided document analysis. Three themes related to network development, evolution and sustainability were identified: (a) Network relationships as system triggers, (b) Network-mediated system responsiveness, and (c) Network practice as political. Study findings have important implications for network organizational development, collaborative practice, interprofessional education, public policy, and public system responsiveness research. Findings suggest it is important to explicitly focus on relationships and multi-level socio-political contexts, such as supportive policy environments, in understanding health networks. The dynamic interplay among the Network members; central supportive and inhibiting factors; and micro-, meso-, and macro-organizational contexts was identified.

  19. Catalyst reforming process

    SciTech Connect

    Swan, G.A. III

    1989-05-23

    This patent describes a process for catalytically reforming a gasoline boiling range naphtha, with hydrogen, in a semi-regenerative or semi-cyclic reforming process unit comprised of serially connected reactors, inclusive of a lead reactor and one or more downstream reactors, the last of which is the tail reactor, each of which contains a halogenated reforming catalyst comprised of a halide, a Group VIII noble metal, and an inorganic oxide support, the improvement which comprises continuously injecting into each downstream reactor a mixture of water and halide at a water to halide ratio from about 20:1 to about 60:1 wherein the specific ratio of water to halide for each individual downstream reactor is chosen so as to maintain the level of halide on catalyst in each downstream reactor from about 0.5 to 1.5 wt. % based on the total weight of the catalyst.

  20. Oxide Nanocrystal Model Catalysts.

    PubMed

    Huang, Weixin

    2016-03-15

    Model catalysts with uniform and well-defined surface structures have been extensively employed to explore structure-property relationships of powder catalysts. Traditional oxide model catalysts are based on oxide single crystals and single crystal thin films, and the surface chemistry and catalysis are studied under ultrahigh-vacuum conditions. However, the acquired fundamental understandings often suffer from the "materials gap" and "pressure gap" when they are extended to the real world of powder catalysts working at atmospheric or higher pressures. Recent advances in colloidal synthesis have realized controlled synthesis of catalytic oxide nanocrystals with uniform and well-defined morphologies. These oxide nanocrystals consist of a novel type of oxide model catalyst whose surface chemistry and catalysis can be studied under the same conditions as working oxide catalysts. In this Account, the emerging concept of oxide nanocrystal model catalysts is demonstrated using our investigations of surface chemistry and catalysis of uniform and well-defined cuprous oxide nanocrystals and ceria nanocrystals. Cu2O cubes enclosed with the {100} crystal planes, Cu2O octahedra enclosed with the {111} crystal planes, and Cu2O rhombic dodecahedra enclosed with the {110} crystal planes exhibit distinct morphology-dependent surface reactivities and catalytic properties that can be well correlated with the surface compositions and structures of exposed crystal planes. Among these types of Cu2O nanocrystals, the octahedra are most reactive and catalytically active due to the presence of coordination-unsaturated (1-fold-coordinated) Cu on the exposed {111} crystal planes. The crystal-plane-controlled surface restructuring and catalytic activity of Cu2O nanocrystals were observed in CO oxidation with excess oxygen. In the propylene oxidation reaction with O2, 1-fold-coordinated Cu on Cu2O(111), 3-fold-coordinated O on Cu2O(110), and 2-fold-coordinated O on Cu2O(100) were identified

  1. Partial oxidation catalyst

    DOEpatents

    Krumpelt, Michael; Ahmed, Shabbir; Kumar, Romesh; Doshi, Rajiv

    2000-01-01

    A two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion. The dehydrogenation portion is a group VIII metal and the oxide-ion conducting portion is selected from a ceramic oxide crystallizing in the fluorite or perovskite structure. There is also disclosed a method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

  2. Catalyst, method of making, and reactions using the catalyst

    DOEpatents

    Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Gao, Yufei [Kennewick, WA

    2009-03-03

    The present invention includes a catalyst having a layered structure with, (1) a porous support, (2) a buffer layer, (3) an interfacial layer, and optionally (4) a catalyst layer. The invention also provides a process in which a reactant is converted to a product by passing through a reaction chamber containing the catalyst.

  3. Catalyst, Method Of Making, And Reactions Using The Catalyst

    DOEpatents

    Tonkovich, Anna Lee Y.; Wang, Yong; Gao, Yufei

    2004-07-13

    The present invention includes a catalyst having a layered structure with, (1) a porous support, (2) a buffer layer, (3) an interfacial layer, and optionally (4) a catalyst layer. The invention also provides a process in which a reactant is converted to a product by passing through a reaction chamber containing the catalyst.

  4. Catalyst, method of making, and reactions using the catalyst

    DOEpatents

    Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Gao, Yufei [Kennewick, WA

    2002-08-27

    The present invention includes a catalyst having a layered structure with, (1) a porous support, (2) a buffer layer, (3) an interfacial layer, and optionally (4) a catalyst layer. The invention also provides a process in which a reactant is converted to a product by passing through a reaction chamber containing the catalyst.

  5. Enhanced photovoltaic performance of Cu-based metal-organic frameworks sensitized solar cell by addition of carbon nanotubes

    PubMed Central

    Lee, Deok Yeon; Shin, Chan Yong; Yoon, Seog Joon; Lee, Haw Young; Lee, Wonjoo; Shrestha, Nabeen K.; Lee, Joong Kee; Han, Sung-Hwan

    2014-01-01

    In the present work, TiO2 nanoparticle and multi-walled carbon nanotubes composite powder is prepared hydrothermally. After doctor blading the paste from composite powder, the resulted composite film is sensitized with Cu-based metal-organic frameworks using a layer-by-layer deposition technique and the film is characterized using FE-SEM, EDX, XRD, UV/Visible spectrophotometry and photoluminescence spectroscopy. The influence of the carbon nanotubes in photovoltaic performance is studied by constructing a Grätzel cell with I3−/I− redox couple containing electrolyte. The results demonstrate that the introduction of carbon nanotubes accelerates the electron transfer, and thereby enhances the photovoltaic performance of the cell with a nearly 60% increment in power conversion efficiency. PMID:24488110

  6. Secret Lives of Catalysts Revealed

    SciTech Connect

    Salmeron, Miquel; Somorjai, Gabor

    2008-01-01

    Miquel Salmeron and Gabor Somorjai of Berkeley Lab's Materials Sciences Division discuss the first-ever glimpse of nanoscale catalysts in action. More information: http://newscenter.lbl.gov/press-releases/2008/10/21/catalysts/

  7. Efficient electrochemical water oxidation in neutral and near-neutral systems with a nanoscale silver-oxide catalyst.

    PubMed

    Joya, Khurram S; Ahmad, Zahoor; Joya, Yasir F; Garcia-Esparza, Angel T; de Groot, Huub J M

    2016-08-11

    In electrocatalytic water splitting systems pursuing for renewable energy using sunlight, developing robust, stable and easily accessible materials operating under mild chemical conditions is pivotal. We present here a unique nanoparticulate type silver-oxide (AgOx-NP) based robust and highly stable electrocatalyst for efficient water oxidation. The AgOx-NP is generated in situ in a HCO3(-)/CO2 system under benign conditions. Micrographs show that they exhibit a nanoscale box type squared nano-bipyramidal configuration. The oxygen generation is initiated at low overpotential, and a sustained O2 evolution current density of >1.1 mA cm(-2) is achieved during prolonged-period water electrolysis. The AgOx-NP electrocatalyst performs exceptionally well in metal-ion free neutral or near-neutral carbonate, phosphate and borate buffers relative to recently reported Co-oxide and Ni-oxide based heterogeneous electrocatalysts, which are unstable in metal-ion free electrolytes and tend to deactivate with time and lose catalytic performance during long-term experimental tests.

  8. Process of making supported catalyst

    DOEpatents

    Schwarz, James A.; Subramanian, Somasundaram

    1992-01-01

    Oxide supported metal catalysts have an additional metal present in intimate association with the metal catalyst to enhance catalytic activity. In a preferred mode, iridium or another Group VIII metal catalyst is supported on a titania, alumina, tungsten oxide, silica, or composite oxide support. Aluminum ions are readsorbed onto the support and catalyst, and reduced during calcination. The aluminum can be added as aluminum nitrate to the iridium impregnate solution, e.g. chloroiridic acid.

  9. A General, Efficient and Functional-Group-Tolerant Catalyst System for the Palladium-Catalyzed Thioetherification of Aryl Bromides and Iodides

    PubMed Central

    Fernández-Rodríguez, Manuel A.; Hartwig, John F.

    2010-01-01

    The cross-coupling reaction of aryl bromides and iodides with aliphatic and aromatic thiols catalyzed by palladium complexes of the bisphosphine ligand CyPF-tBu (1) is reported. Reactions occur in excellent yields, broad scope, high tolerance of functional groups and with turnover numbers that exceed those of previous catalysts by two or three orders of magnitude. These couplings of bromo- and iodoarenes are more efficient than the corresponding reactions of chloroarenes and could be conducted with less catalyst loading and/or milder reaction conditions. Consequently, limitations regarding scope and functional group tolerance previously reported in the coupling of aryl chlorides are now overcome. PMID:19154131

  10. A general, efficient, and functional-group-tolerant catalyst system for the palladium-catalyzed thioetherification of aryl bromides and iodides.

    PubMed

    Fernández-Rodríguez, Manuel A; Hartwig, John F

    2009-02-20

    The cross-coupling reaction of aryl bromides and iodides with aliphatic and aromatic thiols catalyzed by palladium complexes of the bisphosphine ligand CyPF-tBu (1) is reported. Reactions occur in excellent yields, broad scope, high tolerance of functional groups, and with turnover numbers that exceed those of previous catalysts by 2 or 3 orders of magnitude. These couplings of bromo- and iodoarenes are more efficient than the corresponding reactions of chloroarenes and could be conducted with less catalyst loading and/or milder reaction conditions. Consequently, limitations regarding scope and functional group tolerance previously reported in the coupling of aryl chlorides are now overcome.

  11. A simple, efficient and environmentally benign synthetic protocol for the synthesis of spirooxindoles using choline chloride-oxalic acid eutectic mixture as catalyst/solvent system.

    PubMed

    Khandelwal, Sarita; Rajawat, Anshu; Tailor, Yogesh Kumar; Kumar, Mahendra

    2014-01-01

    An efficient and environmentally benign domino protocol has been presented for the synthesis of structurally diverse spirooxindoles spiroannulated with pyranopyridopyrimidines, indenopyridopyrimidines, and chromenopyridopyrimidines involving three-component reaction of aminouracils, isatins and cyclic carbonyl compounds in deep eutectic solvent (choline chloride-oxalic acid: 1:1) which acts as efficient catalyst and environmentally benign reaction medium. The present protocol offers several advantages such as operational simplicity with easy workup, shorter reaction times excellent yields with superior atom economy and environmentally benign reaction conditions with the use of cost-effective, recyclable, non-toxic and bio-degradable DES as catalyst/solvent.

  12. Optimization of furfural production from D-xylose with formic acid as catalyst in a reactive extraction system.

    PubMed

    Yang, Wandian; Li, Pingli; Bo, Dechen; Chang, Heying; Wang, Xiaowei; Zhu, Tao

    2013-04-01

    Furfural is one of the most promising platform chemicals derived from biomass. In this study, response surface methodology (RSM) was utilized to determine four important parameters including reaction temperature (170-210°C), formic acid concentration (5-25 g/L), o-nitrotoluene volume percentage (20-80 vt.%), and residence time (40-200 min). The maximum furfural yield of 74% and selectivity of 86% were achieved at 190°C for 20 g/L formic acid concentration and 75 vt.% o-nitrotoluene by 75 min. The high boiling solvent, o-nitrotoluene, was recommended as extraction solvent in a reactive extraction system to obtain high furfural yield and reduce furfural-solvent separation costs. Although the addition of halides to the xylose solutions enhanced the furfural yield and selectivity, the concentration of halides was not an important factor on the furfural yield and selectivity. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Steric hindrance in a MnSalen expoxidation catalyst

    SciTech Connect

    Jun, K.W.; Wilson, R.B. Jr.; Asaro, M.F.

    1995-12-31

    Many transition metal epoxidation catalysts use porphyrin type ligands, as biomimetic models for the well-studied monooxygenase, Cyt P-450. Recently, non-porphyrin systems based on the Salen ligand have received attention, because high e.e. values are reported using chiral Salen ligands. These systems have yet to be rendered generally practical, however, because the catalyst lifetimes are very short and the turnover numbers low. The original Mn(III) Salen epoxidation catalysts became inactive within 1 h, showing only 5 to 10 turnovers. The modified, chiral Mn(III) Salen complexes show similarly low turnovers. The principal decomposition routes of the MnSalen epoxidation catalysts are not clear. The purpose of the present study is to determine whether incorporation of extreme steric hindrance into the Salen ligand could be used to increase the lifetime of the Mn(III) Salen epoxidation catalysts.

  14. Nuclearity and cooperativity effects in binuclear catalysts and cocatalysts for olefin polymerization.

    PubMed

    Li, Hongbo; Marks, Tobin J

    2006-10-17

    A series of bimetallic organo-group 4 "constrained geometry" catalysts and binuclear bisborane and bisborate cocatalysts have been synthesized to probe catalyst center-catalyst center cooperativity effects on olefin enchainment in homogenous olefin polymerization and copolymerization processes. Significant nuclearity effects are found versus mononuclear controls, and the effect can be correlated with metal-metal approach distances and ion pairing effects. Novel polymer structures can be obtained by using such binuclear catalyst/cocatalyst systems.

  15. Catalyst cartridge for carbon dioxide reduction unit

    NASA Technical Reports Server (NTRS)

    Holmes, R. F. (Inventor)

    1973-01-01

    A catalyst cartridge, for use in a carbon dioxide reducing apparatus in a life support system for space vehicles, is described. The catalyst cartridge includes an inner perforated metal wall, an outer perforated wall space outwardly from the inner wall, a base plate closing one end of the cartridge, and a cover plate closing the other end of the cartridge. The cover plate has a central aperture through which a supply line with a heater feeds a gaseous reaction mixture comprising hydrogen and carbon dioxide at a temperature from about 1000 to about 1400 F. The outer surfaces of the internal wall and the inner surfaces of the outer wall are lined with a ceramic fiber batting material of sufficient thickness to prevent carbon formed in the reaction from passing through it. The portion of the surfaces of the base and cover plates defined within the inner and outer walls are also lined with ceramic batting. The heated reaction mixture passes outwardly through the inner perforated wall and ceramic batting and over the catalyst. The solid carbon product formes is retained within the enclosure containing the catalyst. The solid carbon product formed is retained within the enclosure containing the catalyst. The water vapor and unreacted carbon dioxide and any intermediate products pass through the perforations of the outer wall.

  16. Methane oxidation over dual redox catalysts

    SciTech Connect

    Klier, K.; Herman, R.G.

    1992-01-01

    The objectives of this research were to achieve and understand the partial oxidation of methane to oxygenates and C{sub 2} hydrocarbons over dual redox catalysts. The catalysts were based on oxidic materials that will exhibit structural and thermal stability for long reactor lifetimes. A continuous flow reactor system with oxygen or air as the oxidizing gas, rather than nitrous oxide, was utilized over a wide range of temperatures ({le}1000{degrees}C), with variable gas hourly space velocity, in order to maximize the space time yields of the desired products. All of the investigated processes are catalytic and are aimed at minimizing gas phase reactions.

  17. Methane oxidation over dual redox catalysts

    SciTech Connect

    Klier, K.; Herman, R.G.

    1992-06-01

    The objectives of this research were to achieve and understand the partial oxidation of methane to oxygenates and C{sub 2} hydrocarbons over dual redox catalysts. The catalysts were based on oxidic materials that will exhibit structural and thermal stability for long reactor lifetimes. A continuous flow reactor system with oxygen or air as the oxidizing gas, rather than nitrous oxide, was utilized over a wide range of temperatures ({le}1000{degrees}C), with variable gas hourly space velocity, in order to maximize the space time yields of the desired products. All of the investigated processes are catalytic and are aimed at minimizing gas phase reactions.

  18. Homogeneous catalyst formulations for methanol production

    DOEpatents

    Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

    1991-02-12

    There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.-), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

  19. Homogeneous catalyst formulations for methanol production

    DOEpatents

    Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

    1990-01-01

    There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.13 ), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

  20. Ship-in-a-bottle catalysts

    DOEpatents

    Haw, James F.; Song, Weiguo

    2006-07-18

    In accordance with the present invention there is provided a novel catalyst system in which the catalytic structure is tailormade at the nanometer scale using the invention's novel ship-in-a-bottle synthesis techniques. The invention describes modified forms of solid catalysts for use in heterogeneous catalysis that have a microporous structure defined by nanocages. Examples include zeolites, SAPOs, and analogous materials that have the controlled pore dimensions and hydrothermal stability required for many industrial processes. The invention provides for modification of these catalysts using reagents that are small enough to pass through the windows used to access the cages. The small reagents are then reacted to form larger molecules in the cages.

  1. Catalysts comprising magnesium and a transition metal

    SciTech Connect

    Bujadoux, K.

    1984-10-09

    A catalyst comprising the product obtained by bringing into contact a compound of magnesium comprising at least one species selected from the group consisting of magnesium monohalides (MgX), halo-magnesium hydrides (HMgX) and magnesium hydride (MgH/sub 2/), X being a halogen and the said species MgX or HMgX being obtained by thermal decomposition of a powdery organo-magnesium halide R/sub 1/MgX wherein R/sub 1/ is an organic radical; and at least one halide of a transistion metal selected from the group consisting of titanium and vanadium, the valency of said metal in said halide being lower than or equal to 3, the quantities being such that the atomic ratio of magnesium to said transistion metal is between 1 and 25, and a catalyst system including the catalyst that is suitable for use in the polymerization of olefins and particularly ethylene.

  2. Computational Design of Lignin Depolymerization Catalysts

    SciTech Connect

    Kim, S.; Chmely, S. C.; Sturgeon, M.; Katahira, R.; Paton, R. S.; Beckham, G. T.

    2012-01-01

    Lignin is a major component of plant cell walls that is typically underutilized in selective conversion strategies for renewable fuels and chemicals. The mechanisms by which thermal and catalytic treatments deconstruct lignin remain elusive, for which quantum mechanical calculations can offer fundamental insights. In this work, a computational approach has been used to elucidate the reductive deconstruction pathway of a ruthenium-catalyzed system. Transition states have been computed to determine the rate-limiting steps for a catalyst that cleaves arylether linkages. Our calculations are supported by experimental synthesis and kinetic and thermodynamic measurements of the deconstruction of model lignin dimers by a ruthenium catalyst with the ultimate objective of designing new catalysts to eventually utilize lignin in biorefineries.

  3. Formation of a catalyst for methanol synthesis

    SciTech Connect

    Plyasova, L.M.; Yur`eva, T.M.; Kriger, T.A.

    1995-05-01

    Formation of the structure in a copper-zinc catalyst for methanol synthesis is analyzed at each step of its preparation including hydrogen activation at which catalytically active species are formed. The necessary interaction of the catalyst components in fresh precipitates is provided by formation of mixed copper-zinc hydroxocarbonates. On low-temperature calcination, the interaction is preserved due to the formation of mixed copper-zinc oxides modified by OH{sup -} and CO{sub 3}{sup 2-} anions with copper ions distributed as clusters in a zinc oxide-type structure. The activation with hydrogen results in formation of a proton-stabilized system of zinc oxide with epitaxially bound metallic copper. Both the chemical bond cleavage and spatial phase segregation at any step of the catalyst preparation result in the loss of its catalytic activity.

  4. Synthesis of non-stoichiometric nanocrystalline catalysts

    SciTech Connect

    Tschoepe, A.; Ying, J.Y.

    1995-12-01

    Nanocrystalline catalysts may be synthesized by inert gas condensation method with magnetron sputtering technique. The source material is sputtered in a low Ar pressure, and nanoclusters of similar composition as the source target are collected effectively on a liquid nitrogen cooled modified ground shield. We have generated Ce, La-Ce and Cu-Ce nanoclusters by this approach, and controlled oxidized them to derive non-stoichiometric oxide catalysts. Such novel catalysts are constituted of crystallites < 10 nm, with an ultrahigh surface-to-volume ratio. Multicomponent systems can also be synthesized with excellent homogeneity by this approach, compared to traditional chemical preparation methods. Finally, the significant non-stoichiometry in oxides provides a high concentration of oxygen vacancies and superoxide adsorbed species, which is particularly useful in catalytic redox reactions, such as SO{sub 2} reduction by CO and CO oxidation.

  5. Protein Scaffolding for Small Molecule Catalysts

    SciTech Connect

    Baker, David

    2014-09-14

    We aim to design hybrid catalysts for energy production and storage that combine the high specificity, affinity, and tunability of proteins with the potent chemical reactivities of small organometallic molecules. The widely used Rosetta and RosettaDesign methodologies will be extended to model novel protein / small molecule catalysts in which one or many small molecule active centers are supported and coordinated by protein scaffolding. The promise of such hybrid molecular systems will be demonstrated with the nickel-phosphine hydrogenase of DuBois et. al.We will enhance the hydrogenase activity of the catalyst by designing protein scaffolds that incorporate proton relays and systematically modulate the local environment of the catalyticcenter. In collaboration with DuBois and Shaw, the designs will be experimentally synthesized and characterized.

  6. Reforming with polymetallic catalysts

    SciTech Connect

    Baird, W.C. Jr.

    1988-11-29

    This patent describes a process for catalytically reforming, with hydrogen, a hydrocarbon naphtha feed at reforming conditions, the improvement comprising contacting the naphtha feed, and hydrogen, with a halogenated, supported platinum-rhenium catalyst promoted with iridium agglomerated to exhibit a crystallinity greater than 50 percent, as measured by X-ray.

  7. Zinc sulfide liquefaction catalyst

    DOEpatents

    Garg, Diwakar

    1984-01-01

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

  8. Catalyst, 2000-01.

    ERIC Educational Resources Information Center

    Ryan, Barbara E., Ed.

    2001-01-01

    "Catalyst" is a publication designed to assist higher education in developing alcohol and other drug prevention polices and programs that will foster students' academic and social development and promote campus and community safety. Issue 1 of volume 6 introduces a series of "Presidential Profiles" in which university presidents describe their…

  9. Salesperson, Catalyst, Manager, Leader.

    ERIC Educational Resources Information Center

    Worth, Michael J.; Asp, James W., II

    1996-01-01

    This article examines four roles of the college or university development officer: salesperson (when direct solicitation is seen as the officer's primary role); catalyst (or sales manager, adviser, expert, facilitator); manager (stressing the importance of the overall office functioning); and leader (who exerts a leadership role in the…

  10. Polymerization catalyst, production and use

    SciTech Connect

    Best, S.A.; Etherton, B.P.; Kaus, M.J.

    1989-09-12

    This patent describes a polymerization process. It comprises polymerizing ethylene, alpha-olefins of 3 to 20 carbon atoms or mixtures of ethylene and the alpha-olefins in the presence of a catalyst system. The system comprising: an organo aluminum compound of the formula AIR'''/sub eta/X'''/sub 3-eta/ wherein R''' is hydrogen, hydrocarbyl, or substituted hydrocarbyl having from 1 to 20 carbon atoms, X''' is a halogen and eta is a number from 1 to 3, and a transition metal-containing catalyst component. The component comprising the solid reaction product obtained by treating an inert solid support material in an inert solvent with an organonmetallic compound represented by the formula R/sup 1/MgR/sup 2/ wherein R/sup 1/ and R/sup 2/, which may be the same of different,contain 1 to 20 carbon atoms and are selected from alkyl group, aryl group, cycloalkyl group, aralkyl group, alkadienyl group of group; an alcohol; an acyl halide; a titanium halide; Cl/sub 2/, and prereducing the transition metal-containing product with an aluminum alkyl, with the proviso that the first two ingredients can be added to the inert solid simultaneously, as the reaction product of the first two steps or treatment with step two immediately precedes treatment with step one.

  11. Matchmaking in Catalyst-Transfer Polycondensation: Optimizing Catalysts based on Mechanistic Insight.

    PubMed

    Leone, Amanda K; McNeil, Anne J

    2016-12-20

    Catalyst-transfer polycondensation (CTP) has emerged as a useful living, chain-growth polymerization method for synthesizing conjugated (hetero)arene-based polymers with targetable molecular weights, narrow dispersities, and controllable copolymer sequences-all properties that significantly influence their performance in devices. Over the past decade, several phosphine- and carbene-ligated Ni- and Pd-based precatalysts have been shown to be effective in CTP. One current limitation is that these traditional CTP catalysts lead to nonliving, non-chain-growth behavior when complex monomer scaffolds are utilized. Because these monomers are often found in the highest-performing materials, there is a significant need to identify alternative CTP catalysts. Recent mechanistic insight into CTP has laid the foundation for designing new catalysts to expand the CTP monomer scope. Building off this insight, we have designed and implemented model systems to identify effective catalysts by understanding their underlying mechanistic behaviors and systematically modifying catalyst structures to improve their chain-growth behavior. In this Account, we describe how each catalyst parameter-the ancillary ligand(s), reactive ligand(s), and transition metal-influences CTP. As an example, ancillary ligands often dictate the turnover-limiting step of the catalytic cycle, and perhaps more importantly, they can be used to promote the formation of the key intermediate (a metal-arene associative complex) and its subsequent reactivity. The fidelity of this intermediate is central to the mechanism for the living, chain-growth polymerization. Reactive ligands, on the other hand, can be used to improve catalyst solubility and accelerate initiation. Additional advantages of the reactive ligand include providing access points for postpolymerization modification and synthesizing polymers directly off surfaces. While the most frequently used CTP catalysts contain nickel, palladium-based catalysts

  12. Catalytic Destruction of a Surrogate Organic Hazardous Air Pollutant as a Potential Co-benefit for Coal-fired Selective Catalyst Reduction Systems

    EPA Science Inventory

    Catalytic destruction of benzene (C6H6), a surrogate for organic hazardous air pollutants (HAPs) produced from coal combustion, was investigated using a commercial selective catalytic reduction (SCR) catalyst for evaluating the potential co-benefit of the SCR technology for reduc...

  13. Effect of iron-manganese-sepiolite as heterogeneous Fenton-like catalyst on the performance and microbial community of anaerobic granular sludge treatment system.

    PubMed

    Su, Chengyuan; Li, Weiguang; Chen, Menglin; Huang, Zhi; Wu, Lei

    2016-01-01

    Both short-term and long-term exposure experiments have been carried out to investigate the influence of iron (Fe)-manganese (Mn)-sepiolite, as a heterogeneous Fenton-like catalyst, on the performance and microbial community of anaerobic granular sludge. During the short-term exposure experiments, chemical oxygen demand (COD) removal efficiency decreased from 73.1% to 64.1% with the presence of 100mg/L of catalyst. However, long-term exposure to the catalyst did not significantly affect the COD removal efficiency (81.8%) as compared to the control (83.5%). Meanwhile, the absorption peaks of coenzyme F420 in extracellular polymeric substances (EPS) of sludge samples were remarkable by excitation-emission matrix (EEM) fluorescence spectra. After long-term exposure, the presence of the catalyst increased secretions of EPS from 83.7mg/g VSS to 89.1mg/g VSS. Further investigations with high throughput sequencing indicated that the abundance of Methanosaeta increased from 57.7% to 70.4% after long-term exposure. In bacterial communities, Proteobacteria, Firmicutes, and Synergistetes were predominant.

  14. Catalytic Destruction of a Surrogate Organic Hazardous Air Pollutant as a Potential Co-benefit for Coal-fired Selective Catalyst Reduction Systems

    EPA Science Inventory

    Catalytic destruction of benzene (C6H6), a surrogate for organic hazardous air pollutants (HAPs) produced from coal combustion, was investigated using a commercial selective catalytic reduction (SCR) catalyst for evaluating the potential co-benefit of the SCR technology for reduc...

  15. Hydroprocessing catalyst composition

    SciTech Connect

    Apelian, M.R.; Degnan, T.F. Jr.; Marler, D.O.; Mazzone, D.N.

    1993-07-13

    A bifunctional hydroprocessing catalyst is described which comprises a metal component having hydrogenation/dehydrogenation functionality and a support component comprising an inorganic, non-layered, porous, crystalline phase material having pores with diameters of at least about 13 [angstrom] and exhibiting, after calcination, an X-ray diffraction pattern with at least one peak with a relative intensity of 100 at a d-spacing greater than about 18 [angstrom], the catalyst having a surface area S, where S, expressed in m[sup 2].g[sup [minus]1], is defined by the equation: S[ge]600-13.3X where X is the total metals loading in weight percent and is least 12 weight percent. A second hydroprocessing catalyst is described according to claim 1 in which the crystalline phase has a composition expressed as follows: M[sub n/q](W[sub a]X[sub b]Y[sub c]Z[sub d]O[sub h]) wherein M is one or more ions; n is the charge of the composition excluding M expressed as oxides; q is the weighted molar average valence of M; n/q is the number of moles or mole fraction of M; W is one or more divalent elements; X is one or more trivalent elements; Y is one or more tetravalent elements; Z is one or more pentavalent elements; a, b, c, and d are mole fraction of W, X, Y, and Z, respectively, h is a number of from 1 to 2.5; and (a+b+c+d) = 1. A third hydroprocessing catalyst is described according to claim 1 in which the catalyst is at least one base metal of Group VIA, VIIA or VIIIA of the Periodic Table.

  16. Catalyst support structure, catalyst including the structure, reactor including a catalyst, and methods of forming same

    DOEpatents

    Van Norman, Staci A.; Aston, Victoria J.; Weimer, Alan W.

    2017-05-09

    Structures, catalysts, and reactors suitable for use for a variety of applications, including gas-to-liquid and coal-to-liquid processes and methods of forming the structures, catalysts, and reactors are disclosed. The catalyst material can be deposited onto an inner wall of a microtubular reactor and/or onto porous tungsten support structures using atomic layer deposition techniques.

  17. Molybdenum sulfide/carbide catalysts

    DOEpatents

    Alonso, Gabriel; Chianelli, Russell R.; Fuentes, Sergio; Torres, Brenda

    2007-05-29

    The present invention provides methods of synthesizing molybdenum disulfide (MoS.sub.2) and carbon-containing molybdenum disulfide (MoS.sub.2-xC.sub.x) catalysts that exhibit improved catalytic activity for hydrotreating reactions involving hydrodesulfurization, hydrodenitrogenation, and hydrogenation. The present invention also concerns the resulting catalysts. Furthermore, the invention concerns the promotion of these catalysts with Co, Ni, Fe, and/or Ru sulfides to create catalysts with greater activity, for hydrotreating reactions, than conventional catalysts such as cobalt molybdate on alumina support.

  18. Regeneration of LOHC dehydrogenation catalysts: In-situ IR spectroscopy on single crystals, model catalysts, and real catalysts from UHV to near ambient pressure

    NASA Astrophysics Data System (ADS)

    Amende, Max; Kaftan, Andre; Bachmann, Philipp; Brehmer, Richard; Preuster, Patrick; Koch, Marcus; Wasserscheid, Peter; Libuda, Jörg

    2016-01-01

    The Liquid Organic Hydrogen Carrier (LOHC) concept offers an efficient route to store hydrogen using organic compounds that are reversibly hydrogenated and dehydrogenated. One important challenge towards application of the LOHC technology at a larger scale is to minimize degradation of Pt-based dehydrogenation catalysts during long-term operation. Herein, we investigate the regeneration of Pt/alumina catalysts poisoned by LOHC degradation. We combine ultrahigh vacuum (UHV) studies on Pt(111), investigations on well-defined Pt/Al2O3 model catalysts, and near-ambient pressure (NAP) measurements on real core⿿shell Pt/Al2O3 catalyst pellets. The catalysts were purposely poisoned by reaction with the LOHC perhydro-dibenzyltoluene (H18-MSH) and with dicyclohexylmethane (DCHM) as a simpler model compound. We focus on oxidative regeneration under conditions that may be applied in real dehydrogenation reactors. The degree of poisoning and regeneration under oxidative reaction conditions was quantified using CO as a probe molecule and measured by infrared reflection-absorption spectroscopy (IRAS) and diffuse reflectance Fourier transform IR spectroscopy (DRIFTS) for planar model systems and real catalysts, respectively. We find that regeneration strongly depends on the composition of the catalyst surface. While the clean surface of a poisoned Pt(111) single crystal is fully restored upon thermal treatment in oxygen up to 700 K, contaminated Pt/Al2O3 model catalyst and core⿿shell pellet were only partially restored under the applied reaction conditions. Whereas partial regeneration on facet-like sites on supported catalysts is more facile than on Pt(111), carbonaceous deposits adsorbed at low-coordinated defect sites impede full regeneration of the Pt/Al2O3 catalysts.

  19. Testing zinc chloride as a new catalyst for direct synthesis of cellulose di- and tri-acetate in a solvent free system under microwave irradiation.

    PubMed

    El Nemr, Ahmed; Ragab, Safaa; El Sikaily, Amany

    2016-10-20

    This research demonstrates the effect of ZnCl2 as a catalyst on the esterification of commercial cotton cellulose using acetic anhydride in order to obtain di- and tri-cellulose acetates under microwave irradiation. It was discovered that microwave irradiation significantly increased the yield and reduced the reaction time. It was found that the maximum yield for cellulose triacetates was 95.83% under the reaction conditions that were as follows: 3min reaction time, 200mg of ZnCl2 catalyst and 20ml of Ac2O for 5g cellulose. However, the cellulose acetate obtained in this manner had the highest DS (2.87). The cellulose di-acetate was produced with the maximum yield of 89.97% and with the highest DS (2.69) using 25ml Ac2O, 200mg of ZnCl2 for 5g cellulose and in 3min reaction time. The effect of some factors such as the amount of used catalyst, the quantity of acetic acid anhydride and the reaction time of the esterification process have been investigated. The production of di- and tri-cellulose acetate and the degree of substitution were confirmed using Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR). The thermal stability was investigated using thermo gravimetric analysis (TGA), differential thermal analysis (DTA) and differential scanning calorimetry (DSC). The molecular weight and the degree of polymerization were obtained using Gel Permeation Chromatography (GPC). The analysis confirmed the successful synthesis of di- and tri-cellulose acetate without degradation during the reaction; these results were found to be in contrast to some recent studies. The present study reveals that ZnCl2 is a new catalyst; it is effective as well as inexpensive and is a low toxicity catalyst for usage in cellulose esterification.

  20. Apparatus and Process for Controlled Nanomanufacturing Using Catalyst Retaining Structures

    NASA Technical Reports Server (NTRS)

    Nguyen, Cattien (Inventor)

    2013-01-01

    An apparatus and method for the controlled fabrication of nanostructures using catalyst retaining structures is disclosed. The apparatus includes one or more modified force microscopes having a nanotube attached to the tip portion of the microscopes. An electric current is passed from the nanotube to a catalyst layer of a substrate, thereby causing a localized chemical reaction to occur in a resist layer adjacent the catalyst layer. The region of the resist layer where the chemical reaction occurred is etched, thereby exposing a catalyst particle or particles in the catalyst layer surrounded by a wall of unetched resist material. Subsequent chemical vapor deposition causes growth of a nanostructure to occur upward through the wall of unetched resist material having controlled characteristics of height and diameter and, for parallel systems, number density.

  1. Magnetic nanoparticles conjugated to chiral imidazolidinone as recoverable catalyst

    NASA Astrophysics Data System (ADS)

    Mondini, Sara; Puglisi, Alessandra; Benaglia, Maurizio; Ramella, Daniela; Drago, Carmelo; Ferretti, Anna M.; Ponti, Alessandro

    2013-11-01

    The immobilization of an ad hoc designed chiral imidazolidin-4-one onto iron oxide magnetic nanoparticles (MNPs) is described, to afford MNP-supported MacMillan's catalyst. Morphological and structural analysis of the materials, during preparation, use, and recycle, has been carried out by transmission electron microscopy. The supported catalyst was tested in the Diels-Alder reaction of cyclopentadiene with cinnamic aldehyde, affording the products in good yields and enantiomeric excesses up to 93 %, comparable to those observed with the non-supported catalyst. Recovery of the chiral catalyst has been successfully performed by simply applying an external magnet to achieve a perfect separation of the MNPs from the reaction product. The recycle of the catalytic system has been also investigated. Noteworthy, this immobilized MacMillan's catalyst proved to be able to efficiently promote the reaction in pure water.

  2. Potential application of palladium nanoparticles as selective recyclable hydrogenation catalysts

    NASA Astrophysics Data System (ADS)

    Mukherjee, DebKumar

    2008-03-01

    The search for more efficient catalytic systems that might combine the advantages of both homogeneous (catalyst modulation) and heterogeneous (catalyst recycling) catalysis is one of the most exciting challenges of modern chemistry. More recently with the advances of nanochemistry, it has been possible to prepare soluble analogues of heterogeneous catalysts. These nanoparticles are generally stabilized against aggregation into larger particles by electrostatic or steric protection. Herein we demonstrate the use of room temperature ionic liquid for the stabilization of palladium nanoparticles that are recyclable catalysts for the hydrogenation of carbon-carbon double bonds and application of these catalysts to the selective hydrogenation of internal or terminal C=C bonds in unsaturated primary alcohols. The particles suspended in room temperature ionic liquid show no metal aggregation or loss of catalytic activity even on prolonged use.

  3. Application of a mixed metal oxide catalyst to a metallic substrate

    NASA Technical Reports Server (NTRS)

    Sevener, Kathleen M. (Inventor); Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Wisner, Daniel L. (Inventor)

    2009-01-01

    A method for applying a mixed metal oxide catalyst to a metallic substrate for the creation of a robust, high temperature catalyst system for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in propulsion systems. The method begins by forming a prepared substrate material consisting of a metallic inner substrate and a bound layer of a noble metal intermediate. Alternatively, a bound ceramic coating, or frit, may be introduced between the metallic inner substrate and noble metal intermediate when the metallic substrate is oxidation resistant. A high-activity catalyst slurry is applied to the surface of the prepared substrate and dried to remove the organic solvent. The catalyst layer is then heat treated to bind the catalyst layer to the surface. The bound catalyst layer is then activated using an activation treatment and calcinations to form the high-activity catalyst system.

  4. Computationally Probing the Performance of Hybrid, Heterogeneous, and Homogeneous Iridium-Based Catalysts for Water Oxidation

    SciTech Connect

    García-Melchor, Max; Vilella, Laia; López, Núria; Vojvodic, Aleksandra

    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.

  5. LaRC-developed catalysts for CO2 lasers

    NASA Technical Reports Server (NTRS)

    Upchurch, Billy T.; Kielin, Erik J.; Miller, Irvin M.

    1990-01-01

    Pulsed CO2 lasers have many remote sensing applications from space, airborne, and ground platforms. The NASA Laser Atmospheric Wind Sounder (LAWS) system will be designed to measure wind velocities from polar earth orbit for a period of up to three years. Accordingly, this and other applications require a closed-cycle pulsed CO2 laser which necessitates the use of an efficient CO-O2 recombination catalyst for these dissociation products which otherwise would degrade the laser operation. The required catalyst must not only operate at low temperatures but also must operate efficiently for long time periods. The research effort at NASA LaRC has centered around development and testing of CO oxidation catalysts for closed-cycle, pulsed, common and rare-isotope CO2 lasers. Researchers examined available commercial catalysts both in a laser and under simulated closed-cycle laser conditions with efforts aimed toward a thorough understanding of the fundamental catalytic reaction. These data were used to design and synthesize new catalyst compositions to better meet the catalyst requirements for closed-cycle pulsed CO2 lasers. Syntheses and test results for catalysts developed at Langley Research Center which have significantly better long-term decay characteristics than previously available catalysts and at the same time operate quite well under lower temperature conditions are discussed.

  6. Polymerization catalyst, production and use

    SciTech Connect

    Best, S.A.

    1987-01-06

    A process is described for the polymerization of ethylene and alpha-olefins having from 1 to 20 carbon atoms or mixtures of ethylene, alpha-olefins and diolefins. The process comprises polymerizing in the presence of a catalyst system comprising (a) an organo aluminum compound of the formula ALR''/sub n/X''/sub 3-n/ wherein R is hydrogen or a hydrocarbyl group having from 1 to 20 carbon atoms, X is halogen and is a number from 1 to 3, and (b) a transition metal containing catalyst component comprising the solid reaction product obtained by treating an inert solid support material in an inert solvent. This is done sequentially with (A) an organometallic compounds of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbon group, (B) an oxygen containing compound selected from ketones, aldehydes, alcohols or mixtures thereof, (C) an acyl halide, (D) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal, and (E) a group IIIa metal hydrocarbyl dihalide.

  7. Polymerization catalyst, production and use

    SciTech Connect

    Best, S.A.

    1987-01-06

    A process is described for the polymerization of ethylene and alpha-olefins having from 1 to 20 carbon atoms or mixtures of ethylene, alpha-olefins and diolefins. The process comprises polymerizing in the presence of a catalyst system comprising (a) an organo aluminum compound of the formula AIR''/sub n/X''/sub 3-n/ wherein R'' is hydrogen or a hydrocarbyl group having from 1 to 20 carbon atoms, X is halogen and n is a number from 1 to 3, and (B) a transition metal containing catalyst component comprising the solid reaction product obtained by treating an inert solid support material in an inert solvent. This is done sequentially with, optionally (A) Cl/sub 2/, Br/sub 2/, an interhalogen or mixtures thereof, (B) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbon group, (C) an oxygen containing compound selected from ketones, aldehydes, alcohols or mixtures thereof, (D) an acyl halide, (E) at least one transition metal compound of a Group IVb, VB, VIb or VIII metal, and (F) Cl/sub 2/, Br/sub 2/, an interhalogen or mixtures thereof.

  8. Polymerization catalyst, production and use

    SciTech Connect

    Best, S.A.

    1987-01-06

    A process is described for the polymerization of ethylene and alpha-olefins having from 1 to 20 carbon atoms or mixtures of ethylene, alpha-olefins and diolefins. The process comprises polymerizing in the presence of a catalyst system comprising (a) an organo aluminum compounds of the formula AIR''/sub n/X''/sub 3-n/ wherein R'' is hydrogen or a hydrocarbyl group having from 1 to 20 carbon atoms, X is halogen and n is a number from 1 to 3, and (b) a transition metal containing catalyst component comprising the solid reaction product obtained by treating an inert solid support material in an inert solvent. This is done sequentially with (A) an organometallic compound of a Group IIa, IIb, or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbon group, optionally (B) an oxygen containing compound selected from ketones, aldehydes, alcohols, siloxanes or mixtures thereof, (C) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal, and (D) a group IIIa metal hydrocarbyl dihalide.

  9. Catalysts based on amino acids for asymmetric reactions in water.

    PubMed

    Paradowska, Joanna; Stodulski, Maciej; Mlynarski, Jacek

    2009-01-01

    Asymmetric organometallic and organocatalytic processes in aqueous systems are currently of great interest. A few years ago, only a few practitioners studied the subject; now organic reactions in water have become one of the most exciting research areas. The quest to identify water-compatible catalysts has evoked an intense search for new possibilities. Following nature's lead, the application of amino acids as sources of chiral information seems particularly promising for aqueous systems. Herein we provide an overview of very recent advances in the area of asymmetric catalysis in water with amino acids and their derivatives as effective catalysts or essential components of catalysts.

  10. SCALEUP OF ALUMINUM PHOSPHATE CATALYST FOR PILOT PLANT LPDMEtm RUN

    SciTech Connect

    Andrew W. Wang

    2002-01-01

    The Liquid Phase Dimethyl Ether (LPDME{trademark}) process converts synthesis gas to dimethyl ether in a single slurry bubble column reactor. A mixed slurry of methanol synthesis catalyst and methanol dehydration catalyst in a neutral mineral oil simultaneously synthesizes methanol from syngas and converts some of it to dimethyl ether and water. The reaction scheme is shown below: 2H{sub 2} + CO = CH{sub 3}OH; 2CH{sub 3}OH = CH{sub 3}OCH{sub 3} + H{sub 2}O; H{sub 2}O + CO = CO{sub 2} + H{sub 2}. Most of the water produced in this reaction is converted to hydrogen by reduction with carbon monoxide (water gas shift reaction). This synergy permits higher per pass conversion than methanol synthesis alone. The enhancement in conversion occurs because dehydration of the methanol circumvents the equilibrium constraint of the syngas-to-methanol step. The slurry bubble column reactor provides the necessary heat transfer capacity to handle the greater heat duty associated with high conversion. In order to improve the stability of the catalyst system, non-stoichiometric aluminum phosphate was proposed as the dehydration catalyst for the LPDME{trademark} process. This aluminum phosphate material is a proprietary catalyst. This catalyst system of a standard methanol catalyst and the aluminum phosphate provided stable process performance that met the program targets under our standard test process conditions in the laboratory. These targets are (1) an initial methanol equivalent productivity of 28 gmol/kg/hr, (2) a CO{sub 2}-free, carbon selectivity of 80% to dimethyl ether and (3) stability of both catalysts equivalent to that of the methanol catalyst in the absence of the aluminum phosphate. A pilot plant trial of the LPDME{trademark} process using the aluminum phosphate catalyst was originally planned for March 1998 at the DOE-owned, Air Products (APCI)-operated facility at LaPorte, Texas. Because the aluminum phosphate catalyst is not commercially available, we initiated a

  11. SCALEUP OF ALUMINUM PHOSPHATE CATALYST FOR PILOT PLANT LPDMEtm RUN

    SciTech Connect

    Andrew W. Wang

    2002-05-15

    The Liquid Phase Dimethyl Ether (LPDME{trademark}) process converts synthesis gas to dimethyl ether in a single slurry bubble column reactor. A mixed slurry of methanol synthesis catalyst and methanol dehydration catalyst in a neutral mineral oil simultaneously synthesizes methanol from syngas and converts some of it to dimethyl ether and water. The reaction scheme is: 2H{sub 2} + CO = CH{sub 3}OH 2CH{sub 3}OH = CH{sub 3}OCH{sub 3} + H{sub 2}O H{sub 2}O + CO = CO{sub 2} + H{sub 2}. Most of the water produced in this reaction is converted to hydrogen by reduction with carbon monoxide (water gas shift reaction). This synergy permits higher per pass conversion than methanol synthesis alone. The enhancement in conversion occurs because dehydration of the methanol circumvents the equilibrium constraint of the syngas-to-methanol step. The slurry bubble column reactor provides the necessary heat transfer capacity to handle the greater heat duty associated with high conversion. In order to improve the stability of the catalyst system, non-stoichiometric aluminum phosphate was proposed as the dehydration catalyst for the LPDME{trademark} process. This aluminum phosphate material is a proprietary catalyst. This catalyst system of a standard methanol catalyst and the aluminum phosphate provided stable process performance that met the program targets under our standard test process conditions in the laboratory. These targets are (1) an initial methanol equivalent productivity of 28 gmol/kg/hr, (2) a CO{sub 2}-free, carbon selectivity of 80% to dimethyl ether and (3) stability of both catalysts equivalent to that of the methanol catalyst in the absence of the aluminum phosphate. A pilot plant trial of the LPDME{trademark} process using the aluminum phosphate catalyst was originally planned for March 1998 at the DOE-owned, Air Products (APCI)-operated facility at LaPorte, Texas. Because the aluminum phosphate catalyst is not commercially available, we initiated a scaleup project

  12. Binary ferrihydrite catalysts

    DOEpatents

    Huffman, G.P.; Zhao, J.; Feng, Z.

    1996-12-03

    A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered. 3 figs.

  13. Binary ferrihydrite catalysts

    DOEpatents

    Huffman, Gerald P.; Zhao, Jianmin; Feng, Zhen

    1996-01-01

    A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered.

  14. Fluorination process using catalyst

    DOEpatents

    Hochel, Robert C.; Saturday, Kathy A.

    1985-01-01

    A process for converting an actinide compound selected from the group consisting of uranium oxides, plutonium oxides, uranium tetrafluorides, plutonium tetrafluorides and mixtures of said oxides and tetrafluorides, to the corresponding volatile actinide hexafluoride by fluorination with a stoichiometric excess of fluorine gas. The improvement involves conducting the fluorination of the plutonium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3, AgF.sub.2 and NiF.sub.2, whereby the fluorination is significantly enhanced. The improvement also involves conducting the fluorination of one of the uranium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3 and AgF.sub.2, whereby the fluorination is significantly enhanced.

  15. Fluorination process using catalysts

    DOEpatents

    Hochel, R.C.; Saturday, K.A.

    1983-08-25

    A process is given for converting an actinide compound selected from the group consisting of uranium oxides, plutonium oxides, uranium tetrafluorides, plutonium tetrafluorides and mixtures of said oxides and tetrafluorides, to the corresponding volatile actinide hexafluoride by fluorination with a stoichiometric excess of fluorine gas. The improvement involves conducting the fluorination of the plutonium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF/sub 3/, AgF/sub 2/ and NiF/sub 2/, whereby the fluorination is significantly enhanced. The improvement also involves conducting the fluorination of one of the uranium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF/sub 3/ and AgF/sub 2/, whereby the fluorination is significantly enhanced.

  16. External Catalyst Breakup Phenomena

    DTIC Science & Technology

    1976-06-01

    anhydrous amonia cylinder and associated valve is revealed in the background. Nominal instrumentation for the reactor tests consisted of Temperatures...above the catalyst bed. Liquid, anhydrous ammonia was selected as the quench medium after consideration of the influence water might have on...corresponding to this G Iading and temperature at an amonia dissociation fraction of 0.5 and Lhamber pressure of 200 psia is 18.4 ft/sec. A typical five pound

  17. FCC catalyst selection

    SciTech Connect

    Carter, G.D.L. ); McElhiney, G. )

    1989-09-01

    This paper discusses a commonly used technique for comparing FCC catalytic selectivities based on the ASTM microactivity test (MAT) procedure, ASTM D-3907-80. In its original form the ASTM test provides only very limited information on selectivity. However, extension of the ASTM MAT procedure by using additional product analyses gives a microselectivity test capable of providing detailed yield structure information. This modified MAT procedure thus provides a cost-effective and rapid means of comparing many catalysts.

  18. Selective hydrogenolysis of glycerol to propylene glycol on Cu-ZnO composite catalysts: structural requirements and reaction mechanism.

    PubMed

    Wang, Shuai; Zhang, Yichi; Liu, Haichao

    2010-05-03

    Cu-ZnO catalysts were prepared by homogeneous coprecipitation with varying Cu/Zn atomic ratios (0.4-2:1). The catalysts were examined in selective hydrogenolysis of glycerol to propylene glycol. Although propylene glycol selectivities remained essentially constant (over 93%) on the different Cu-ZnO catalysts, the turnover frequencies changed markedly with the Cu/Zn ratio, and reached the greatest value at the ratio of 1:1. Such activity dependence on the Cu/Zn ratio was in parallel with the change in the interaction between Cu and ZnO and in the Cu microstrain, as a consequence of the effects on the crystalline phases of hydroxycarbonate precursors for the Cu-ZnO catalysts, reflecting the structural requirements for glycerol hydrogenolysis. The hydrogenolysis mechanism was also examined and apparently involves kinetically relevant glycerol dehydrogenation to glyceraldehyde on Cu-ZnO and subsequent glyceraldehyde dehydration and hydrogenation to propylene glycol. The mechanism is consistent with the observed superior activities of the more strained Cu particles, and the higher propylene glycol selectivities obtained at higher glycerol and hydrogen concentrations. These findings provide a rationale for the design of more effective Cu-based catalysts in selective hydrogenolysis of glycerol and other biomass-derived polyols, for example, by synthesis of highly strained Cu particles strongly interacting with ZnO or other oxide supports.

  19. Steam reforming catalyst

    DOEpatents

    Kramarz, Kurt W.; Bloom, Ira D.; Kumar, Romesh; Ahmed, Shabbir; Wilkenhoener, Rolf; Krumpelt, Michael

    2001-01-01

    A method of forming a hydrogen rich gas from a source of hydrocarbon fuel. A vapor of the hydrocarbon fuel and steam is brought in contact with a two-part catalyst having a dehydrogenation powder portion and an oxide-ion conducting powder portion at a temperature not less than about 770.degree.C. for a time sufficient to generate the hydrogen rich. The H.sub.2 content of the hydrogen gas is greater than about 70 percent by volume. The dehydrogenation portion of the catalyst includes a group VIII metal, and the oxide-ion conducting portion is selected from a ceramic oxide from the group crystallizing in the fluorite or perovskite structure and mixtures thereof. The oxide-ion conducting portion of the catalyst is a ceramic powder of one or more of ZrO.sub.2, CeO.sub.2, Bi.sub.2 O.sub.3, (BiVO).sub.4, and LaGaO.sub.3.

  20. Guanidinium groups act as general-acid catalysts in phosphoryl transfer reactions: a two-proton inventory on a model system.

    PubMed

    Piatek, Anna M; Gray, Mark; Anslyn, Eric V

    2004-08-18

    Cleavage/transesterification of phosphodiesters is catalyzed by various acidic groups in solution and with enzymes. General-acid catalysts can transfer protons to the developing phosphorane intermediate, resulting in a monoprotic-monoanionic intermediate, giving the so-called "triester mechanism". Using a proton inventory on a model compound (1) possessing an intramolecular hydrogen bond between a phosphodiester and a guanidinium group, we find that two protons move in the rate-determining step for cleavage/transesterification. In contrast, HPNP shows a single-proton inventory and is a substrate well accepted to react with the movement of only one proton at the transition state. We therefore propose a mechanism for 1 that involves general-acid catalysis by the guanidinium group. This leads one to conclude that other, more acidic groups, such as ammonium and imidazolium, would also act as general-acid catalysts.

  1. New pyridinium-based ionic liquid as an excellent solvent-catalyst system for the one-pot three-component synthesis of 2,3-disubstituted quinolines.

    PubMed

    Anvar, Salma; Mohammadpoor-Baltork, Iraj; Tangestaninejad, Shahram; Moghadam, Majid; Mirkhani, Valiollah; Khosropour, Ahmad Reza; Landarani Isfahani, Amir; Kia, Reza

    2014-03-10

    The synthesis of a variety of 2,3-disubstituted quinolines has been achieved successfully via a one-pot three-component reaction of arylamines, arylaldehydes and aliphatic aldehydes in the presence of butylpyridinium tetrachloroindate(III), [bpy][InCl4], ionic liquid as a green catalyst and solvent. Mild conditions with excellent conversions, and simple product isolation procedure are noteworthy advantages of this method. The recyclability of the ionic liquid makes this protocol environmentally benign.

  2. Structure and function of real catalysts

    NASA Astrophysics Data System (ADS)

    Klier, K.

    1984-11-01

    This paper addresses issues such as the relation between the physical and chemical nature of active centers, activation of reactant molecules, mechanisms of catalytic reactions and distribution of promoters in real catalysts which are invariably multicomponent multiphase systems. Interactions among the catalyst components and phases often result in the formation of compounds and defects that do not exist in the separate components. Although such interactions give rise to a great variety of morphologic, chemical, and electronic properties of the real catalysts, they can be controlled, mostly by careful preparation and doping procedures, to the degree that the catalyst displays reproducible activity and selectivity. Most of the examples given in this paper are based on the results from the author's laboratory concerning the activity and selectivity of copper-based catalysts for the hydrogenation of carbon monoxide and carbon dioxide, the water gas shift reaction, and some reactions of amines. Evidence is presented for the interactions between the copper and zinc oxide then analyzed in terms of defect equilibria using models and constants partially known from the literature and adapted for the present system. It is shown on the basis of boundary layer theory for small particles that charge transfer between copper metal particles, also present in the system, and the zinc oxide phase is insignificant. On the other hand, electron equilibria between the solute copper species and the zinc oxide matrix are dictated primarily by intrinsic ionization Cu 0 → Cu + + e - and oxygen vacancy formation. Optical absorption spectroscopy strongly corroborates the theoretical contention that a significant portion of the copper is in electron deficient state, and there is some evidence based on Auger spectroscopy for the presence of Cu + species on the catalyst surface. It is reiterated, as has been proposed before in our earlier work, that these copper species activate substrates

  3. Vacancy trapping by solute atoms during quenching in Cu-based dilute alloys studied by positron annihilation spectroscopy

    NASA Astrophysics Data System (ADS)

    Yabuuchi, A.; Yamamoto, Y.; Ohira, J.; Sugita, K.; Mizuno, M.; Araki, H.; Shirai, Y.

    2009-11-01

    Frozen-in vacancies and the recovery have been investigated in some Cu-based dilute alloys by using positron annihilation lifetime spectroscopy. Cu-0.5at%Sb, Cu-0.5at%Sn and Cu-0.5at%In dilute bulk alloys were quenched to ice water from 1223 K. A pure-Cu specimen was also quenched from the same temperature. As a result, no frozen-in vacancies have been detected in as-quenched pure-Cu specimen. On the other hand, as-quenched Cu-0.5at%Sb alloy contained frozen-in thermal equilibrium vacancies with concentration of 3 × 10-5. Furthermore, these frozen-in vacancies in Cu-0.5at%Sb alloy were stable until 473 K, and began to migrate at 523 K. Finally, the Cu-Sb alloy were recovered to the fully annealed state at 823 K. This thermal stability clearly implies some interaction exists between a vacancy and Sb atom and due to the interaction, thermal equilibrium vacancies are trapped by Sb atoms during quenching.

  4. Corrosion aspects of Ni-Cr-Fe based and Ni-Cu based steam generator tube materials

    NASA Astrophysics Data System (ADS)

    Dutta, R. S.

    2009-09-01

    This paper reviews corrosion related issues of Ni-Cr-Fe based (in a general sense) and Ni-Cu based steam generator tube materials for nuclear power plants those have been dealt with for last more than four decades along with some updated information on corrosion research. The materials include austenitic stainless steels (SSs), Alloy 600, Monel 400, Alloy 800 and Alloy 690. Compatibility related issues of these alloys are briefly discussed along with the alloy chemistry and microstructure. For austenitic SSs, stress corrosion cracking (SCC) behaviour in high temperature aqueous environments is discussed. For Alloy 600, intergranular cracking in high temperature water including hydrogen-induced intergranular cracking is highlighted along with the interactions of material in various environments. In case of Monel 400, intergranular corrosion and pitting corrosion at ambient temperature and SCC behaviour at elevated temperature are briefly described. For Alloy 800, the discussion covers SCC behaviour, surface characterization and microstructural aspects of pitting, whereas hydrogen-related issues are also highlighted for Alloy 690.

  5. Interface Development in Cu-Based Structures Transient Liquid Phase (TLP) Bonded with Thin Al Foil Intermediate Layers

    SciTech Connect

    Chen, Ke; Meng, Wen Jin; Eastman, J. A.

    2014-05-20

    Proper bonding and assembly techniques are essential for fabrication of functional metal-based microdevices. Transient liquid phase (TLP) bonding is a promising technique for making enclosed metallic microchannel devices. In this paper, we report results of TLP bonding of Cu-based structures at temperatures between 550ºC and 610ºC with thin elemental Al foils as intermediate boding layers. In-situ X-ray diffraction was utilized to examine the structure of Cu/Al interface in real time, resulting in a proposed sequence of structural evolution of the Cu/Al/Cu TLP bonding interface region. Three different types of bonding interface structures, the “γ1 structure”, the “eutectoid structure” (“E structure”), and the “E/γ1/E structure”, were observed through electron microscopy, and related to the proposed sequence of interfacial structural evolution. Tensile fracture tests were conducted on TLP bonded Cu/Al/Cu coupon assemblies. Hardness of the various phases within the bonding interface region was probed with instrumented nanoindentation. Results of mechanical testing were correlated to the structure of the bonding interface region. The present results provide an understanding of the structural evolution within the Cu/Al/Cu TLP bonding interface region, and offer guidance to future bonding of Cubased microsystems.

  6. Characterization of Free Volume Changes Associated with Shear Band Formation in Zr- and Cu-Based Bulk Metallic Glasses

    SciTech Connect

    Flores, K M; Glade, S C; Asoka-Kumar, P; Kanungo, B

    2003-11-14

    The free volume model for flow in metallic glasses predicts a significant increase in free volume at the onset of plastic deformation. The details of these structural changes are unclear, however, particularly during strain localization in shear bands. In this study, the free volume changes associated with inhomogeneous plastic deformation of a Cu-based bulk metallic glass were examined using positron annihilation spectroscopy (PAS). PAS results indicated that there was a distribution of free volume site sizes in both the as-quenched and rolled glasses, and that the concentration of larger sites increased with deformation. Differential scanning calorimetry (DSC) was also used to observe the glass transition behaviors of Cu- and Zr-based glasses after rolling and annealing. Annealing resulted in an increase in the height of the endothermic glass transition peak, consistent with structural relaxation relative to the as-quenched material. Deformation resulted in both a lower endothermic peak height and an earlier and deeper exothermic peak associated with structural relaxation, indicating a more disordered structure with more free volume.

  7. High-throughput heterogeneous catalyst research

    NASA Astrophysics Data System (ADS)

    Turner, Howard W.; Volpe, Anthony F., Jr.; Weinberg, W. H.

    2009-06-01

    With the discovery of abundant and low cost crude oil in the early 1900's came the need to create efficient conversion processes to produce low cost fuels and basic chemicals. Enormous investment over the last century has led to the development of a set of highly efficient catalytic processes which define the modern oil refinery and which produce most of the raw materials and fuels used in modern society. Process evolution and development has led to a refining infrastructure that is both dominated and enabled by modern heterogeneous catalyst technologies. Refineries and chemical manufacturers are currently under intense pressure to improve efficiency, adapt to increasingly disadvantaged feedstocks including biomass, lower their environmental footprint, and continue to deliver their products at low cost. This pressure creates a demand for new and more robust catalyst systems and processes that can accommodate them. Traditional methods of catalyst synthesis and testing are slow and inefficient, particularly in heterogeneous systems where the structure of the active sites is typically complex and the reaction mechanism is at best ill-defined. While theoretical modeling and a growing understanding of fundamental surface science help guide the chemist in designing and synthesizing targets, even in the most well understood areas of catalysis, the parameter space that one needs to explore experimentally is vast. The result is that the chemist using traditional methods must navigate a complex and unpredictable diversity space with a limited data set to make discoveries or to optimize known systems. We describe here a mature set of synthesis and screening technologies that together form a workflow that breaks this traditional paradigm and allows for rapid and efficient heterogeneous catalyst discovery and optimization. We exemplify the power of these new technologies by describing their use in the development and commercialization of a novel catalyst for the

  8. Reactive adsorption of ammonia on Cu-based MOF/graphene composites.

    PubMed

    Petit, Camille; Mendoza, Barbara; Bandosz, Teresa J

    2010-10-05

    New composites based on HKUST-1 and graphene layers are tested for ammonia adsorption at room temperature in both dry and moist conditions. The materials are characterized by X-ray diffraction, FT-IR spectroscopy, adsorption of nitrogen, and thermal analyses. Unlike other MOF/GO composites reported in previous studies, these materials are water-stable. Ammonia adsorption capacities on the composites are higher than the ones calculated for the physical mixture of components, suggesting the presence of a synergetic effect between the MOF and graphene layers. The increased porosity and dispersive forces being the consequence of the presence of graphene layers are responsible for the enhanced adsorption. In addition to its retention via physical forces, ammonia is also adsorbed via binding to the copper sites in HKUST-1 and then, progressively, via reaction with the MOF component. This reactive adsorption is visible through two successive changes of the adsorbents' color during the breakthrough tests. More ammonia is adsorbed in moist conditions than in dry conditions owing to its dissolution in a water film present in the pore system.

  9. Removal of Disinfection By-Products from Contaminated Water Using a Synthetic Goethite Catalyst via Catalytic Ozonation and a Biofiltration System·

    PubMed Central

    Wang, Yu-Hsiang; Chen, Kuan-Chung

    2014-01-01

    The effects of synthetic goethite (α-FeOOH) used as the catalyst in catalytic ozonation for the degradation of disinfection by-product (DBP) precursors are investigated. A biofiltration column applied following the catalytic ozonation process is used to evaluate the efficiency of removing DBP precursors via biotreatment. Ozone can rapidly react with aromatic compounds and oxidize organic compounds, resulting in a decrease in the fluorescence intensity of dissolved organic matter (DOM). In addition, catalytic ozonation can break down large organic molecules, which causes a blue shift in the emission-excitation matrix spectra. Water treated with catalytic ozonation is composed of low-molecular structures, including soluble microbial products (SMPs) and other aromatic proteins (APs). The DOM in SMPs and APs is removed by subsequent biofiltration. Catalytic ozonation has a higher removal efficiency for dissolved organic carbon and higher ultraviolet absorbance at 254 nm compared to those of ozonation without a catalyst. The use of catalytic ozonation and subsequent biofiltration leads to a lower DBP formation potential during chlorination compared to that obtained using ozonation and catalytic ozonation alone. Regarding DBP species during chlorination, the bromine incorporation factor (BIF) of trihalomethanes and haloacetic acids increases with increasing catalyst dosage in catalytic ozonation. Moreover, the highest BIF is obtained for catalytic ozonation and subsequent biofiltration. PMID:25211774

  10. Nitrogen enriched mesoporous organic polymer anchored copper(II) material: an efficient and reusable catalyst for the synthesis of esters and amides from aromatic systems.

    PubMed

    Molla, Rostam Ali; Iqubal, Md Asif; Ghosh, Kajari; Kamaluddin; Islam, Sk Manirul

    2015-04-14

    A new copper-grafted mesoporous poly-melamine-formaldehyde (Cu-mPMF) has been synthesized from melamine and paraformaldehyde in DMSO medium, followed by grafting of Cu(ii) at its surface. Cu-mPMF has been characterized by elemental analysis, powder XRD, HR TEM, FE-SEM, N2 adsorption study, FT-IR, UV-vis DRS, TGA-DTA, EPR spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The Cu-grafted mesoporous material showed very good catalytic activity in methyl esterification of benzylic alcohols and amidation of nitriles. Moreover, the catalyst is easily recoverable and can be reused seven times without appreciable loss of catalytic activity in the above reactions. The highly dispersed and strongly bound Cu(ii) sites in the Cu-grafted mesoporous polymer could be responsible for the observed high activities of the Cu-mPMF catalyst. Due to strong binding with the functional groups of the polymer, no evidence of leached copper from the catalyst during the course of reaction emerged, suggesting true heterogeneity in the catalytic process.

  11. Decoupling HZSM-5 catalyst activity from deactivation during upgrading of pyrolysis oil vapors.

    PubMed

    Wan, Shaolong; Waters, Christopher; Stevens, Adam; Gumidyala, Abhishek; Jentoft, Rolf; Lobban, Lance; Resasco, Daniel; Mallinson, Richard; Crossley, Steven

    2015-02-01

    The independent evaluation of catalyst activity and stability during the catalytic pyrolysis of biomass is challenging because of the nature of the reaction system and rapid catalyst deactivation that force the use of excess catalyst. In this contribution we use a modified pyroprobe system in which pulses of pyrolysis vapors are converted over a series of HZSM-5 catalysts in a separate fixed-bed reactor controlled independently. Both the reactor-bed temperature and the Si/Al ratio of the zeolite are varied to evaluate catalyst activity and deactivation rates independently both on a constant surface area and constant acid site basis. Results show that there is an optimum catalyst-bed temperature for the production of aromatics, above which the production of light gases increases and that of aromatics decrease. Zeolites with lower Si/Al ratios give comparable initial rates for aromatics production, but far more rapid catalyst deactivation rates than those with higher Si/Al ratios.

  12. Solid waste management of a chemical-looping combustion plant using Cu-based oxygen carriers.

    PubMed

    García-Labiano, Francisco; Gayán, Pilar; Adánez, Juan; De Diego, Luis F; Forero, Carmen R

    2007-08-15

    Waste management generated from a Chemical-Looping Combustion (CLC) plant using copper-based materials is analyzed by two ways: the recovery and recycling of the used material and the disposal of the waste. A copper recovery process coupled to the CLC plant is proposed to avoid the loss of active material generated by elutriation from the system. Solid residues obtained from a 10 kWth CLC prototype operated during 100 h with a CuO-Al2O3 oxygen carrier prepared by impregnation were used as raw material in the recovery process. Recovering efficiencies of approximately 80% were obtained in the process, where the final products were an eluate of Cu(NO3)2 and a solid. The eluate was used for preparation of new oxygen carriers by impregnation, which exhibited high reactivity for reduction and oxidation reactions as well as adequate physical and chemical properties to be used in a CLC plant. The proposed recovery process largely decreases the amount of natural resources (Cu and Al203) employed in a CLC power plant as well as the waste generated in the process. To determine the stability of the different solid streams during deposition in a landfill, these were characterized with respect to their leaching behavior according to the European Union normative. The solid residue finally obtained in the CLC plant coupled to the recovery process (composed by Al2O3 and CuAl2O4) can be classified as a stable nonreactive hazardous waste acceptable at landfills for nonhazardous wastes.

  13. Catalyst Additives to Enhance Mercury Oxidation and Capture

    SciTech Connect

    Alex J. Berry; Thomas K. Gale

    2005-09-30

    Preliminary research has shown that SCR catalysts employed for nitrogen-oxide reduction can effectively oxidize mercury. This report discusses initial results from fundamental investigations into the behavior of mercury species in the presence of SCR catalysts at Southern Research Institute. The testing was performed at Southern Research's Catalyst Test Facility, a bench-scale reactor capable of simulating gas-phase reactions occurring in coal-fired utility pollution-control equipment. Three different SCR catalysts are currently being studied in this project - honeycomb-type, plate-type, and a hybrid-type catalyst. The catalysts were manufactured and supplied by Cormetech Inc., Hitachi America Ltd., and Haldor-Topsoe Inc., respectively. Parametric testing was performed to investigate the contribution of flue-gas chemistry on mercury oxidation via SCR catalysts. Methods and procedures for experimental testing continue to be developed to produce the highest quality mercury-oxidation data. Most experiments so far have focused on testing the catalysts in a simulated Powder River Basin (PRB) flue-gas environment, which contains lower sulfur and chlorine than produced by other coals. Future work to characterize flue gas simulations typically derived from low and high sulfur bituminous coal will be performed in a stepwise manner, to avoid the constant interruptions in testing that occur when leaks in the system are generated during temperature transitions. Specifically, chlorine concentration vs. mercury oxidation graph will be developed for each catalyst. The contributions of temperature and later sulfur will be investigated after this is complete. Also, last quarter's tests showed a potential linear relationship between SO3 conversion and mercury oxidation. As a result, SO3 samples will be taken more frequently to investigate each catalyst's ability to selectively oxidize mercury.

  14. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, W.M.H.; Tzou, M.S.; Jiang, H.J.

    1987-03-31

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  15. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, Wolfgang M. H.; Tzou, Ming-Shin; Jiang, Hui-Jong

    1987-01-01

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  16. Scoping economics for the commercial manufacture of metallocene catalysts

    SciTech Connect

    Brockmeier, N.F.

    1994-05-26

    This study assumes that commercial-scale production of propylene-based isotactic polymers with metallocene catalyst systems will become a reality. The challenge that must be overcome for commercial success with these propylene polymers is to discover a metallocene system recipe that will give sufficient catalyst activity along with the requisite stereo-selectivity at reasonable cost. Anticipating such a discovery, it is assumed here that the economics are well-represented by a catalyst system that consists in part of a silylene-bridged cyclopentadienyl zirconocene made in a batchwise process having an annual capacity of 15,000 pounds. Activation will be achieved with a cocatalyst such as methylaluminoxane (MAO), coated in conjunction with the catalyst on a support such as silica. The MAO at an estimated $100/lb contributes $1800/lb cost to the finished catalyst with an assumed recipe of 18:1 mass ratio of MAO to zirconocene. Based on a 20% return on investment, the selling price for the supported zirconocene system is estimated to be $2915/lb. The required capital investment to make 735,000 lb/yr of the total supported system is 9 million dollars. These estimates have {plus_minus}50% range of uncertainty. Payback period for this plant in a sold-out condition is three years. The catalyst system cost in ethylene-propylene copolymer is 3.9 cents per pound with a productivity of 75,000 lb polymer/lb of zirconocene. An Appendix includes some economic details.

  17. Novel Intermetallic Catalysts to Enhance PEM Membrane Durability

    SciTech Connect

    Francis J. DiSalvo

    2009-01-06

    The research examined possible sources of degradation of platinum based anode catalysts under long term use. Scientists at the United Technologies Research Center had shown that the anode as well as the cathode catalysts degrade in hydrogen fuel cells. This goal of this research was to see if mechanisms of anode degradation could be understood using forefront electrochemical techniques in an aqueous system. We found that this method is limited by the very low levels of impurities (perhaps less than a part per trillion) in the electrolyte. This limitation comes from the relatively small catalyst surface area (a few sq cm or less) compared to the electrolyte volume of 10 to 25 ml. In real fuel cells this ratio is completelyreversed: high catalyst surface area and low electrolyte violume, making the system much less sensitive to impurities in the electrolyte. We conclude that degradation mechanisms should be studied in real fuel cell systems, rather than in ex-situ, large electrolyte volume experiments.

  18. Characterization and reactivity of nanoscale La(Co,Cu)O 3 perovskite catalyst precursors for CO hydrogenation

    NASA Astrophysics Data System (ADS)

    Tien-Thao, Nguyen; Alamdari, Houshang; Kaliaguine, Serge

    2008-08-01

    The characterization of La(Co,Cu)O 3 perovskites has been performed by several techniques including XRD, BET, H 2-TPR, O 2-TPO, TPRS, and the solids tested as catalysts for the hydrogenation of CO. The reducibility of the perovskites is strongly affected by the preparation route, calcination temperature, catalyst morphology, and the amount of remnant alkali. Compared with the citrate-derived perovskite, LaCoO 3 sample prepared by mechano-synthesis has various distinct Co 3+ ions in perovskite lattice, which are reduced at different temperatures. Under typical conditions, the reduction of cobalt ions occurs in two consecutive steps: Co 3+/Co 2+ and Co 2+/Co 0, while the intra-lattice copper ions are directly reduced from Cu 2+ to Cu 0. The reducibility of cobalt ions is promoted by the presence of metallic copper, which is formed at a lower reduction temperature. The re-oxidation of the reduced lanthanum cobaltite perovskite could regenerate the original structure, whereas that of the reduced Co-Cu-based samples is less reversible under the same experimental conditions. The cobalt atom in the reduced perovskites plays an important role in the dissociation of CO, but the presence of a neighboring copper along with remnant sodium ions on the catalyst surface has remarkably affected the reactivity of cobalt for CO hydrogenation. The addition of copper into the perovskite framework leads to a change in the product distribution of CO hydrogenation and a decrease in reaction temperature. An increased copper content leads to a substantial decline in the rate of methanation and an increase in the formation of higher alcohols. A close proximity between cobalt and copper sites on the Na +-modified catalyst surface of the reduced nanocrystalline Co-Cu-based perovskites plays a crucial role in the synthesis of higher alcohols from syngas.

  19. Routes for deactivation of different autothermal reforming catalysts

    NASA Astrophysics Data System (ADS)

    Pasel, Joachim; Wohlrab, Sebastian; Kreft, Stefanie; Rotov, Mikhail; Löhken, Katrin; Peters, Ralf; Stolten, Detlef

    2016-09-01

    Fuel cell systems with integrated autothermal reforming units require active and robust catalysts for H2 production. In pursuit of this, an experimental screening of catalysts utilized in the autothermal reforming of commercial diesel fuels is performed. The catalysts incorporate a monolithic cordierite substrate, an oxide support (γ-Al2O3, La-Al2O3, CeO2, Gd-CeO2, ZrO2, Y-ZrO2) and Rh as the active phase. Experiments are run by widely varying the O2/C and H2O/C molar ratios at different gas hourly space velocities. In most cases, this provokes accelerated catalyst deactivation and permits an informative comparison of the catalysts. Fresh and aged catalysts are characterized by temperature-programmed methods, thermogravimetry and transmission electron microscopy to find correlations with catalytic activity and stability. Using this approach, routes for catalyst deactivation are identified, together with causes of different catalytic activities. Suitable reaction conditions can be derived from our results for the operation of reactors for autothermal reforming at steady-state and under transient reaction conditions, which helps improve the efficiency and the stability of fuel cell systems.

  20. Development of GREET Catalyst Module

    SciTech Connect

    Wang, Zhichao; Benavides, Pahola T.; Dunn, Jennifer B.; Cronauer, Donald C.

    2015-09-01

    In this report, we develop energy and material flows for the production of five different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5], Mo/Co/ γ-Al2O3, and Pt/ γ-Al2O3) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module.

  1. Oxygen-reducing catalyst layer

    DOEpatents

    O'Brien, Dennis P [Maplewood, MN; Schmoeckel, Alison K [Stillwater, MN; Vernstrom, George D [Cottage Grove, MN; Atanasoski, Radoslav [Edina, MN; Wood, Thomas E [Stillwater, MN; Yang, Ruizhi [Halifax, CA; Easton, E Bradley [Halifax, CA; Dahn, Jeffrey R [Hubley, CA; O'Neill, David G [Lake Elmo, MN

    2011-03-22

    An oxygen-reducing catalyst layer, and a method of making the oxygen-reducing catalyst layer, where the oxygen-reducing catalyst layer includes a catalytic material film disposed on a substrate with the use of physical vapor deposition and thermal treatment. The catalytic material film includes a transition metal that is substantially free of platinum. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

  2. Spent catalyst processing with electrochemistry

    SciTech Connect

    Silva, L.J.; Bray, L.A.; Frye, J.G.; Buehler, M.F.

    1994-11-01

    Increasing concern for pollution prevention and waste disposal has created a need for clean alternatives for spent catalyst processing. In addition, expanded use of catalysts for the production of fuels and chemical feedstocks will continue in response to (1) economic pressure to upgrade heavier crudes and other feeds having high levels of impurities; (2) competitive pressure to achieve higher conversions using less energy; and (3) pressure to increase reaction selectivities to minimize waste production. While the incentives for using catalysts are great, all catalysts gradually lose activity through coking; poisoning by metals, sulfur, or halides; or loss of surface area from sintering at high process temperatures. Regeneration is possible where the catalyst deactivation can easily be reversed. Electrochemical dissolution is a new technique to oxidize catalyst contaminants and dissolve catalyst metals in an aqueous solution for further recovery of the raw materials. The key to this process is adding spent catalyst to a solution containing small amounts of species that form kinetically active, strongly oxidizing ions such as cerium(IV) or silver(II). The oxidizing ions are regenerated at the anode; they act in a catalytic manner carrying electrons from the solid surface to the anode of the electrochemical cell. A cerium oxidizer was used for the experiments described in this paper. For this procedure, solution is added to the anode side of an electrochemical cell. At the anode, aqueous cerium(III) is oxidized to cerium(IV). The cerium(IV), in turn, oxidizes organic material adhered to the catalyst to carbon dioxide and water. Many spent catalysts used in hydrogenations contain metal sulfides that have contaminated the catalyst surface during processing. Metal sulfides are oxidized to dissolved metal ions and sulfur species. Because cerium is continuously reoxidized to cerium(IV) at the anode, a small amount of cerium is needed to oxidize the spent catalyst.

  3. Mixed Alcohol Synthesis Catalyst Screening 2007 Progress Report

    SciTech Connect

    Gerber, Mark A.; White, J. F.; Gray, Michel J.; Stevens, Don J.

    2007-11-01

    Pacific Northwest National Laboratory (PNNL) and National Renewable Energy Laboratory (NREL) are researching the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). PNNL is obtaining commercially available mixed alcohol or preparing promising mixed-alcohol catalysts and screening them in a laboratory-scale reactor system. The most promising catalysts are provided to NREL for testing using a slipstream from a pilot-scale biomass gasifier. After a review of the literature in 2006 and conversations with companies that produce catalysts, it was determined that no commercial mixed-alcohol synthesis catalysts were available. One manufacturer supplied a modified methanol catalyst that was tested in the PNNL laboratory-scale system and provided to NREL for further testing. PNNL also prepared and tested the behavior of 10 other catalysts representing the distinct catalyst classes for mixed alcohol syntheses. Based on those results,testing in 2007 focused on the performance of the rhodium-based catalysts. The effects of adding promoters to the rhodium catalysts in addition to the manganese already being used were examined. The iron and rhenium promoters both stood out as achieving higher carbon selectivities , followed by Cu. Iridium and Li, on the other hand, had low carbon selectivity ratios of 0.27 and 0.22, respectively. Although testing of candidate promoters is not complete, it appears that Ir and Li promoters warrant further optimization and possibly combination to further improve STYs and carbon selectivities to C2+ oxygenates. However, using these promoters, it will be necessary to incorporate a separate hydrogenation catalyst to improve the yield of C2+ alcohols with respect to the other oxygenates. Fe, Re, and Cu stand out as possible candidates in this respect, but additional research is needed to examine whether they can be combined with the other promoters on the Rh-based catalyst or need to be optimized on a separate catalyst

  4. Results of catalyst testing using iron-based catalysts

    SciTech Connect

    Linehan, J.C.; Darab, J.G.; Matson, D.W.

    1993-03-01

    As coal liquefaction catalysts, iron-based products are generally inferior to the more expensive molybdenum, cobalt, or nickel-based materials. However, the lower costs of production and recovery (or in the case of some iron catalysts, non-recovery) give the iron-based materials a potential economic advantage over the more efficient precious and semi-precious metal catalysts for this application. Recent research has shown that a number of different iron-containing materials can be successfully utilized as coal liquefaction catalysts or as catalyst. Pyrrhotite (Fe{sub 1-x}S) or a similar iron-sulfide phase is commonly believed to be the active catalyst in coal liquefaction and model compound pyrolysis reactions, although no specific phase has been yet been isolated as the actual catalyst species. The active iron-containing catalyst is usually generated in situ from an iron-oxide precursor and an elemental sulfur source under reducing conditions in the reactor vessel. Most research has concentrated on the use of common iron-oxide phases such as hematite or goethite (and their derivatives) as the iron-bearing precursor, or on non-specific iron materials produced by the reaction of various iron salts and compounds in the coal or liquefaction reactor. To our knowledge there has been no systematic effort to determine the optimum iron-containing precursor phase for producing active coal liquefaction catalysts, despite the fact that there are over ten iron-(hydroxy)oxide phases which can be easily synthesized in the laboratory. We have undertaken a systematic study to identify the most active iron-oxide catalyst precursor phases, the co-catalysts, and the coal pretreatments which will provide optimum yields in coal liquefaction processes.

  5. Results of catalyst testing using iron-based catalysts

    SciTech Connect

    Linehan, J.C.; Darab, J.G.; Matson, D.W.

    1993-03-01

    As coal liquefaction catalysts, iron-based products are generally inferior to the more expensive molybdenum, cobalt, or nickel-based materials. However, the lower costs of production and recovery (or in the case of some iron catalysts, non-recovery) give the iron-based materials a potential economic advantage over the more efficient precious and semi-precious metal catalysts for this application. Recent research has shown that a number of different iron-containing materials can be successfully utilized as coal liquefaction catalysts or as catalyst. Pyrrhotite (Fe[sub 1-x]S) or a similar iron-sulfide phase is commonly believed to be the active catalyst in coal liquefaction and model compound pyrolysis reactions, although no specific phase has been yet been isolated as the actual catalyst species. The active iron-containing catalyst is usually generated in situ from an iron-oxide precursor and an elemental sulfur source under reducing conditions in the reactor vessel. Most research has concentrated on the use of common iron-oxide phases such as hematite or goethite (and their derivatives) as the iron-bearing precursor, or on non-specific iron materials produced by the reaction of various iron salts and compounds in the coal or liquefaction reactor. To our knowledge there has been no systematic effort to determine the optimum iron-containing precursor phase for producing active coal liquefaction catalysts, despite the fact that there are over ten iron-(hydroxy)oxide phases which can be easily synthesized in the laboratory. We have undertaken a systematic study to identify the most active iron-oxide catalyst precursor phases, the co-catalysts, and the coal pretreatments which will provide optimum yields in coal liquefaction processes.

  6. Catalyst for producing lower alcohols

    DOEpatents

    Rathke, Jerome W.; Klingler, Robert J.; Heiberger, John J.

    1987-01-01

    A process and system for the production of the lower alcohols such as methanol, ethanol and propanol involves the reaction of carbon monoxide and water in the presence of a lead salt and an alkali metal formate catalyst combination. The lead salt is present as solid particles such as lead titanate, lead molybdate, lead vanadate, lead zirconate, lead tantalate and lead silicates coated or in slurry within molten alkali metal formate. The reactants, carbon monoxide and steam are provided in gas form at relatively low pressures below 100 atmospheres and at temperatures of 200-400.degree. C. The resulted lower alcohols can be separated into boiling point fractions and recovered from the excess reactants by distillation.

  7. Nano Catalysts for Diesel Engine Emission Remediation

    SciTech Connect

    Narula, Chaitanya Kumar; Yang, Xiaofan; Debusk, Melanie Moses; Mullins, David R; Mahurin, Shannon Mark; Wu, Zili

    2012-06-01

    conditions were provided by our collaborators at John Deere Power Systems. Among various zeolites reported here, CuFe-SSZ-13 offers the best NO{sub x} conversion activity in 150-650 C range and is hydrothermally stable when tested under accelerated aging conditions. It is important to note that Cu-SSZ-13 is now a commercial catalyst for NO{sub x} treatment on diesel passenger vehicles. Thus, our catalyst performs better than the commercial catalyst under fast SCR conditions. We initially focused on fast SCR tests to enable us to screen catalysts rapidly. Only the catalysts that exhibit high NO{sub x} conversion at low temperatures are selected for screening under varying NO{sub 2}:NO{sub x} ratio. The detailed tests of CuFe-SSZ-13 show that CuFe-SSZ-13 is more effective than commercial Cu-SSZ-13 even at NO{sub 2}:NO{sub x} ratio of 0.1. The mechanistic studies, employing stop-flow diffuse reflectance FTIR spectroscopy (DRIFTS), suggest that high concentration of NO{sup +}, generated by heterobimetallic zeolites, is probably responsible for their superior low temperature NO{sub x} activity. The results described in this report clearly show that we have successfully completed the first step in a new emission treatment catalyst which is synthesis and laboratory testing employing simulated exhaust. The next step in the catalyst development is engine testing. Efforts are in progress to obtain follow-on funding to carry out scale-up and engine testing to facilitate commercialization of this technology.

  8. Supported Dendrimer-Encapsulated Metal Clusters: Toward Heterogenizing Homogeneous Catalysts.

    PubMed

    Ye, Rong; Zhukhovitskiy, Aleksandr V; Deraedt, Christophe V; Toste, F Dean; Somorjai, Gabor A

    2017-08-15

    Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles-some without homogeneous analogues-for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimize and expand the scope of their reactivity and selectivity. Ongoing efforts in our laboratories are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence, and structural uniformity, dendrimers have proven to be versatile scaffolds for the synthesis and stabilization of small nanoclusters. Then these dendrimer-encapsulated metal clusters (DEMCs) are adsorbed onto mesoporous silica. Through this method, we have achieved selective transformations that had been challenging to accomplish in a heterogeneous setting, e.g., π-bond activation and aldol reactions. Extensive investigation into the catalytic systems under reaction conditions allowed us to correlate the structural features (e.g., oxidation states) of the catalysts and their activity. Moreover, we have

  9. Extended Catalyst Longevity Via Supercritical Isobutane Regeneration of a Partially Deactivated USY Alkylation Catalyst

    SciTech Connect

    Daniel M. Ginosar; David N. Thompson; Kyle C. Burch; David J. Zalewski

    2005-05-01

    Off-line, in situ activity recovery of a partially deactivated USY zeolite catalyst used for isobutane/butene alkylation was examined in a continuous-flow reaction system employing supercritical isobutane. Catalyst samples were deactivated in a controlled manner by running them to either to a fixed butene conversion level of 95% or a fixed time on stream of three hours, and then exposing the catalyst to supercritical isobutane to restore activity. Activity recovery was determined by comparing alkylation activity before and after the regeneration step. Both single and multiple regenerations were performed. Use of a 95% butene conversion level criterion to terminate the reaction step afforded 86% activity recovery for a single regeneration and provided nine sequential reaction steps for the multiple regeneration studies. Employing a fixed 3 h time on stream criterion resulted in nearly complete activity recovery for a single regeneration, and 24 reaction steps were demonstrated in sequence for the multiple regeneration process, producing only minor product yield declines per step. This resulted in a 12-fold increase in catalyst longevity versus unregenerated catalyst.

  10. Use of ionic liquids as coordination ligands for organometallic catalysts

    DOEpatents

    Li, Zaiwei; Tang, Yongchun; Cheng; Jihong

    2009-11-10

    Aspects of the present invention relate to compositions and methods for the use of ionic liquids with dissolved metal compounds as catalysts for a variety of chemical reactions. Ionic liquids are salts that generally are liquids at room temperature, and are capable of dissolving a many types of compounds that are relatively insoluble in aqueous or organic solvent systems. Specifically, ionic liquids may dissolve metal compounds to produce homogeneous and heterogeneous organometallic catalysts. One industrially-important chemical reaction that may be catalyzed by metal-containing ionic liquid catalysts is the conversion of methane to methanol.

  11. DEHYDROGENATION CATALYST FOR PRODUCTION OF MTBE

    EPA Science Inventory

    The objectives of this project were to better understand the effect of different catalyst preparation parameters, the effect of different catalyst treatment parameters, and the mechanism of deactivation. Accordingly, catalysts were made using various preparation methods and with...

  12. DEHYDROGENATION CATALYST FOR PRODUCTION OF MTBE

    EPA Science Inventory

    The objectives of this project were to better understand the effect of different catalyst preparation parameters, the effect of different catalyst treatment parameters, and the mechanism of deactivation. Accordingly, catalysts were made using various preparation methods and with...

  13. Molecular water oxidation catalyst

    DOEpatents

    Gratzel, Michael; Munavalli, Shekhar; Pern, Fu-Jann; Frank, Arthur J.

    1993-01-01

    A dimeric composition of the formula: ##STR1## wherein L', L", L'", and L"" are each a bidentate ligand having at least one functional substituent, the ligand selected from bipyridine, phenanthroline, 2-phenylpyridine, bipyrimidine, and bipyrazyl and the functional substituent selected from carboxylic acid, ester, amide, halogenide, anhydride, acyl ketone, alkyl ketone, acid chloride, sulfonic acid, phosphonic acid, and nitro and nitroso groups. An electrochemical oxidation process for the production of the above functionally substituted bidentate ligand diaqua oxo-bridged ruthenium dimers and their use as water oxidation catalysts is described.

  14. Novel Reforming Catalysts

    SciTech Connect

    Pfefferle, Lisa D; Haller, Gary L

    2012-10-16

    Aqueous phase reforming is useful for processing oxygenated hydrocarbons to hydrogen and other more useful products. Current processing is hampered by the fact that oxide based catalysts are not stable under high temperature hydrothermal conditions. Silica in the form of structured MCM-41 is thermally a more stable support for Co and Ni than conventional high surface area amorphous silica but hydrothermal stability is not demonstrated. Carbon nanotube supports, in contrast, are highly stable under hydrothermal reaction conditions. In this project we show that carbon nanotubes are stable high activity/selectivity supports for the conversion of ethylene glycol to hydrogen.

  15. Tandem hydroformylation/hydrogenation of alkenes to normal alcohols using Rh/Ru dual catalyst or Ru single component catalyst.

    PubMed

    Takahashi, Kohei; Yamashita, Makoto; Nozaki, Kyoko

    2012-11-14

    The catalyst system for tandem hydroformylation/hydrogenation of terminal alkenes to the corresponding homologated normal alcohol was developed. The reaction mechanism for the Rh/Ru dual catalyst was investigated by real-time IR monitoring experiments and (31)P NMR spectroscopy, which proved the mutual orthogonality of Rh-catalyzed hydroformylation and Ru-catalyzed hydrogenation. Detailed investigation about Ru-catalyzed hydrogenation of undecanal under H(2)/CO pressure clarified different kinetics from the hydrogenation under H(2) and gave a clue to design more active hydrogenation catalysts under H(2)/CO atmosphere. The solely Ru-catalyzed normal selective hydroformylation/hydrogenation is also reported.

  16. Cyclic alkyl amino carbene (CAAC) ruthenium complexes as remarkably active catalysts for ethenolysis

    SciTech Connect

    Marx, Vanessa M.; Sullivan, Alexandra H.; Melaimi, Mohand; Virgil, Scott C.; Keitz, Benjamin K.; Weinberger, David S.; Bertrand, Guy; Grubbs, Robert H.

    2014-12-17

    In this paper, an expanded family of ruthenium-based metathesis catalysts bearing cyclic alkyl amino carbene (CAAC) ligands was prepared. These catalysts exhibited exceptional activity in the ethenolysis of the seed-oil derivative methyl oleate. In many cases, catalyst turnover numbers (TONs) of more than 100,000 were achieved, at a catalyst loading of only 3 ppm. Remarkably, the most active catalyst system was able to achieve a TON of 340 000, at a catalyst loading of only 1 ppm. Finally, this is the first time a series of metathesis catalysts has exhibited such high performance in cross-metathesis reactions employing ethylene gas, with activities sufficient to render ethenolysis applicable to the industrial-scale production of linear α-olefins (LAOs) and other terminal-olefin products.

  17. Cyclic alkyl amino carbene (CAAC) ruthenium complexes as remarkably active catalysts for ethenolysis

    DOE PAGES

    Marx, Vanessa M.; Sullivan, Alexandra H.; Melaimi, Mohand; ...

    2014-12-17

    In this paper, an expanded family of ruthenium-based metathesis catalysts bearing cyclic alkyl amino carbene (CAAC) ligands was prepared. These catalysts exhibited exceptional activity in the ethenolysis of the seed-oil derivative methyl oleate. In many cases, catalyst turnover numbers (TONs) of more than 100,000 were achieved, at a catalyst loading of only 3 ppm. Remarkably, the most active catalyst system was able to achieve a TON of 340 000, at a catalyst loading of only 1 ppm. Finally, this is the first time a series of metathesis catalysts has exhibited such high performance in cross-metathesis reactions employing ethylene gas, withmore » activities sufficient to render ethenolysis applicable to the industrial-scale production of linear α-olefins (LAOs) and other terminal-olefin products.« less

  18. Aqueous phase reforming of glycerol over Ni-based catalysts for hydrogen production.

    PubMed

    Cho, Su Hyun; Moon, Dong Ju

    2011-08-01

    Aqueous phase reforming of glycerol over Ni-based catalysts for hydrogen production was carried out at 225 degrees C, 23 bar and LHSV = 4 h(-1). The Ni-based catalyst was prepared by an incipient wetness impregnation method. The catalysts before and after the reaction were characterized by N2 physisorption, CO chemisorption, XRD, TPR, SEM and TEM techniques. It was found that Ni(20 wt%)-Co(3 wt%)/gamma-Al2O3 catalyst showed higher glycerol conversion and hydrogen selectivity than Ni(20 wt%)/gamma-Al2O3 catalyst. There are no major changes in Ni particles after the reaction over Ni-Co/gamma-Al2O3 catalyst. The results suggest that the Ni-Co/gamma-Al2O3 catalyst can be applied to the hydrogen production system using APR of glycerol.

  19. Ultrasound-assisted phase-transfer catalysis: benzoylation of sodium 4-acetylphenoxide by dual-site phase-transfer catalyst in a tri-liquid system.

    PubMed

    Yang, Hung-Ming; Chiu, Chun-Cheng

    2011-01-01

    A novel dual-site phase-transfer catalyst (PTC) was prepared and used to conduct the benzoylation of sodium 4-acetylphenoxide by ultrasound-assisted third-liquid phase-transfer catalysis. The catalyst 1,4-bis(tributylammoniomethyl)benzene dibromide (BTBAMBB) was synthesized from the reaction of p-xylylene dibromide and tributylamine in toluene at 70°C. The dual-site PTC was employed to form the third-liquid phase by extra addition of 0.04-0.05 mol of NaCl into 10 cm(3) of water. In the condition of 0.0425 mol of NaCl at 30°C, the catalytic intermediate in the third-liquid phase reached a maximum value. Almost 80% of the catalyst was transferred from the aqueous phase into the third-liquid phase. The distributions of the catalytic intermediate and dual-site PTC between phases and the kinetics of benzoylation of sodium 4-acetylphenoxide catalyzed by BTBAMBB with ultrasound irradiation were performed. The pseudo-first-order kinetic equation was applied to describe the overall reaction. Under ultrasound irradiation (28 kHz/300 W) in a batch reactor, the yield of product 4-acetylphenyl benzoate in the organic phase was 98.1% in 2 min at 30°C and 250 rpm with the apparent rate constant k(app) to be 0.0075 s(-1), which was 6 times faster than that without using ultrasound (yield=14.4%, k(app)=0.0013 s(-1)). The present study provides a green method to synthesize esters by ultrasound-assisted third-liquid phase-transfer catalysis. Copyright © 2010 Elsevier B.V. All rights reserved.

  20. Alkene metathesis: the search for better catalysts.

    PubMed

    Deshmukh, Prashant H; Blechert, Siegfried

    2007-06-28

    Alkene metathesis catalyst development has made significant progress over recent years. Research in metathesis catalyst design has endeavoured to tackle three key issues: those of (i) catalyst efficiency and activity, (ii) substrate scope and selectivity--particularly stereoselective metathesis reactions--and (iii) the minimization of metal impurities and catalyst recycling. This article describes a brief history of metathesis catalyst development, followed by a survey of more recent research, with a particular emphasis on ruthenium catalysts.

  1. Quantified MS analysis applied to combinatorial heterogeneous catalyst libraries.

    PubMed

    Wang, Hua; Liu, Zhongmin; Shen, Jianghan

    2003-01-01

    A high-throughput screening system for secondary catalyst libraries has been developed by incorporation of an 80-pass reactor and a quantified multistream mass spectrometer screening (MSMSS) technique. With a low-melting alloy as the heating medium, a uniform reaction temperature could be obtained in the multistream reactor (maximum temperature differences are less than 1 K at 673 K). Quantification of the results was realized by combination of a gas chromatogram with the MSMSS, which could provide the product selectivities of each catalyst in a heterogeneous catalyst library. Because the catalyst loading of each reaction tube is comparable to that of the conventional microreaction system and because the parallel reactions could be operated under identical conditions (homogeneous temperature, same pressure and WHSV), the reaction results of a promising catalyst selected from the library could be reasonably applied to the further scale-up of the system. The aldol condensation of acetone, with obvious differences in the product distribution over different kind of catalysts, was selected as a model reaction to validate the screening system.

  2. Fischer-Tropsch Synthesis on Ceramic Monolith-Structured Catalysts

    SciTech Connect

    Wang, Yong; Liu, Wei

    2009-04-19

    This paper reports recent research results about impact of different catalyst bed configurations on FT reaction product distribution. A CoRe/γ-alumina catalyst is prepared in bulk particle form and tested in the packed bed reactor at a size of 60 to 100 mesh. The same catalyst is ball milled and coated on a ceramic monolith support structure of channel size about 1mm. The monolith catalyst module is tested in two different ways, as a whole piece and as well-defined channels. Steady-state reaction conversion is measured at various temperatures under constant H2/CO feed ratio of 2 and reactor pressure of 25 bar. Detailed product analysis is performed. Significant formation of wax is evident with the packed particle bed and with the monolith catalyst that is improperly packed. By contrast, the wax formation is not detected in the liquid product by confining the reactions inside the monolith channel. This study presents an important finding about the structured catalyst/reactor system that the product distribution highly depends on the way how the structured reactor is set up. Even if the same catalyst and same reaction conditions (T, P, H2/oil ratio) are used, hydrodynamics (or flow conditions) inside a structured channel can have a significant impact on the product distribution.

  3. The generation of efficient supported (Heterogeneous) olefin metathesis catalysts

    SciTech Connect

    Grubbs, Robert H

    2013-04-05

    Over the past decade, a new family of homogeneous metathesis catalysts has been developed that will tolerate most organic functionalities as well as water and air. These homogeneous catalysts are finding numerous applications in the pharmaceutical industry as well as in the production of functional polymers. In addition the catalysts are being used to convert seed oils into products that can substitute for those that are now made from petroleum products. Seed oils are unsaturated, contain double bonds, and are a ready source of linear hydrocarbon fragments that are specifically functionalized. To increase the number of applications in the area of biomaterial conversion to petrol chemicals, the activity and efficiency of the catalysts need to be as high as possible. The higher the efficiency of the catalysts, the lower the cost of the conversion and a larger number of practical applications become available. Active supported catalysts were prepared and tested in the conversion of seed oils and other important starting materials. The outcome of the work was successful and the technology has been transferred to a commercial operation to develop viable applications of the discovered systems. A biorefinery that converts seed oils is under construction in Indonesia. The catalysts developed in this study will be considered for the next generation of operations.

  4. Electrochemical Catalyst-Support Effects and Their Stabilizing Role for IrOx Nanoparticle Catalysts during the Oxygen Evolution Reaction.

    PubMed

    Oh, Hyung-Suk; Nong, Hong Nhan; Reier, Tobias; Bergmann, Arno; Gliech, Manuel; Ferreira de Araújo, Jorge; Willinger, Elena; Schlögl, Robert; Teschner, Detre; Strasser, Peter

    2016-09-28

    Redox-active support materials can help reduce the noble-metal loading of a solid chemical catalyst while offering electronic catalyst-support interactions beneficial for catalyst durability. This is well known in heterogeneous gas-phase catalysis but much less discussed for electrocatalysis at electrified liquid-solid interfaces. Here, we demonstrate experimental evidence for electronic catalyst-support interactions in electrochemical environments and study their role and contribution to the corrosion stability of catalyst/support couples. Electrochemically oxidized Ir oxide nanoparticles, supported on high surface area carbons and oxides, were selected as model catalyst/support systems for the electrocatalytic oxygen evolution reaction (OER). First, the electronic, chemical, and structural state of the catalyst/support couple was compared using XANES, EXAFS, TEM, and depth-resolved XPS. While carbon-supported oxidized Ir particle showed exclusively the redox state (+4), the Ir/IrOx/ATO system exhibited evidence of metal/metal-oxide support interactions (MMOSI) that stabilized the metal particles on antimony-doped tin oxide (ATO) in sustained lower Ir oxidation states (Ir(3.2+)). At the same time, the growth of higher valent Ir oxide layers that compromise catalyst stability was suppressed. Then the electrochemical stability and the charge-transfer kinetics of the electrocatalysts were evaluated under constant current and constant potential conditions, where the analysis of the metal dissolution confirmed that the ATO support mitigates Ir(z+) dissolution thanks to a stronger MMOSI effect. Our findings raise the possibility that MMOSI effects in electrochemistry-largely neglected in the past-may be more important for a detailed understanding of the durability of oxide-supported nanoparticle OER catalysts than previously thought.

  5. Methane oxidation over dual redox catalysts

    SciTech Connect

    Klier, K.; Herman, R.G.; Sojka, Z.; DiCosimo, J.I.; DeTavernier, S.

    1992-06-01

    Catalytic oxidation of methane to partial oxidation products, primarily formaldehyde and C[sub 2] hydrocarbons, was found to be directed by the catalyst used. In this project, it was discovered that a moderate oxidative coupling catalyst for C[sub 2] hydrocarbons, zinc oxide, is modified by addition of small amounts of Cu and Fe dopants to yield fair yields of formaldehyde. A similar effect was observed with Cu/Sn/ZnO catalysts, and the presence of a redox Lewis acid, Fe[sup III] or Sn[sup IV], was found to be essential for the selectivity switch from C[sub 2] coupling products to formaldehyde. The principle of double doping with an oxygen activator (Cu) and the redox Lewis acid (Fe, Sn) was pursued further by synthesizing and testing the CuFe-ZSM-5 zeolite catalyst. The Cu[sup II](ion exchanged) Fe[sup III](framework)-ZSM-5 also displayed activity for formaldehyde synthesis, with space time yields exceeding 100 g/h-kg catalyst. However, the selectivity was low and earlier claims in the literature of selective oxidation of methane to methanol over CuFe-ZSM-5 were not reproduced. A new active and selective catalytic system (M=Sb,Bi,Sn)/SrO/La[sub 2]O[sub 3] has been discovered for potentially commercially attractive process for the conversion of methane to C[sub 2] hydrocarbons, (ii) a new principle has been demonstrated for selectivity switching from C[sub 2] hydrocarbon products to formaldehyde in methane oxidations over Cu,Fe-doped zinc oxide and ZSM-5, and (iii) a new approach has been initiated for using ultrafine metal dispersions for low temperature activation of methane for selective conversions. Item (iii) continues being supported by AMOCO while further developments related to items (i) and (ii) are the objective of our continued effort under the METC-AMOCO proposed joint program.

  6. Direct liquefaction of wood using nickel catalysts

    SciTech Connect

    Boocock, D.G.B.; Mackay, D.; Franco, H.

    1980-01-01

    In most the studies hydrogen has been used as a reducing agent and Raney nickel has been employed as catalyst, but in view of the low hydrogen uptake observed with mature catalyst some experiments were performed in the absence of hydrogen and these have yielded very encouraging results. An earlier paper described the complete liquefaction and gasification of fast-growing hybrid poplar. The wood (< 0.5 mm mesh) was suspended in water and treated with hydrogen in a well stirred and sparged autoclave using an initial pressure (24/sup 0/C) of 10.3 MPa and reaction temperatures of 325 to 375/sup 0/C. In all cases Raney-nickel was used as catalyst. In these single batch reactions hydrogen uptake was high and considerable wood gasification occurred. For example, for the highest catalyst/wood mass ratio of 0.2, 50g of wood at 350/sup 0/C consumed 3.8g of hydrogen and produced 1.3g of carbon dioxide, 16.0g of methane, 4.4g of saturated C/sub 2/ to C/sub 4/ alkanes and 8.0g of oil. No carbon monoxide was produced. The oil products contained 10 to 12 per cent oxygen and had viscosities of 700 to 2200 MPa.s at room temperature and heating values of 37 to 41 MJ.kg/sup -1/. The beneficial effect of prolonged use of the catalyst in extended batch reactions has now been examined. Reported are some results from these extended batch reactions and from runs in which hydrogen was not used. Also addressed is the problem of the wood feed system for possible commercial application.

  7. Microstructural and auger microanalytical characterization of Cu-Hf and Cu-Ti catalysts.

    PubMed

    Pisarek, M; Janik-Czachor, M

    2006-06-01

    Degradation processes occurring at the surface and in the bulk of Cu-based amorphous alloys during cathodic hydrogen charging were used for promoting the catalytic activity of such alloys. These processes modifying the structure, composition, and morphology of the substrate proved to be useful methods for transforming Cu-Hf and inactive Cu-Ti amorphous alloy precursors into active and durable catalysts. Indeed, their catalytic activity for dehydrogenation of 2-propanol increased up to a conversion level of approximately 60% at selectivities to acetone of about 99% for Cu-Ti and to conversion of approximately 90% at selectivities of approximately 95% for Cu-Hf. Previous attempts carried out by aging in air or hydrogen charging from the gas phase resulted in a maximum conversion level up to 15% for Cu-Hf and up to 3% for Cu-Ti. High resolution Auger spectroscopy allowed changes occurring during the activation process to be identified, namely, the formation of small Cu particles on the HfO2 surface and the formation of highly porous particles containing mostly Cu and some Ti and O (Cu-Ti-O) on a Cu-Ti substrate. Differences in the chemistry and structure of both catalysts are discussed, and the implications for catalytic function are considered. A probable configuration of active sites on the Cu-Ti-O/Ti-O-Cu catalyst for dehydrogenation of 2-propanol is proposed.

  8. Influence of nano-Al2O3-reinforced oxide-dispersion-strengthened Cu on the mechanical and tribological properties of Cu-based composites

    NASA Astrophysics Data System (ADS)

    Zhao, Xiang; Guo, Lei-chen; Zhang, Long; Jia, Ting-ting; Chen, Cun-guang; Hao, Jun-jie; Shao, Hui-ping; Guo, Zhi-meng; Luo, Ji; Sun, Jun-bin

    2016-12-01

    The mechanical and tribological properties of Cu-based powder metallurgy (P/M) friction composites containing 10wt%-50wt% oxide-dispersion-strengthened (ODS) Cu reinforced with nano-Al2O3 were investigated. Additionally, the friction and wear behaviors as well as the wear mechanism of the Cu-based composites were characterized by scanning electron microscopy (SEM) in conjunction with energy-dispersive X-ray spectroscopy (EDS) elemental mapping. The results indicated that the Cu-based friction composite containing 30wt% ODS Cu exhibited the highest hardness and shear strength. The average and instantaneous friction coefficient curves of this sample, when operated in a high-speed train at a speed of 300 km/h, were similar to those of a commercial disc brake pad produced by Knorr-Bremse AG (Germany). Additionally, the lowest linear wear loss of the obtained samples was (0.008 ± 0.001) mm per time per face, which is much lower than that of the Knorr-Bremse pad ((0.01 ± 0.001) mm). The excellent performance of the developed pad is a consequence of the formation of a dense oxide composite layer and its close combination with the pad body.

  9. Catalysts for electrochemical generation of oxygen

    NASA Technical Reports Server (NTRS)

    Hagans, P.; Yeager, E.

    1978-01-01

    Single crystal surfaces of platinum and gold and transition metal oxides of the spinel type were studied to find more effective catalysts for the electrolytic evolution of oxygen and to understand the mechanism and kinetics for the electrocatalysis in relation to the surface electronic and lattice properties of the catalyst. The single crystal studies involve the use of low energy electron diffraction (LEED) and Auger electron spectroscopy as complementary tools to the electrochemical measurements. Modifications to the transfer system and to the thin-layer electrochemical cell used to facilitate the transfer between the ultrahigh vacuum environment of the electron surface physics equipment and the electrochemical environment with a minimal possibility of changes in the surface structure, are described. The electrosorption underpotential deposition of Pb onto the Au(111), (100) and (110) single crystal surfaces with the thin-layer cell-LEED-Auger system is discussed as well as the synthesis of spinels for oxygen evolution studies.

  10. Startup procedure for reforming catalysts

    SciTech Connect

    McHale, W.D.; Schoennagel, H.J.

    1984-08-14

    Process for reforming a hydrocarbon charge under reforming conditions in a reforming zone containing a sulfur-sensitive metal containing reforming catalyst wherein over-cracking of the charge stock and excessive temperature rise in the reforming zone is suppressed by pre-conditioning the catalyst, prior to contact with the charge, with a reformate of specified octane number and aromatics content.

  11. Catalysts for low temperature oxidation

    DOEpatents

    Toops, Todd J.; Parks, III, James E.; Bauer, John C.

    2016-03-01

    The invention provides a composite catalyst containing a first component and a second component. The first component contains nanosized gold particles. The second component contains nanosized platinum group metals. The composite catalyst is useful for catalyzing the oxidation of carbon monoxide, hydrocarbons, oxides of nitrogen, and other pollutants at low temperatures.

  12. Transition metal sulfide loaded catalyst

    DOEpatents

    Maroni, V.A.; Iton, L.E.; Pasterczyk, J.W.; Winterer, M.; Krause, T.R.

    1994-04-26

    A zeolite-based catalyst is described for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C[sub 2]+ hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

  13. Transition metal sulfide loaded catalyst

    DOEpatents

    Maroni, Victor A.; Iton, Lennox E.; Pasterczyk, James W.; Winterer, Markus; Krause, Theodore R.

    1994-01-01

    A zeolite based catalyst for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C.sub.2 + hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

  14. Doped palladium containing oxidation catalysts

    SciTech Connect

    Mohajeri, Nahid

    2014-02-18

    A supported oxidation catalyst includes a support having a metal oxide or metal salt, and mixed metal particles thereon. The mixed metal particles include first particles including a palladium compound, and second particles including a precious metal group (PMG) metal or PMG metal compound, wherein the PMG metal is not palladium. The oxidation catalyst may also be used as a gas sensor.

  15. Catalysts to reduce NO.sub.x in an exhaust gas stream and methods of preparation

    DOEpatents

    Koermer, Gerald S [Basking Ridge, NJ; Moini, Ahmad [Princeton, NJ; Furbeck, Howard [Hamilton, NJ; Castellano, Christopher R [Ringoes, NJ

    2012-05-08

    Catalysts, systems and methods are described to reduce NO.sub.x emissions of an internal combustion engine. In one embodiment, an emissions treatment system for an exhaust stream is provided having a catalyst comprising silver on a particulate alumina support, the silver having a diameter of less than about 20 nm. Methods of manufacturing catalysts are described in which ionic silver is impregnated on particulate hydroxylated alumina particles.

  16. Catalysts to reduce NO.sub.x in an exhaust gas stream and methods of preparation

    DOEpatents

    Castellano, Christopher R.; Moini, Ahmad; Koermer, Gerald S.; Furbeck, Howard; Schmieg, Steven J.; Blint, Richard J.

    2011-05-17

    Catalysts, systems and methods are described to reduce NO.sub.x emissions of an internal combustion engine. In one embodiment, an emissions treatment system for an exhaust stream is provided having a catalyst comprising silver and a platinum group metal on a particulate alumina support, the atomic fraction of the platinum group metal being less than or equal to about 0.25. Methods of manufacturing catalysts are described in which silver is impregnated on alumina particles.

  17. Zeolites for reforming catalysts

    SciTech Connect

    Kao, J.L.; Nadler, M.; Potter, M.J.; Martir, R.V.

    1991-01-22

    This patent describes a reforming catalyst exhibiting enhanced selectivity, activity, and activity maintenance. It comprises: zeolite crystals having a pH within the range of 9.4 to 10.0, wherein the pH is determined by measuring pH of supernatent liquid from a mixture of one part of the zeolite crystals with ten parts of dionized water by weight, and comprising exchangeable cations and at least one catalytically active metal selected from the group consisting of Group VII of the Periodic Table of Elements, tin and germanium. This patten also describes a process for treating zeolite to have a pH within a range effective in imparting enhanced activity, selectivity and activity maintenance to catalysts loaded onto the zeolite. The process comprising washing zeolite with an aqueous liquid in a manner so as to result with zeolite having a pH within the pH range of 9.4 to 10.0. The PH of supernatent liquid from a mixture of one part of the zeolite crystals with ten parts of dionized water by weight.

  18. Catalyst design for biorefining.

    PubMed

    Wilson, Karen; Lee, Adam F

    2016-02-28

    The quest for sustainable resources to meet the demands of a rapidly rising global population while mitigating the risks of rising CO2 emissions and associated climate change, represents a grand challenge for humanity. Biomass offers the most readily implemented and low-cost solution for sustainable transportation fuels, and the only non-petroleum route to organic molecules for the manufacture of bulk, fine and speciality chemicals and polymers. To be considered truly sustainable, biomass must be derived from resources which do not compete with agricultural land use for food production, or compromise the environment (e.g. via deforestation). Potential feedstocks include waste lignocellulosic or oil-based materials derived from plant or aquatic sources, with the so-called biorefinery concept offering the co-production of biofuels, platform chemicals and energy; analogous to today's petroleum refineries which deliver both high-volume/low-value (e.g. fuels and commodity chemicals) and low-volume/high-value (e.g. fine/speciality chemicals) products, thereby maximizing biomass valorization. This article addresses the challenges to catalytic biomass processing and highlights recent successes in the rational design of heterogeneous catalysts facilitated by advances in nanotechnology and the synthesis of templated porous materials, as well as the use of tailored catalyst surfaces to generate bifunctional solid acid/base materials or tune hydrophobicity.

  19. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Technical progress report, March--May 1992

    SciTech Connect

    Klier, K.; Herman, R.G.; Richards-Babb, M.

    1992-06-01

    During this quarter, the high pressure (up to 100 atm), high temperature (up to 350{degrees}C) catalyst testing system was rebuilt with clean tubing, etc. A new preparation of MoS{sub 2} catalyst was carried out, and this catalyst will be doped with alkali and tested during the next quarter of research.

  20. Supported molten-metal catalysts

    DOEpatents

    Datta, Ravindra; Singh, Ajeet; Halasz, Istvan; Serban, Manuela

    2001-01-01

    An entirely new class of catalysts called supported molten-metal catalysts, SMMC, which can replace some of the existing precious metal catalysts used in the production of fuels, commodity chemicals, and fine chemicals, as well as in combating pollution. SMMC are based on supporting ultra-thin films or micro-droplets of the relatively low-melting (<600.degree. C.), inexpensive, and abundant metals and semimetals from groups 1, 12, 13, 14, 15 and 16, of the periodic table, or their alloys and intermetallic compounds, on porous refractory supports, much like supported microcrystallites of the traditional solid metal catalysts. It thus provides orders of magnitude higher surface area than is obtainable in conventional reactors containing molten metals in pool form and also avoids corrosion. These have so far been the chief stumbling blocks in the application of molten metal catalysts.

  1. Catalysts Encapsulated in Molecular Machines.

    PubMed

    Pan, Tiezheng; Liu, Junqiu

    2016-06-17

    Smart catalysts offer the control of chemical processes and sequences of transformations, and catalysts with unique catalytic behavior can afford chiral products or promote successive polymerization. To meet advanced demands, the key to constructing smart catalysts is to incorporate traditional catalytic functional groups with trigger-induced factors. Molecular machines with dynamic properties and particular topological structures have typical stimulus-responsive features. In recent years, scientists have made efforts to utilize molecular machines (molecular switches, rotaxanes, motors, etc.) as scaffolds to develop smart catalysts. This Minireview focuses on the achievements of developing catalysts encapsulated in molecular machines and their remarkable specialties. This strategy is believed to provide more potential applications in switchable reactions, asymmetric synthesis, and processive catalysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Zero-valent iron supported on nitrogen-doped carbon xerogel as catalysts for the oxidation of phenol by fenton-like system.

    PubMed

    Messele, S A; Soares, O S G P; Órfão, J J M; Bengoa, C; Font, J

    2017-09-03

    Nitrogen-free and nitrogen-doped carbon xerogel materials, from urea and melamine precursors, were prepared at different pH and evaluated as adsorbents/catalysts in the removal of phenol. Then, zero-valent iron (ZVI) was supported on these carbon xerogel materials and its activity was again evaluated for phenol removal by adsorption and catalytic wet peroxide oxidation (CWPO). The prepared samples were characterized by N2 adsorption at -196°C, pH at the point of zero charge (pHPZC) and elemental analysis. The textural properties of the N-free and N-doped carbon xerogels are strongly influenced by pH of the preparation solution and precursor used. The presence of ZVI on all carbon xerogel supports improved the phenol removal efficiency. ZVI supported on urea- and melamine-doped carbon xerogels show a good performance, reaching above 87% phenol conversion after 60 min of CWPO. On the contrary, pure adsorption and CWPO using the same materials without the presence of ZVI gives low phenol removal efficiency. A correlation was found between the activity of ZVI catalysts in CWPO and the N-content of the supports.

  3. Surface structure and functionality of bauxite-based catalysts in the hydrotreating of heavy crudes

    SciTech Connect

    Vecchi, C.; Marengo, S.; Iannibello, A.; Girelli, A.

    1982-09-01

    The functionality of Mo- and W-containing catalysts in the hydrotreating of heavy feedstocks in trickle flow conditions was compared. The catalysts included a bauxite support with an absorbed layer of Mo and/or W prepared by a step addition technique. Alumina-supported catalysts were studied also, and a strict correlation was observed between the properties of the bauxite-based catalysts and those of the corresponding alumina-based systems. The Mo-based systems performed better as catalysts than the W systems. NMR results revealed a deeper insight into the structural modifications induced in the feedstock by catalytic hydroprocessing with these catalysts. The catalysis studies of the feedstocks showed that the removal of the ethero-atoms lowered the aromaticity of the samples and the degree of condensation of the aromatic structures with only a moderate amount of hydrogenation of the aromatic rings. (BLM)

  4. Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

    NASA Technical Reports Server (NTRS)

    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.

  5. Development plus kinetic and mechanistic studies of a prototype supported-nanoparticle heterogeneous catalyst formation system in contact with solution: Ir(1,5-COD)Cl/gamma-Al2O3 and its reduction by H2 to Ir(0)n/gamma-Al2O3.

    PubMed

    Mondloch, Joseph E; Wang, Qi; Frenkel, Anatoly I; Finke, Richard G

    2010-07-21

    An important question and hence goal in catalysis is how best to transfer the synthetic and mechanistic insights gained from the modern revolution in nanoparticle synthesis, characterization, and catalysis to prepare the next generation of improved, supported-nanoparticle heterogeneous catalysts. It is precisely this question and to-date somewhat elusive goal which are addressed by the present work. More specifically, the global hypothesis investigated herein is that the use of speciation-controlled, well-characterized, solid oxide supported-organometallic precatalysts in contact with solution will lead to the next generation of better composition, size- and shape-controlled, as well as highly active and reproducible, supported-nanoparticle heterogeneous catalysts-ones that can also be understood kinetically and mechanistically. Developed herein are eight criteria defining a prototype system for supported-nanoparticle heterogeneous catalyst formation in contact with solution. The initial prototype system explored is the precatalyst, Ir(1,5-COD)Cl/gamma-Al(2)O(3) (characterized via ICP, CO adsorption, IR, and XAFS spectroscopies), and the well-defined product, Ir(0)(n)/gamma-Al(2)O(3) (characterized by reaction stoichiometry, TEM, and XAFS). The Ir(0)(n)/gamma-Al(2)O(3) system proved to be a highly active and long-lived catalyst in the simple test reaction of cyclohexene hydrogenation and in comparison to two literature Ir(0)(n)/Al(2)O(3) heterogeneous catalysts examined under identical conditions. High activity (2.2-4.8-fold higher than that of the literature Ir(0)(n)/Al(2)O(3) catalysts tested under the same conditions) and good lifetime (> or = 220,000 total turnovers of cyclohexene hydrogenation) are observed, in part by design since only acetone solvent, cyclohexene, and H(2) are possible ligands in the resultant "weakly ligated/labile-ligand" supported nanoclusters. Significantly, the Ir(1,5-COD)Cl/gamma-Al(2)O(3) + H(2) --> Ir(0)(n)/gamma-Al(2)O(3

  6. Evaluation of Regenerated Catalyst for Mercury Speciation

    SciTech Connect

    Dennis Laudal

    2007-06-01

    In March of 2005, U.S. Environmental Protection Agency (EPA) promulgated the Clean Air Mercury Rule (CAMR). Mercury from coal-fired power plants was to be reduced from the current 48 to 38 tons/yr by 2010 and then 15 tons/yr by 2018. It is expected that the first phase reduction of {approx}21% will be achieved by cobenefits that will occur as a result of installing additional selective catalytic reduction (SCR) and flue gas desulfurization (FGD) systems to meet the new Clean Air Interstate Rule (CAIR). Detroit Edison (DTE) is installing SCR at all four units at its Monroe Station and will eventually install wet-FGD systems. As such, the Electric Power Research Institute (EPRI), the U.S. Department of Energy (DOE), and DTE have contracted with the Energy & Environmental Research Center (EERC) to determine the extent of mercury oxidation that occurs at Monroe Station. The EERC originally did mercury speciation sampling at Monroe Station in 2004 and then went back in 2005 to determine if any changes occurred as a result of catalyst aging. During the second test, in addition to measuring the mercury speciation at the inlet and outlet of the SCR, the EERC also completed sampling at a location between the catalyst layers. The results are shown in Table 1. In Table 1, the results show that {approx}40% of the Hg was in oxidized form (Hg{sup 2+}) at the inlet and nearly 100% Hg{sup 2+} at the outlet. The results at the midpoint were between 40% and 100%. As part of their overall strategy to reduce SCR costs, utilities and SCR vendors are attempting to regenerate catalyst layers that have degenerated over time. If these regenerated catalysts are used, the question remains as to the effect this process will have on the ability of these catalysts to oxidize mercury as well as reduce NO{sub x}. The current project is designed to measure the Hg speciation across an SCR using a regenerated catalyst. The results were compared to previous results to determine what, if any, changes

  7. Regeneration of a deactivated USY alkylation catalyst using supercritical isobutane

    SciTech Connect

    Daniel M. Ginosar; David N. Ghompson; Kyle C. Burch

    2005-01-01

    Off-line, in-situ alkylation activity recovery from a completely deactivated solid acid catalyst was examined in a continuous-flow reaction system employing supercritical isobutane. A USY zeolite catalyst was initially deactivated during the liquid phase alkylation of butene with isobutane in a single-pass reactor and then varying amounts of alkylation activity were recovered by passing supercritical isobutane over the catalyst bed at different reactivation conditions. Temperature, pressure and regeneration time were found to play important roles in the supercritical isobutane regeneration process when applied to a completely deactivated USY zeolite alkylation catalyst. Manipulation of the variables that influence solvent strength, diffusivity, surface desorption, hydride transfer rates, and coke aging, strongly influence regeneration effectiveness.

  8. Elucidation of the inorganic chemistry of hydrotreating catalysts

    SciTech Connect

    DeCanio, E.C.; Edwards, J.C.; Storm, D.A.; Bruno, J.W.

    1993-12-31

    New environmental regulations are making it necessary to developed improved hydrotreating catalysts for the removal of sulfur, nitrogen and aromatics from refinery streams. In order to develop better catalysts, the authors must gain a more detailed understanding of the inorganic chemistry of these catalysts. Commercial catalysts typically contain ca. 15 wt% molybdenum or tungsten oxides and ca. 4 wt% nickel or cobalt. Additives, such as phosphate and fluoride, are often added to improve the catalytic activity. However, the role of these additives is not fully understood. The authors have, therefore, carried out studies on alumina supported phosphate and flouride materials using FT-IR, powder x-ray diffraction, and solid-state NMR ({sup 31}P, {sup 27}Al, and {sup 1}H). The results of this work have enabled the authors to determine the structures of the various compounds formed on the alumina system when fluoride or phosphate is present.

  9. On the performance of low pressure die-cast Al-Cu based automotive alloys: Role of additives

    NASA Astrophysics Data System (ADS)

    Zaki, Gergis Adel

    The present study focuses on the effect of alloying elements, namely, strontium (Sr), titanium (Ti), zirconium (Zr), scandium (Sc) and silver(Ag) individually or in combination, on the performance of a newly developed Al-2%Cu based alloy. A total of thirteen alloy compositions were used in the study. Tensile test bar castings were prepared employing the low pressure die casting (LPDC) technique. The test bars were solution heat treated at 495°C for 8 hours, followed by quenching in warm water, and then subjected to different isochronal aging treatments using an aging time of 5 hours and aging temperatures of 155°C, 180°C, 200°C, 240°C and 300°C. Tensile testing of as-cast and heat-treated test bars was carried out at room temperature using a strain rate of 4 x 10-4s-1. Five test bars were used per alloy composition/condition. Hardness measurements were also carried out on these alloys using a Brinell hardness tester. The microstructures of selected samples were examined using optical microscopy and electron probe microanalysis (EPMA). The results showed that adding Ti in the amount of 0.15 wt% in the form of Al-5%Ti-1%B master alloy is sufficient to refine the grains in the cast structure in the presence of 200 ppm Sr (0.02 wt%). Addition of Zr and Sc did not contribute further to the grain refining effect. The main role of addition of these two elements appeared in the formation of complex compounds with Al and Ti. Their presence resulted in extending the aging temperature range before the onset of softening. Mathematical analysis of the hardness and tensile data was carried out using the Minitab statistical software program. It was determined that the alloy containing (0.5wt% Zr + 0.15wt% Ti) is the most effective in maximizing the alloy tensile strength over the range of aging temperatures, from 155°C to 300°C. Addition of Ag is beneficial at high aging temperatures, in the range of 240°C-300°C. However, it is less effective compared to the (Zr + Ti

  10. Catalytic cracking catalysts

    SciTech Connect

    Chiang, R.L.; Perigard, R.G.; Rabo, J.A.

    1986-05-13

    A process is described for preparing a catalyst comprising the following steps: (i) contacting a mixture of a large pore zeolite and an inorganic oxide matrix, with a fluoro salt of the formula A/sub (n-m)/(MF/sub n/)/sub z/ wherein ''A'' is an organic or inorganic ionic moiety; (MF/sub n/)/sub z/ is a fluoroanion moiety comprising the element ''M''; ''M'' is an element selected from the group of elements from Groups VB, VIB, VIIB, VIII, IIIA, IVA and VA of the Periodic Table of Elements; ''n'' is the coordination number of ''M''; ''m'' is the valence of ''M''; and ''z'' is the valence or charge associated with ''A''; at a pH greater than about 3, at effective conditions of temperature and time.

  11. Full Scale Alternative Catalyst Testing for Bosch Reactor Optimization

    NASA Technical Reports Server (NTRS)

    Barton, Katherine; Abney, Morgan B.

    2011-01-01

    Current air revitalization technology onboard the International Space Station (ISS) cannot provide complete closure of the oxygen and hydrogen loops. This makes re-supply necessary, which is possible for missions in low Earth orbit (LEO) like the ISS, but unviable for long term space missions outside LEO. In comparison, Bosch technology reduces carbon dioxide with hydrogen, traditionally over a steel wool catalyst, to create water and solid carbon. The Bosch product water can then be fed to the oxygen generation assembly to produce oxygen for crew members and hydrogen necessary to reduce more carbon dioxide. Bosch technology can achieve complete oxygen loop closure, but has many undesirable factors that result in a high energy, mass, and volume system. Finding a different catalyst with an equal reaction rate at lower temperatures with less catalyst mass and longer lifespan would make a Bosch flight system more feasible. Developmental testing of alternative catalysts for the Bosch has been performed using the Horizontal Bosch Test Stand. Nickel foam, nickel shavings, and cobalt shavings were tested at 500 C and compared to the original catalyst, steel wool. This paper presents data and analysis on the performance of each catalyst tested at comparable temperatures and recycle flow rates.

  12. Catalyst deactivation in residue hydrocracking

    SciTech Connect

    Oballa, M.C.; Wong, C.; Krzywicki, A.

    1994-12-31

    The existence of a computer-controlled bench scale hydrocracking units at the authors site has made cheaper the non-stop running of experiments for long periods of time. It was, therefore possible to show, at minimal costs, when three hydrocracking catalysts in service reach their maximum lifetime. Different parameters which are helpful for catalyst life and activity predictions were calculated, e.g., relative catalyst age and the effectiveness factor. Experimental results compared well with model, giving them the minimum and maximum catalyst lifetime, as well as the deactivation profile with regard to sulfur and metals removal. Reaction rate constants for demetallization and desulfurization were also determined. Six commercial catalysts were evaluated at short term runs and the three most active were used for long term runs. Out of three catalysts tested for deactivation at long term runs, it was possible to choose one whose useful life was higher than the others. All runs were carried out in a Robinson-Mahoney continuous flow stirred tank reactor, using 50/50 volumetric mixture of Cold Lake/Lloydminster atmospheric residue and NiMo/Al{sub 2}O{sub 3} catalyst.

  13. Ceramic catalyst materials

    SciTech Connect

    Sault, A.G.; Gardner, T.J.; Hanprasopwattanna, A.; Reardon, J.; Datye, A.K.

    1995-08-01

    Hydrous titanium oxide (HTO) ion-exchange materials show great potential as ceramic catalyst supports due to an inherently high ion-exchange capacity which allows facile loading of catalytically active transition metal ions, and an ability to be cast as thin films on virtually any substrate. By coating titania and HTO materials onto inexpensive, high surface area substrates such as silica and alumina, the economics of using these materials is greatly improved, particularly for the HTO materials, which are substantially more expensive in the bulk form than other oxide supports. In addition, the development of thin film forms of these materials allows the catalytic and mechanical properties of the final catalyst formulation to be separately engineered. In order to fully realize the potential of thin film forms of titania and HTO, improved methods for the deposition and characterization of titania and HTO films on high surface area substrates are being developed. By varying deposition procedures, titania film thickness and substrate coverage can be varied from the submonolayer range to multilayer thicknesses on both silica and alumina. HTO films can also be formed, but the quality and reproducibility of these films is not nearly as good as for pure titania films. The films are characterized using a combination of isopropanol dehydration rate measurements, point of zero charge (PZC) measurements, BET surface area, transmission electron microscopy (TEM), and elemental analysis. In order to assess the effects of changes in film morphology on catalytic activity, the films are being loaded with MoO{sub 3} using either incipient wetness impregnation or ion-exchange of heptamolybdate anions followed by calcining. The MoO{sub 3} is then sulfided to form MOS{sub 2}, and tested for catalytic activity using pyrene hydrogenation and dibenzothiophene (DBT) desulfurization, model reactions that simulate reactions occurring during coal liquefaction.

  14. Emission Abatement System

    DOEpatents

    Bromberg, Leslie; Cohn, Daniel R.; Rabinovich, Alexander

    2003-05-13

    Emission abatement system. The system includes a source of emissions and a catalyst for receiving the emissions. Suitable catalysts are absorber catalysts and selective catalytic reduction catalysts. A plasma fuel converter generates a reducing gas from a fuel source and is connected to deliver the reducing gas into contact with the absorber catalyst for regenerating the catalyst. A preferred reducing gas is a hydrogen rich gas and a preferred plasma fuel converter is a plasmatron. It is also preferred that the absorber catalyst be adapted for absorbing NO.sub.x.

  15. Development of GREET Catalyst Module

    SciTech Connect

    Wang, Zhichao; Dunn, Jennifer B.; Cronauer, Donald C.

    2014-09-01

    Catalysts are critical inputs for many pathways that convert biomass into biofuels. Energy consumption and greenhouse gas (GHG) emissions during the production of catalysts and chemical inputs influence the life-cycle energy consumption, and GHG emissions of biofuels and need to be considered in biofuel life-cycle analysis (LCA). In this report, we develop energy and material flows for the production of three different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5]) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module. They were selected because they are consumed in existing U.S. Department of Energy (DOE) analyses of biofuel processes. For example, a thermochemical ethanol production pathway (indirect gasification and mixed alcohol synthesis) developed by the National Renewable Energy Laboratory (NREL) uses olivine, DEPG, and tar reforming and alcohol synthesis catalysts (Dutta et al., 2011). ZSM-5 can be used in biofuel production pathways such as catalytic upgrading of sugars into hydrocarbons (Biddy and Jones, 2013). Other uses for these compounds and catalysts are certainly possible. In this report, we document the data sources and methodology we used to develop material and energy flows for the catalysts and compounds in the GREET catalyst module. In Section 2 we focus on compounds used in the model Dutta et al. (2011) developed. In Section 3, we report material and energy flows associated with ZSM-5 production. Finally, in Section 4, we report results.

  16. Toward efficient asymmetric carbon-carbon bond formation: continuous flow with chiral heterogeneous catalysts.

    PubMed

    Tsubogo, Tetsu; Yamashita, Yasuhiro; Kobayashi, Shū

    2012-10-22

    A chiral Ca catalyst based on CaCl(2) with a chiral ligand was developed and applied to the asymmetric 1,4-addition of 1,3-dicarbonyl compounds to nitroalkenes as a model system. To address product inhibition issues, the Ca catalyst was applied to continuous flow with a chiral heterogeneous catalyst. The continuous flow system using a newly synthesized, polymer-supported Pybox was successfully employed, and the TON was improved 25-fold compared with those of the previous Ca(OR)(2) catalysts.

  17. On-demand Hydrogen Production from Organosilanes at Ambient Temperature Using Heterogeneous Gold Catalysts

    PubMed Central

    Mitsudome, Takato; Urayama, Teppei; Kiyohiro, Taizo; Maeno, Zen; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi

    2016-01-01

    An environmentally friendly (“green”), H2-generation system was developed that involved hydrolytic oxidation of inexpensive organosilanes as hydrogen storage materials with newly developed heterogeneous gold nanoparticle catalysts. The gold catalyst functioned well at ambient temperature under aerobic conditions, providing efficient production of pure H2. The newly developed size-selective gold nanoparticle catalysts could be separated easily from the reaction mixture containing organosilanes, allowing an on/off-switchable H2-production by the introduction and removal of the catalyst. This is the first report of an on/off-switchable H2-production system employing hydrolytic oxidation of inexpensive organosilanes without requiring additional energy. PMID:27883063

  18. On-demand Hydrogen Production from Organosilanes at Ambient Temperature Using Heterogeneous Gold Catalysts

    NASA Astrophysics Data System (ADS)

    Mitsudome, Takato; Urayama, Teppei; Kiyohiro, Taizo; Maeno, Zen; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi

    2016-11-01

    An environmentally friendly (“green”), H2-generation system was developed that involved hydrolytic oxidation of inexpensive organosilanes as hydrogen storage materials with newly developed heterogeneous gold nanoparticle catalysts. The gold catalyst functioned well at ambient temperature under aerobic conditions, providing efficient production of pure H2. The newly developed size-selective gold nanoparticle catalysts could be separated easily from the reaction mixture containing organosilanes, allowing an on/off-switchable H2-production by the introduction and removal of the catalyst. This is the first report of an on/off-switchable H2-production system employing hydrolytic oxidation of inexpensive organosilanes without requiring additional energy.

  19. Developing physicians as catalysts for change.

    PubMed

    George, Aaron E; Frush, Karen; Michener, J Lloyd

    2013-11-01

    Failures in care coordination are a reflection of larger systemic shortcomings in communication and in physician engagement in shared team leadership. Traditional medical care and medical education neither focus on nor inspire responses to the challenges of coordinating care across episodes and sites. The authors suggest that the absence of attention to gaps in the continuum of care has led physicians to attempt to function as the glue that holds the health care system together. Further, medical students and residents have little opportunity to provide feedback on care processes and rarely receive the training and support they need to assess and suggest possible improvements.The authors argue that this absence of opportunity has driven cynicism, apathy, and burnout among physicians. They support a shift in culture and medical education such that students and residents are trained and inspired to act as catalysts who initiate and expedite positive changes. To become catalyst physicians, trainees require tools to partner with patients, staff, and faculty; training in implementing change; and the perception of this work as inherent to the role of the physician.The authors recommend that medical schools consider interprofessional training to be a necessary component of medical education and that future physicians be encouraged to grow in areas outside the "purely clinical" realm. They conclude that both physician catalysts and teamwork are essential for improving care coordination, reducing apathy and burnout, and supporting optimal patient outcomes.

  20. Chalcogen catalysts for polymer electrolyte fuel cell

    DOEpatents

    Zelenay, Piotr; Choi, Jong-Ho; Alonso-Vante, Nicolas; Wieckowski, Andrzej; Cao, Dianxue

    2010-08-24

    A methanol-tolerant cathode catalyst and a membrane electrode assembly for fuel cells that includes such a cathode catalyst. The cathode catalyst includes a support having at least one transition metal in elemental form and a chalcogen disposed on the support. Methods of making the cathode catalyst and membrane electrode assembly are also described.