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Sample records for model three-way catalysts

  1. Characterization of three-way automotive catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kenik, E.A.; More, K.L. [Oak Ridge National Laboratory, TN (United States); LaBarge, W. [General Motors-AC Delco Systems, Flint, MI (United States)] [and others

    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.

  2. Characterization of three-way automotive catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kenik, E.A.; More, K.L. [Oak Ridge National Lab., TN (United States); LaBarge, W. [Delphi Automotive Systems, Flint, MI (United States)] [and others

    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.

  3. Detailed surface reaction mechanism in a three-way catalyst.

    Science.gov (United States)

    Chatterjee, D; Deutschmann, O; Warnatz, J

    2001-01-01

    Monolithic three-way catalysts are applied to reduce the emission of combustion engines. The design of such a catalytic converter is a complex process involving the optimization of different physical and chemical parameters (in the simplest case, e.g., length, cell densities or metal coverage of the catalyst). Numerical simulation can be used as an effective tool for the investigation of the catalytic properties of a catalytic converter and for the prediction of the performance of the catalyst. To attain this goal, a two-dimensional flow-field description is coupled with a detailed surface reaction model (gas-phase reactions can be neglected in three-way catalysts). This surface reaction mechanism (with C3H6 taken as representative of unburnt hydrocarbons) was developed using sub-mechanisms recently developed for hydrogen, carbon monoxide and methane oxidation, literature values for C3H6 oxidation, and estimates for the remaining unknown reactions. Results of the simulation of a monolithic single channel are used to validate the surface reaction mechanism. The performance of the catalyst was simulated under lean, nearly stoichiometric and rich conditions. For these characteristic conditions, the oxidation of propene and carbon monoxide and the reduction of NO on a typical Pt/Rh coated three-way catalyst were simulated as a function of temperature. The numerically predicted conversion data are compared with experimentally measured data. The simulation further reveals the coupling between chemical reactions and transport processes within the monolithic channel.

  4. Part I: A Comparative Thermal Aging Study on the Regenerability of Rh/Al2O3 and Rh/CexOy-ZrO2 as Model Catalysts for Automotive Three Way Catalysts

    Directory of Open Access Journals (Sweden)

    Qinghe Zheng

    2015-10-01

    Full Text Available The rhodium (Rh component in automotive three way catalysts (TWC experiences severe thermal deactivation during fuel shutoff, an engine mode (e.g., at downhill coasting used for enhancing fuel economy. In a subsequent switch to a slightly fuel rich condition, in situ catalyst regeneration is accomplished by reduction with H2 generated through steam reforming catalyzed by Rh0 sites. The present work reports the effects of the two processes on the activity and properties of 0.5% Rh/Al2O3 and 0.5% Rh/CexOy-ZrO2 (CZO as model catalysts for Rh-TWC. A very brief introduction of three way catalysts and system considerations is also given. During simulated fuel shutoff, catalyst deactivation is accelerated with increasing aging temperature from 800 °C to 1050 °C. Rh on a CZO support experiences less deactivation and faster regeneration than Rh on Al2O3. Catalyst characterization techniques including BET surface area, CO chemisorption, TPR, and XPS measurements were applied to examine the roles of metal-support interactions in each catalyst system. For Rh/Al2O3, strong metal-support interactions with the formation of stable rhodium aluminate (Rh(AlO2y complex dominates in fuel shutoff, leading to more difficult catalyst regeneration. For Rh/CZO, Rh sites were partially oxidized to Rh2O3 and were relatively easy to be reduced to active Rh0 during regeneration.

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

    Science.gov (United States)

    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.

  6. Quaternary Oxide of Cerium, Terbium, Praseodymium and Zirconium for Three-Way Catalysts

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Oxygen storagecapacity (OSC), oxygen buffer capacity (OBC), X-ray diffraction and electron diffraction pattern, high resolution electron microscopy were used to study the quaternary oxides, i.e., of Ce, Tb, Pr and Zr. (Ce0.6Tb0.2Zr0.2O2-δ and Ce0.6Pr0.2Zr0.2O2-δ). OSC and OBC data indicate that these oxides have very good oxygen transfer capacity (OTC) and their pseudo-solid solutions exhibit fluorite-type structure. These oxides may act as a good candidate for three-way catalysts (TWC).

  7. Carbon monoxide trend, meteorology, and three-way catalysts in Mexico City.

    Science.gov (United States)

    Riveros, H G; Alba, A; Ovalle, P; Silva, B; Sandoval, E

    1998-05-01

    From the analysis of data of the Inspection/Maintenance (I/M) program, and of the long-term trend of ambient CO concentrations in Mexico City, it is inferred that three-way catalysts (TWCs) have a 45% efficiency, well below the expected 90% value. The most probable causes are sulfur poisoning, lead contamination, and ceramic breakage due to bumps and potholes on the streets. Also, we have found a ratio between the average daily peak value of atmospheric CO and gasoline consumption: (11 +/- 1) ppbCO/MLm (million liters of gasoline per month) in 1988 decaying to (10 +/- 1) in 1991 for Mexico City before the introduction of TWCs. In addition, we found a correlation between the monthly averages of CO daily peak and meteorological variables, explaining most of the seasonal changes using only the intensity of the inversion layer and surface wind speed.

  8. From trash to resource: recovered-Pd from spent three-way catalysts as a precursor of an effective photo-catalyst for H 2 production

    KAUST Repository

    Gombac, V.

    2016-01-06

    The successful production of a nanostructured and highly dispersed Pd-TiO2 photo-catalyst, using [Pd(Me2dazdt)2](I3)2 (Me2dazdt = N,N′-dimethyl-perhydrodiazepine-2,3-dithione) salt, obtained through the selective and safe recovery of palladium from model exhaust three-way catalysts (TWCs), is reported here. The photo-catalyst prepared by the impregnation/photo-reduction of palladium on the support showed improved performance in H2 production from methanol and in glycerol photo-reforming compared to reference photo-catalysts obtained from conventional Pd-salts. The reported results represent a case of successful palladium “recovery and re-employment” and thus constitute an example of green chemistry by providing, in one route, the environmentally friendly recovery of a critical metal and its employment in the renewable energy field.

  9. Properties of and algorithms for fitting three-way component models with offset terms

    NARCIS (Netherlands)

    Kiers, Henk A. L.

    2006-01-01

    Prior to a three-way component analysis of a three-way data set, it is customary to preprocess the data by centering and/or rescaling them. Harshman and Lundy (1984) considered that three-way data actually consist of a three-way model part, which in fact pertains to ratio scale measurements, as welt

  10. Novel high-temperature reactors for in situ studies of three-way catalysts using turbo-XAS.

    Science.gov (United States)

    Guilera, Gemma; Gorges, Bernard; Pascarelli, Sakura; Vitoux, Hugo; Newton, Mark A; Prestipino, Carmelo; Nagai, Yasutaka; Hara, Naoyuki

    2009-09-01

    Two novel high-temperature reactors for in situ X-ray absorption spectroscopy (XAS) measurements in fluorescence are presented, each of them being optimized for a particular purpose. The powerful combination of these reactors with the turbo-XAS technique used in a dispersive-XAS beamline permits the study of commercial three-way catalysts under realistic gas composition and temporal conditions.

  11. Promoter of (Ce-Zr)O2 Solid Solution Modified by Praseodymia in Three-Way Catalysts

    Institute of Scientific and Technical Information of China (English)

    汪文栋; 林培琰; 孟明; 伏义路; 胡天斗; 谢亚宁; 刘涛

    2003-01-01

    The three-way catalysts (TWCs) promoters (Ce-Zr)O2, (Pr-Ce-Zr)O2 and (Pr-Zr)O2 were prepared by sol-gel like method. They were characterized by XRD, EXAFS and BET surface area determination. The reduction features of the promoters were measured by temperature-programmed reduction (TPR) of H2 to access the potential for the promoters containing praseodymia as oxygen storage component in three-way catalyst. The (Pr-Zr)O2 cubic solid solution is formed at high temperature up to 800 ℃, which makes it more reducible than the (Ce-Zr)O2 solid solution. For the (Pr-Ce-Zr)O2 samples, the ternary solid solution plays an important role in the reduction process. The performance of the three-way catalysts with fully formulated Pt, Pd and Rh is proceeded by using both light-off temperature under a stoichiometric gas composition and the conversion of CO, C3H6 and NO under changing air/fuel ratio at a constant reaction temperature 400 ℃. The results indicate that a small amount of praseodymia doping into (Ce-Zr)O2 favors the light-off temperature of C3H6 and NO, and all the catalysts containing praseodymia obviously exhibits enhanced width of S value for NO conversion at lean region (S≥1.00).

  12. Structured Perovskite-Based Catalysts and Their Application as Three-Way Catalytic Converters—A Review

    Directory of Open Access Journals (Sweden)

    Sylvain Keav

    2014-07-01

    Full Text Available Automotive Three-Way Catalysts (TWC were introduced more than 40 years ago. Despite that, the development of a sustainable TWC still remains a critical research topic owing to the increasingly stringent emission regulations together with the price and scarcity of precious metals. Among other material classes, perovskite-type oxides are known to be valuable alternatives to conventionally used TWC compositions and have demonstrated to be suitable for a wide range of automotive applications, ranging from TWC to Diesel Oxidation Catalysts (DOC, from NOx Storage Reduction catalysts (NSR to soot combustion catalysts. The interest in these catalysts has been revitalized in the past ten years by the introduction of the concept of catalyst regenerability of perovskite-based TWC, which is in principle well applicable to other catalytic processes as well, and by the possibility to reduce the amounts of critical elements, such as precious metals without seriously lowering the catalytic performance. The aim of this review is to show that perovskite-type oxides have the potential to fulfil the requirements (high activity, stability, and possibility to be included into structured catalysts for implementation in TWC.

  13. In operando Detection of Three-Way Catalyst Aging by a Microwave-Based Method: Initial Studies

    Directory of Open Access Journals (Sweden)

    Gregor Beulertz

    2015-07-01

    Full Text Available Initial studies on aging detection of three way catalysts with a microwave cavity perturbation method were conducted. Two physico-chemical effects correlate with the aging state. At high temperatures, the resonance frequencies for oxidized catalysts (λ = 1.02 are not influenced by aging, but are significantly affected by aging in the reduced case (λ = 0.98. The catalyst aging state can therefore potentially be inferred from the resonance frequency differences between reduced and oxidized states or from the resonance frequency amplitudes during lambda oscillations. Secondly, adsorbed water at low temperatures strongly affects the resonance frequencies. Light-off experiment studies showed that the resonance frequency depends on the aging state at temperatures below the oxygen storage light-off. These differences were attributed to different water sorption capabilities of differently aged samples due to a surface area decrease with proceeding aging. In addition to the aging state, the water content in the feed gas and the temperature affect the amount of adsorbed water, leading to different integral electrical material properties of the catalyst and changing the resonance properties of the catalyst-filled canning. The classical aging-related properties of the catalyst (oxygen storage capacity, oxygen storage light-off, surface area, agreed very well with data obtained by the microwave-based method.

  14. Steam effects over Pd/Ce0.67Zr0.33O2 three-way catalyst

    Institute of Scientific and Technical Information of China (English)

    WANG Jianqiang; SHEN Meiqing; WANG Jun; Wang Wulin

    2011-01-01

    In the purification process of automobile exhaust, existing water plays an important role as an oxidant, which converts CO and hydrocarbons (HCs) by the water-gas shift (WGS) and the steam reforming (SR) reactions, respectively, especially at high temperatures. Meanwhile it is major component of the exhaust which can affect significantly the thermal stability of the three-way catalyst. Activity experiments were carried out close to the real operation conditions (GHSV, concentration, etc.) with a Pd/Ce0.67Zr0.33O2 catalyst supplying information on the CO and C3H8 oxidation reactions in feedstream formed by different reactant combinations. The obtained results showed that the activity of the CO and C3Hs oxidation was promoted by the addition of steam due to the WGS and SR reactions. The WGS and SR reaction were competitive under oxygen-lean conditions. The kinetic analysis was considered for WGS and SR reactions.

  15. A nanometric Rh overlayer on a metal foil surface as a highly efficient three-way catalyst

    Science.gov (United States)

    Misumi, Satoshi; Yoshida, Hiroshi; Hinokuma, Satoshi; Sato, Tetsuya; Machida, Masato

    2016-07-01

    Pulsed arc-plasma (AP) deposition of an Rh overlayer on an Fe–Cr–Al stainless steel foil produced a composite material that exhibited high activity for automotive three-way catalysis (TWC). The AP pulses deposited metallic Rh nanoparticles 1–3 nm in size, whose density on the surface increased with the number of pulses. This led to coalescence and grain growth on the foil surface and the eventual formation of a uniform two-dimensional Rh overlayer. Full coverage of the 51 μm-thick flat foil by a 3.2 nm-thick Rh overlayer was achieved after 1,000 pulses. A simulated TWC reaction using a miniature honeycomb fabricated using flat and corrugated foils with the Rh overlayers exhibited successful light-off at a practical gaseous hourly space velocity of 1.2 × 105 h‑1. The turnover frequency for the NO–CO reaction over the metallic honeycomb catalyst was ca. 80-fold greater than that achieved with a reference Rh/ZrO2-coated cordierite honeycomb prepared using a conventional wet impregnation and slurry coating procedure. Despite the nonporosity and low surface area of the foil-supported Rh overlayer compared with conventional powder catalysts (Rh/ZrO2), it is a promising alternative design for more efficient automotive catalysts that use less Rh loading.

  16. A nanometric Rh overlayer on a metal foil surface as a highly efficient three-way catalyst

    Science.gov (United States)

    Misumi, Satoshi; Yoshida, Hiroshi; Hinokuma, Satoshi; Sato, Tetsuya; Machida, Masato

    2016-01-01

    Pulsed arc-plasma (AP) deposition of an Rh overlayer on an Fe–Cr–Al stainless steel foil produced a composite material that exhibited high activity for automotive three-way catalysis (TWC). The AP pulses deposited metallic Rh nanoparticles 1–3 nm in size, whose density on the surface increased with the number of pulses. This led to coalescence and grain growth on the foil surface and the eventual formation of a uniform two-dimensional Rh overlayer. Full coverage of the 51 μm-thick flat foil by a 3.2 nm-thick Rh overlayer was achieved after 1,000 pulses. A simulated TWC reaction using a miniature honeycomb fabricated using flat and corrugated foils with the Rh overlayers exhibited successful light-off at a practical gaseous hourly space velocity of 1.2 × 105 h−1. The turnover frequency for the NO–CO reaction over the metallic honeycomb catalyst was ca. 80-fold greater than that achieved with a reference Rh/ZrO2-coated cordierite honeycomb prepared using a conventional wet impregnation and slurry coating procedure. Despite the nonporosity and low surface area of the foil-supported Rh overlayer compared with conventional powder catalysts (Rh/ZrO2), it is a promising alternative design for more efficient automotive catalysts that use less Rh loading. PMID:27388976

  17. A nanometric Rh overlayer on a metal foil surface as a highly efficient three-way catalyst.

    Science.gov (United States)

    Misumi, Satoshi; Yoshida, Hiroshi; Hinokuma, Satoshi; Sato, Tetsuya; Machida, Masato

    2016-07-08

    Pulsed arc-plasma (AP) deposition of an Rh overlayer on an Fe-Cr-Al stainless steel foil produced a composite material that exhibited high activity for automotive three-way catalysis (TWC). The AP pulses deposited metallic Rh nanoparticles 1-3 nm in size, whose density on the surface increased with the number of pulses. This led to coalescence and grain growth on the foil surface and the eventual formation of a uniform two-dimensional Rh overlayer. Full coverage of the 51 μm-thick flat foil by a 3.2 nm-thick Rh overlayer was achieved after 1,000 pulses. A simulated TWC reaction using a miniature honeycomb fabricated using flat and corrugated foils with the Rh overlayers exhibited successful light-off at a practical gaseous hourly space velocity of 1.2 × 10(5) h(-1). The turnover frequency for the NO-CO reaction over the metallic honeycomb catalyst was ca. 80-fold greater than that achieved with a reference Rh/ZrO2-coated cordierite honeycomb prepared using a conventional wet impregnation and slurry coating procedure. Despite the nonporosity and low surface area of the foil-supported Rh overlayer compared with conventional powder catalysts (Rh/ZrO2), it is a promising alternative design for more efficient automotive catalysts that use less Rh loading.

  18. Preparation of ceria-zirconia by modified coprecipitation method and its supported Pd-only three-way catalyst.

    Science.gov (United States)

    Lan, Li; Chen, Shanhu; Cao, Yi; Zhao, Ming; Gong, Maochu; Chen, Yaoqiang

    2015-07-15

    A CeO2-ZrO2 compound with mixed phase composition (CZ4) was prepared by modified co-precipitation method, and for comparison, single-phase Ce(0.2)Zr(0.8)O2, Ce(0.5)Zr(0.5)O2 and Ce(0.8)Zr(0.2)O2 were synthesized via simultaneous co-precipitation method. The textural, structural and redox properties, together with the catalytic performance of the supported Pd-only three-way catalysts were investigated systematically. The results revealed that the generation of numerous interface sites in Pd/CZ4 due to its mixed phase composition (as confirmed by TEM observation) had a positive influence on modifying its structural, redox properties and thermal stability. The XRD and Raman results revealed that the highest structural stability was obtained by Pd/CZ4 with negligible lattice variation and slightest grain growth after aging treatment. The XPS analysis demonstrated that the compositional heterogeneity of Pd/CZ4 could facilitate the formation of Ce(3+), and was beneficial to preserve high dispersion of Pd as well as maintain Pd at a more oxidized state. The H2-TPR and oxygen storage capacity measurements indicated that Pd/CZ4 possessed highest reduction ability as well as largest oxygen storage capacity regardless of thermal aging treatment. And consequently Pd/CZ4 exhibited improved three-way catalytic activity compared with the catalysts supported on single-phase Ce(x)Zr(1-x)O2 both before and after thermal aging treatment.

  19. Improved activity and durability of Rh-based three-way catalyst under diverse aging atmospheres by ZrO2 support.

    Science.gov (United States)

    Cao, Yidan; Ran, Rui; Wu, Xiaodong; Zhao, Baohuai; Weng, Duan

    2017-02-01

    The catalytic activity and durability of Rh/ZrO2 catalyst were investigated compared with Rh/Al2O3 catalyst under diverse aging atmospheres, including lean, rich and lean-rich cyclic aging atmospheres, to simulate the real working conditions of three-way catalyst. Oxidation states and microstructures of rhodium species were investigated to correlate with the catalytic performance of the catalysts. The catalytic performance and durability of the Rh catalyst under diverse aging atmospheres were drastically enhanced by ZrO2 support. ZrO2 support was confirmed to be able to effectively inhibit rhodium sintering even under diverse aging conditions. It can also successfully keep Rh species in an active low-valence state on the surface of the catalyst. The superiority of ZrO2 support compared to Al2O3 was verified by the Rh-based monolith catalyst.

  20. Chemical and toxicological properties of emissions from CNG transit buses equipped with three-way catalysts compared to lean-burn engines and oxidation catalyst technologies

    Science.gov (United States)

    Yoon, Seungju; Hu, Shaohua; Kado, Norman Y.; Thiruvengadam, Arvind; Collins, John F.; Gautam, Mridul; Herner, Jorn D.; Ayala, Alberto

    2014-02-01

    Chemical and toxicological properties of emissions from compressed natural gas (CNG) fueled transit buses with stoichiometric combustion engines and three-way catalyst (TWC) exhaust control systems were measured using a chassis dynamometer testing facility and compared to the data from earlier CNG engine and exhaust control technologies. Gaseous and particulate matter emissions from buses with stoichiometric engines and TWC were significantly lower than the emissions from buses with lean-burn engines. Carbonyls and volatile organic compounds (VOCs) from buses with stoichiometric engines and TWC were lower by more than 99% compared to buses with lean-burn engines. Elemental and organic carbons (EC and OC), polycyclic aromatic hydrocarbons (PAHs), and trace elements from buses with stoichiometric engines and TWC were effectively controlled and significantly lower than the emissions from buses with lean-burn engines. Potential mutagenicity measured using a microsuspension modification of the Salmonella/microsome assay was lower by more than 99% for buses with stoichiometric engines and TWC, compared to buses with lean-burn engines and OxC.

  1. Preparation and properties of nanophase (Ce, Zr, PrO2-doped alumina coating on cordierite ceramic honeycomb for three-way catalysts

    Directory of Open Access Journals (Sweden)

    Jiuying Tian

    2012-03-01

    Full Text Available Nanophase (Ce, Zr, PrO2-doped alumina coatings were prepared by impregnating the cordierite ceramic honeycomb in the sol or in the slurry of already calcined powder, respectively. The effects of preparation methods on the crystal phase, texture, oxygen storage capacity (OSC, reducibility, surface morphology and thermal stability of coatings were investigated by X-ray diffraction (XRD, the Brunauer Emmet Teller (BET method, the oxygen pulsing technique, H2-temperature-programmed reduction (H2-TPR and scanning electron microscopy (SEM. These nanophase (Ce, Zr, PrO2-doped alumina coatings were used as supports to prepare Pd-only three-way catalysts, and evaluated with respect to catalytic activities. The results indicate that the nanophase (Ce, Zr, PrO2-doped alumina coatings prepared by the two methods have high thermal stability. However, the coating derived from the sol shows better crystalline structure, texture, reducibility and oxygen storage capacity than the coating derived from the slurry. SEM observation shows that the morphology of the coating derived from the sol is uniform and smooth. The Pd-only catalyst derived from the sol exhibits high three-way catalytic activity at low temperature and thermal stability, suggesting a great potential for applications.

  2. Preparation and properties of nanophase (Ce, Zr, Pr)O{sub 2}-doped alumina coating on cordierite ceramic honeycomb for three-way catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Jiuying; Lu, Jusheng [School of Chemistry and Chemical Engineering, Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Xuzhou Normal University, Xuzhou P.R. (China)

    2012-01-15

    Nanophase (Ce, Zr, Pr)O{sub 2}-doped alumina coatings were prepared by impregnating the cordierite ceramic honeycomb in the sol or in the slurry of already calcined powder, respectively. The effects of preparation methods on the crystal phase, texture, oxygen storage capacity (OSC), reducibility, surface morphology and thermal stability of coatings were investigated by X-ray diffraction (XRD), the Brunauer Emmet Teller (BET) method, the oxygen pulsing technique, H2-temperature-programmed reduction (H2-TPR) and scanning electron microscopy (SEM). These nanophase (Ce, Zr, Pr)O{sub 2}-doped alumina coatings were used as supports to prepare Pd-only three-way catalysts, and evaluated with respect to catalytic activities. The results indicate that the nanophase (Ce, Zr, Pr)O{sub 2}-doped alumina coatings prepared by the two methods have high thermal stability. However, the coating derived from the sol shows better crystalline structure, texture, reducibility and oxygen storage capacity than the coating derived from the slurry. SEM observation shows that the morphology of the coating derived from the sol is uniform and smooth. The Pd-only catalyst derived from the sol exhibits high three-way catalytic activity at low temperature and thermal stability, suggesting a great potential for applications. (author)

  3. Study of Pt-Rh/CeO2-ZrO2-MxOy (M = Y, La)/Al2O3 three-way catalysts

    Science.gov (United States)

    Jiaxiu, Guo; Zhonghua, Shi; Dongdong, Wu; Huaqiang, Yin; Maochu, Gong; Yaoqiang, Chen

    2013-05-01

    CeO2-ZrO2-MxOy (M = Y; La) mixed oxides, prepared by co-precipitation method and characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), Raman spectra (RM) and oxygen pulse reaction, were comparatively investigated to elucidate the combinational effects of Y and/or La oxide promoters on the catalytic activity and anti-aging performance of monolithic cordierite honeycomb catalysts with low Pt and Rh content. The catalytic activities, water-gas shift (WGS) and steam reforming reaction (SR) were studied under a simulated gas mixture. The catalysts were also characterized by H2-temperature-programmed reduction (H2-TPR) and O2-temperature-programmed desorption (O2-TPD). The results showed that the prepared CeO2-ZrO2-MxOy oxides have a face-centered cubic fluorite structure and are nanosize. La3+ ions can significantly improve thermal stability and efficiently retard CeO2-ZrO2 crystal sintering and growth. Doped CeO2-ZrO2 with Y3+ and La3+ has 105 and 60 m2/g surface area and 460 and 390 μmol/g OSC before and after aging. The T50 of fresh Pt-Rh/CZYL/LA is 170 °C for CO, 222 °C for C3H8 and 189 °C for NO, and shift to 205, 262 and 228 °C after hydrothermal aging, which are better than those of Pt-Rh/CZY/LA or Pt-Rh/CZL/LA. WGS and SR are relate to the OSC of oxygen storage materials and absorbed oxygen species on the catalyst surface and affect the three-way catalytic activities of catalysts. The reductive property of noble metals and the dissociatively adsorbed O2 on the surface of catalysts are closely related to the catalytic activities.

  4. Influence of Ce0.35Zr0.55Y0.10 Solid Solution on Performance of Pt-Rh Three-Way Catalysts

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Ce0.35Zr0.55Y0.10 solid solution was prepared by co-precipitation technique and characterized by specific surface area measurements (BET) and X-ray diffraction (XRD). Ce0.35Zr0.55Y0.10 was used to prepare low Pt-Rh three-way catalyst (TWC), and its influence on the performance of TWC was investigated. The results revealed that Ce0.35Zr0.55Y0.10 had a cubic structure similar to Ce0.50Zr0.50O2 and its specific surface area can maintain higher than Ce0.50Zr0.50O2 after 1000 ℃ calcination for 5 h. Being hydrothermal aged at 1000 ℃ for 5 h, the catalyst containing Ce0.35Zr0.55Y0.10 still exhibited higher conversion of C3H8, CO and NO and lower light-off temperature in comparison with Ce0.50Zr0.50O2 TWC.

  5. Burnout Disrupts Anxiety Buffer Functioning Among Nurses: A Three-Way Interaction Model

    Science.gov (United States)

    Trifiletti, Elena; Pedrazza, Monica; Berlanda, Sabrina; Pyszczynski, Tom

    2017-01-01

    Over the last 40 years, job burnout has attracted a great deal of attention among researchers and practitioners and, after decades of research and interventions, it is still regarded as an important issue. With the aim of extending the Anxiety Buffer Disruption Theory (ABDT), in this paper we argue that high levels of burnout may disrupt the anxiety buffer functioning that protects people from death concerns. ABDT was developed from Terror Management Theory (TMT). According to TMT, reminders of one’s mortality are an essential part of humans’ daily experience and have the potential to awake paralyzing fear and anxiety. In order to cope with death concerns, people typically activate an anxiety-buffering system centered on their cultural worldview and self-esteem. Recent ABDT research shows that individuals with post-traumatic stress disorder are unable to activate such anxiety buffering defenses. In line with these results, we hypothesized that the burnout syndrome may have similar effects, and that individuals with higher levels of burnout will be less likely to activate an anxiety buffering response when their mortality is made salient. Participants were 418 nurses, who completed a questionnaire including: a mortality salience (MS) manipulation, a delay manipulation, and measures of burnout, work-related self-efficacy, and representation of oneself as a valuable caregiver. Nurses are daily exposed both to the risk of burnout and to mortality reminders, and thus constituted an ideal population for this study. In line with an anxiety buffer disruption hypothesis, we found a significant three-way interaction between burnout, MS and delay. Participants with lower levels of burnout reported higher levels of self-efficacy and a more positive representation as caregivers in the MS condition compared to the control condition, when there was a delay between MS manipulation and the assessment of the dependent measures. The difference was non-significant for participants

  6. Burnout Disrupts Anxiety Buffer Functioning Among Nurses: A Three-Way Interaction Model.

    Science.gov (United States)

    Trifiletti, Elena; Pedrazza, Monica; Berlanda, Sabrina; Pyszczynski, Tom

    2017-01-01

    Over the last 40 years, job burnout has attracted a great deal of attention among researchers and practitioners and, after decades of research and interventions, it is still regarded as an important issue. With the aim of extending the Anxiety Buffer Disruption Theory (ABDT), in this paper we argue that high levels of burnout may disrupt the anxiety buffer functioning that protects people from death concerns. ABDT was developed from Terror Management Theory (TMT). According to TMT, reminders of one's mortality are an essential part of humans' daily experience and have the potential to awake paralyzing fear and anxiety. In order to cope with death concerns, people typically activate an anxiety-buffering system centered on their cultural worldview and self-esteem. Recent ABDT research shows that individuals with post-traumatic stress disorder are unable to activate such anxiety buffering defenses. In line with these results, we hypothesized that the burnout syndrome may have similar effects, and that individuals with higher levels of burnout will be less likely to activate an anxiety buffering response when their mortality is made salient. Participants were 418 nurses, who completed a questionnaire including: a mortality salience (MS) manipulation, a delay manipulation, and measures of burnout, work-related self-efficacy, and representation of oneself as a valuable caregiver. Nurses are daily exposed both to the risk of burnout and to mortality reminders, and thus constituted an ideal population for this study. In line with an anxiety buffer disruption hypothesis, we found a significant three-way interaction between burnout, MS and delay. Participants with lower levels of burnout reported higher levels of self-efficacy and a more positive representation as caregivers in the MS condition compared to the control condition, when there was a delay between MS manipulation and the assessment of the dependent measures. The difference was non-significant for participants

  7. Microwave-Based Oxidation State and Soot Loading Determination on Gasoline Particulate Filters with Three-Way Catalyst Coating for Homogenously Operated Gasoline Engines

    Directory of Open Access Journals (Sweden)

    Markus Dietrich

    2015-09-01

    Full Text Available Recently, a novel method emerged to determine the oxygen storage degree of three way catalysts (TWC by a microwave-based method. Up to now, this method has been investigated only in lab-scale reactors or under steady state conditions. This work expands those initial studies. A TWC-coated gasoline particulate filter was investigated in a dynamic engine test bench simulating a typical European driving cycle (NEDC. It could be shown that both the oxygen storage degree and the soot loading can be monitored directly, but not simultaneously due to their competitive effects. Under normal driving conditions, no soot accumulation was observed, related to the low raw emissions and the catalytic coating of the filter. For the first time, the quality factor of the cavity resonator in addition to the resonance frequency was used, with the benefit of less cross sensitivity to inconstant temperature and water. Therefore, a temperature dependent calibration of the microwave signal was created and applied to monitor the oxidation state in transient driving cycles. The microwave measurement mirrors the oxidation state determined by lambda probes and can be highly beneficial in start-stop phases (where lambda-probes do not work and to determine the oxygen storage capacity (OSC without unnecessary emissions.

  8. Preparation of FexCe1-xOy solid solution and its application in Pd-only three-way catalysts

    Institute of Scientific and Technical Information of China (English)

    Jianqiang Wang; Meiqing Shen; Jun Wang; Mingshan Cui; Jidong Gao; Jie Ma; Shuangxi Liu

    2012-01-01

    FeOx-CeO2 mixed oxides with increasing Fe/(Ce+Fe) atomic ratio (1-20 mol%) were prepared by sol-gel method and characterized by X-ray powder diffraction (XRD),Brunauer-Emmett-Teller (BET) and Hydrogen temperature-programmed reduction (H2-TPR) techniques.The dynamic oxygen storage capacity (DOSC) was investigated by mass spectrometry with CO/O2 transient pulses.The powder XRD data following Rietveld refinement revealed that the solubility limit of iron oxides in the CeO2 was 5 mol% based on Fe/(Ce+Fe).The lattice parameters experienced a decrease followed by an increase due to the influence of the maximum solubility limit of iron oxides in the CeO2.TPR analysis revealed that Fe introduction into ceria strongly modified the textual and structural properties,which influenced the oxygen handling properties.DOSC results revealed that Ce-based materials containing Fe oxides with multiple valences contribute to the majority of DOSC.The kinetic analysis indicated that the calculated apparent kinetic parameters obey the compensation effect.The three-way catalytic performance for Pd-only catalysts based on the Fe doping support exhibited the redundant iron species separated out of the CeO2 and interacted with the ceria and Pd species on the surface,which seriously influenced the catalytic properties,especially after hydrothermal aging treatment.

  9. A new approach of CeO2 and La2O3 effects on the three-way catalysts containing low precious metals

    Institute of Scientific and Technical Information of China (English)

    WANG, Wen-Dong; ZHANG, Xiao-Peng; MENG, Ming; YU, Shou-Ming; FU, Yi-Lu; LIN, Pei-Yan

    2000-01-01

    A series of three-way catalysts (TWCs), containing a small amount of precious metals ( PMs, including Pt, Pd and Rh ) and a large amount of promoters CeO2 and La2O3, were pre pared with different precursor compotmds and various doped mtaners. Crystal phases, dispersion of cerium and lan thamun, textural structure and thermal stability of the cata lysts were investigated by XRD, XPS and pore parameters de termination. The catalytic performance was studied by the measurements of CO, C3H6 and NO conversions on depen dence of temperature at stoichimetric nunber point (S = 1.00), and from S=0.75 to 1.30 at 280℃C or 340℃C for fresh or aged samples, respectively. The correlation between the catalytic performance and the characteristics of fresh and aged samples were discussed. The results show that the sampie, in which CeO2 and La2Os are doped with mixed oxide powders, possesses poor dispersion and less thermal stability, and the conversions of NO and C3H6 are apparently lower than those of the samples aged at 850℃C. The main reason is due to the ianthamum enriclument on the surface. The precious metals and cerium may be covered and enveloped, and the PMs lo cated on the internal microporous su-face where no cerium and lanthanum exist, are easier to sinter and oxidize. For the sample doped with La(NO3)3 and Ce(NO3)3 aqueous solu tions, high dispersion and thermal stable CeO2-La2O3 solid so lution on all the surface of microporous γ-Al2O3 is identified. The solid solution CeO2-La2O3 also possessed high dispersion in the sample doped with La2O3 powder and Ce(NO3)3 aque ous soltion The last two aged samples keep higher NO eon version at S>1 region.

  10. Part II: Oxidative Thermal Aging of Pd/Al2O3 and Pd/CexOy-ZrO2 in Automotive Three Way Catalysts: The Effects of Fuel Shutoff and Attempted Fuel Rich Regeneration

    Directory of Open Access Journals (Sweden)

    Qinghe Zheng

    2015-10-01

    Full Text Available The Pd component in the automotive three way catalyst (TWC experiences deactivation during fuel shutoff, a process employed by automobile companies for enhancing fuel economy when the vehicle is coasting downhill. The process exposes the TWC to a severe oxidative aging environment with the flow of hot (800 °C–1050 °C air. Simulated fuel shutoff aging at 1050 °C leads to Pd metal sintering, the main cause of irreversible deactivation of 3% Pd/Al2O3 and 3% Pd/CexOy-ZrO2 (CZO as model catalysts. The effect on the Rh component was presented in our companion paper Part I. Moderate support sintering and Pd-CexOy interactions were also experienced upon aging, but had a minimal effect on the catalyst activity losses. Cooling in air, following aging, was not able to reverse the metallic Pd sintering by re-dispersing to PdO. Unlike the aged Rh-TWCs (Part I, reduction via in situ steam reforming (SR of exhaust HCs was not effective in reversing the deactivation of aged Pd/Al2O3, but did show a slight recovery of the Pd activity when CZO was the carrier. The Pd+/Pd0 and Ce3+/Ce4+ couples in Pd/CZO are reported to promote the catalytic SR by improving the redox efficiency during the regeneration, while no such promoting effect was observed for Pd/Al2O3. A suggestion is made for improving the catalyst performance.

  11. Simplicity transformations for three-way arrays with symmetric slices, and applications to Tucker-3 models with sparse core arrays

    NARCIS (Netherlands)

    Tendeiro, Jorge N.; Ten Berge, Jos M.F.; Kiers, Henk A.L.

    2009-01-01

    Tucker three-way PCA and Candecomp/Parafac are two well-known methods of generalizing principal component analysis to three way data. Candecomp/Parafac yields component matrices A (e.g., for subjects or objects), B (e.g., for variables) and C (e.g., for occasions) that are typically unique up to joi

  12. Regeneration of Three-Way Automobile Catalysts using Biodegradable Metal Chelating Agent – S, S-Ethylenediamine Disuccinic Acid (S, S-EDDS)

    Science.gov (United States)

    Regeneration of the activity of three-way catalytic converters (TWCs) was tested for the first time using a biodegradable metal chelating agent (S, S. Ethylenediamine disuccinic acid (S, S-EDDS). The efficiency of this novel environmentally friendly solvent in removing various c...

  13. Steam effects over Pd/Ce0.67Zr0.33O2-Al2O3 three-way catalyst

    Institute of Scientific and Technical Information of China (English)

    WANG Jianqiang; SHEN Meiqing; WANG Jun; GAO Jidong; MA Jie; LIU Shuangxi

    2012-01-01

    Ceria-zirconia-alumina (CZA) solid solution was prepared by sol-gel method in the presem study.0.5 wt.% Pd supported on CZA was prepared by incipient wetness impregnation.The steam effects for CO and C3H8 oxidation,three-way catalytic activity and stoichiometric window property were studied.The light-off temperature of the CO oxidation reaction shifted to a lower temperature due to the water-gas shift (WGS) reactions.The oxidation of C3H8 was enhanced due to the steam reforming (SR) reactions.The steam promoted the C3H8 oxidation and NO reduction in three-way catalytic reaction.The amplitude of stoichiometric window was amplified by the addition of water to the feed stream.

  14. Distinguishing between chemical and physical promotion mechanisms by CeO{sub 2} in Pt, Rh three-way automotive catalysts under practical industrial conditions

    Energy Technology Data Exchange (ETDEWEB)

    Robota, H.J.; Nunan, J.G. [Allied-Signal Research and Technology, Des Plains, IL (United States)

    1993-12-31

    Under practical industrial conditions, aged, rather than fresh, catalyst performances is required to meet various regulatory emissions levels. While CeO{sub 2} is recognized as critical in allowing practically aged Pt, Rh catalysts to meet these performance targets, debate continues concerning the physicochemical mechanisms responsible for the performance enhancement. Suppressed precious metal sintering and stabilization of support {gamma}-Al{sub 2}O{sub 3} against surface area loss and structural phase changes are the principle physical mechanisms suggested. Chemical promotion by CeO2 has been attributed to oxygen storage, enhanced water gas shift activity, and enhanced CO oxidation activity through a precious metal-CeO2 coupling mechanisms. The authors have attempted to distinguish the relative contributions of these physical and chemical mechanisms to the performance of practical Pt, Rh catalysts. Two catalysts were aged in tandem using standard dynamometer methods. One was a fully formulated reference catalyst and the other was a CeO{sub 2}-free catalyst. Several potential chemical promotional mechanisms of CO oxidation via a more facile reaction pathway involving coupling between the precious metals and CeO{sub 2}.

  15. Ce-Zr-La/Al2O3 prepared in a continuous stirred-tank reactor: a highly thermostable support for an efficient Rh-based three-way catalyst.

    Science.gov (United States)

    Wang, Su-Ning; Lan, Li; Hua, Wei-Bo; Shi, Zhong-Hua; Chen, Yao-Qiang; Gong, Mao-Chu; Zhong, Lin

    2015-12-21

    Two Ce-Zr-La/Al2O3 composite oxides, CZLA-C and CZLA-B, were synthesized using a co-precipitation method in a continuous stirred-tank reactor (CSTR) and a batch reactor (BR), respectively. Two Rh-based three-way catalysts (TWCs), Rh/CZLA-C and Rh/CZLA-B were obtained by a wet-impregnation method using the two composites as the supports. The physicochemical properties of the samples before and after thermal treatment at 1000 °C were characterized by N2 adsorption-desorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), H2-temperature programmed reduction (H2-TPR) and CO chemisorption. The results indicated that CZLA-C shows higher thermal stability than CZLA-B due to a sparsely-agglomerated morphology. Compared with Rh/CZLA-B, Rh/CZLA-C displayed better reducibility and higher thermal stability and exhibited significantly higher activity in the catalytic removal of the simulated gasoline vehicle exhaust emission (NO, CO and C3H8). Our work can provide a facile and economical synthesis route to advanced support materials and catalysts for exhaust emission control.

  16. Synthesis of neodymium modified CeO2-ZrO2-Al2O3 support materials and their application in Pd-only three-way catalysts

    Institute of Scientific and Technical Information of China (English)

    PENG Na; ZHOU Jufa; CHEN Shanhu; LUO Xiuchao; CHEN Yaoqiang; GONG Maochu

    2012-01-01

    Ce-Zr-Al-Nd2O3 (CZAN) support materials were prepared by co-precipitation and impregnation methods,respectively.They were characterized by X-ray diffraction (XRD),low temperature nitrogen adsorption-desorption,oxygen pulsing technique,H2-temperature programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS).The Pd-only three-way catalysts (Pd-TWC) supported on these materials were prepared by incipient wetness method and studied by activity tests.The results demonstrated that the CZAN supports obtained by the two methods showed better structural,textural and redox properties than the CZA without Nd3O3,and the addition of Nd2O3 improved the catalytic activity of TWC.Especially,the CZAN-i support prepared by impregnation method had better thermal stability and redox property.Meanwhile,the Pd/CZAN-i catalyst exhibited the best catalytic performance.XPS measurements indicated that the Nd-modified sampies possessed more Ce3+ and oxygen vacancies on the surface of samples,which led to a better redox property.The excellent redox property of support materials helped to improve the catalytic activity of TWC.

  17. Confidence Intervals and "F" Tests for Intraclass Correlation Coefficients Based on Three-Way Mixed Effects Models

    Science.gov (United States)

    Zhou, Hong; Muellerleile, Paige; Ingram, Debra; Wong, Seok P.

    2011-01-01

    Intraclass correlation coefficients (ICCs) are commonly used in behavioral measurement and psychometrics when a researcher is interested in the relationship among variables of a common class. The formulas for deriving ICCs, or generalizability coefficients, vary depending on which models are specified. This article gives the equations for…

  18. Confidence Intervals and "F" Tests for Intraclass Correlation Coefficients Based on Three-Way Mixed Effects Models

    Science.gov (United States)

    Zhou, Hong; Muellerleile, Paige; Ingram, Debra; Wong, Seok P.

    2011-01-01

    Intraclass correlation coefficients (ICCs) are commonly used in behavioral measurement and psychometrics when a researcher is interested in the relationship among variables of a common class. The formulas for deriving ICCs, or generalizability coefficients, vary depending on which models are specified. This article gives the equations for…

  19. Study of Pt–Rh/CeO{sub 2}–ZrO{sub 2}–M{sub x}O{sub y} (M = Y, La)/Al{sub 2}O{sub 3} three-way catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Jiaxiu, Guo, E-mail: guojiaxiu@scu.edu.cn [College of Architecture and Environment, Sichuan University, Chengdu 610065 (China); National Engineering Research Center for Flue Gas Desulfurization, Chengdu 610065 (China); Zhonghua, Shi, E-mail: shizh96@scu.edu.cn [College of Chemistry, Sichuan University, Chengdu 610064 (China); Dongdong, Wu [College of Chemistry, Sichuan University, Chengdu 610064 (China); Huaqiang, Yin [College of Architecture and Environment, Sichuan University, Chengdu 610065 (China); National Engineering Research Center for Flue Gas Desulfurization, Chengdu 610065 (China); Maochu, Gong [College of Chemistry, Sichuan University, Chengdu 610064 (China); Yaoqiang, Chen, E-mail: chenyaoqiang@scu.edu.cn [College of Chemistry, Sichuan University, Chengdu 610064 (China); National Engineering Research Center for Flue Gas Desulfurization, Chengdu 610065 (China)

    2013-05-15

    CeO{sub 2}–ZrO{sub 2}–M{sub x}O{sub y} (M = Y; La) mixed oxides, prepared by co-precipitation method and characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), Raman spectra (RM) and oxygen pulse reaction, were comparatively investigated to elucidate the combinational effects of Y and/or La oxide promoters on the catalytic activity and anti-aging performance of monolithic cordierite honeycomb catalysts with low Pt and Rh content. The catalytic activities, water-gas shift (WGS) and steam reforming reaction (SR) were studied under a simulated gas mixture. The catalysts were also characterized by H{sub 2}-temperature-programmed reduction (H{sub 2}-TPR) and O{sub 2}-temperature-programmed desorption (O{sub 2}-TPD). The results showed that the prepared CeO{sub 2}–ZrO{sub 2}–M{sub x}O{sub y} oxides have a face-centered cubic fluorite structure and are nanosize. La{sup 3+} ions can significantly improve thermal stability and efficiently retard CeO{sub 2}–ZrO{sub 2} crystal sintering and growth. Doped CeO{sub 2}–ZrO{sub 2} with Y{sup 3+} and La{sup 3+} has 105 and 60 m{sup 2}/g surface area and 460 and 390 μmol/g OSC before and after aging. The T{sub 50} of fresh Pt–Rh/CZYL/LA is 170 °C for CO, 222 °C for C{sub 3}H{sub 8} and 189 °C for NO, and shift to 205, 262 and 228 °C after hydrothermal aging, which are better than those of Pt–Rh/CZY/LA or Pt–Rh/CZL/LA. WGS and SR are relate to the OSC of oxygen storage materials and absorbed oxygen species on the catalyst surface and affect the three-way catalytic activities of catalysts. The reductive property of noble metals and the dissociatively adsorbed O{sub 2} on the surface of catalysts are closely related to the catalytic activities.

  20. Determination of the N{sub 2}O composition parameters on a three way catalyst in a synthesis gas reactor; Ermittlung der N{sub 2}O-Bildungsparameter am geregelten Dreiwegekatalysator von Kraftfahrzeugen in einem Hochtemperatur-Stroemungsreaktor

    Energy Technology Data Exchange (ETDEWEB)

    Meyer-Pittroff, R.; Gifhorn, A.; Rabl, H.P.

    1998-10-01

    The determination of the N{sub 2}O composition parameters on three-way catalysts (TWC) took place on an engine bench and in a high temperature flow reactor. The influences of exhaust gas components, temperature, air fuel ratio, gas hour space velocity, precious metal loading, catalyst aging and oxygen storage capacity were checked with transient and intransient experiments. 16 different catalyst samples were tested. The experiments show that the N{sub 2}O formation is a function of the catalyst temperature and the air fuel ratio. Under rich conditions N{sub 2}O formed in a temperature range that is limited by the beginning of the NO conversion at lower temperatures and by the oxidation of all reducing components at higher temperatures; under rich conditions range is limited by the beginning of the NO conversion and the dissociation of N{sub 2}O at TWC. It is a result of catalyst aging that at aged TWC samples the NO conversion and the N{sub 2}O formation is shifted up to higher temperatures. Another important influence is the TWC coating. The investigations show that the absolute as well as the selective N{sub 2}O formation at TWC samples coated with Pt/Pd/Rh- and Pd/Rh is higher than the N{sub 2}O formation at TWC samples coated with Pt/Rh. Simultaneously it could be observed that Pt/Pd/Rh samples show a higher oxygen storage capacity than Pt/Rh. (orig.) [Deutsch] Die Ermittlung der N{sub 2}O-Bildungsparameter an Dreiwegekatalysatoren erfolgte an einem Motorpruefstand und an einem Modellabgasreaktor. In stationaeren und instationaeren Versuchen wurden die Einfluesse von einzelnen Ottomotorabgaskomponenten, Temperatur, Luftverhaeltnis, Raumgeschwindigkeit, Edelmetallbeschichtung, Katalysatoralterung, Sauerstoffspeicherfaehigkeit untersucht. Fuer die Untersuchung standen 16 verschiedene Beschichtungen zur Verfuegung. Die N{sub 2}O-Bildung wird entscheidend vom Luftverhaeltnis und der Katalysatortemperatur bestimmt. Bei unterstoechiometrischen Abgaszusammensetzungen

  1. Multistage Three-Way Decisions of Spam SMS Filtering Model%多阶段三支决策垃圾短信过滤模型

    Institute of Scientific and Technical Information of China (English)

    李建林; 黄顺亮

    2014-01-01

    提出了一种多阶段三支决策垃圾短信过滤模型。该模型使用不同的信息粒度对短信进行表示,运用序列决策(即多阶段、多步骤决策),在不同的决策阶段基于不同的信息粒度分别进行三支决策,有效地避免了当信息粒度太大或信息量不足时进行不合理的决策,对于不能满足当前决策条件的信息,可以通过补充足够的粒度信息作进一步的决策。最后通过实验证明了该模型的合理性和有效性。%This paper proposes a multistage three-way decisions of spam SMS (short messaging service) filtering model. By using different granularity information to express the SMS, with the sequence decisions (i.e., multistage, multiple steps in decision-making), at different decision-making stages, based on different information granularity respectively three-way decision-making, those can avoid to make irrational decisions when the message size is too big or insufficient information. If the information does not meet the current decision-making conditions, this model can add enough granularity information before making a further decision. Finally, the experimental results prove the rationality and validity of the model.

  2. Enhanced fluorescence sensitivity by coupling yttrium-analyte complexes and three-way fast high-performance liquid chromatography data modeling

    Energy Technology Data Exchange (ETDEWEB)

    Alcaraz, Mirta R.; Culzoni, María J., E-mail: mculzoni@fbcb.unl.edu.ar; Goicoechea, Héctor C., E-mail: hgoico@fbcb.unl.edu.ar

    2016-01-01

    The present study reports a sensitive chromatographic method for the analysis of seven fluoroquinolones (FQs) in environmental water samples, by coupling yttrium-analyte complex and three-way chromatographic data modeling. This method based on the use of HPLC-FSFD does not require complex or tedious sample treatments or enrichment processes before the analysis, due to the significant fluorescence increments of the analytes reached by the presence of Y{sup 3+}. Enhancement achieved for the FQs signals obtained after Y{sup 3+} addition reaches 103- to 1743-fold. Prediction results corresponding to the application of MCR-ALS to the validation set showed relative error of prediction (REP%) values below 10% in all cases. A recovery study that includes the simultaneous determination of the seven FQs in three different environmental aqueous matrices was conducted. The recovery studies assert the efficiency and the accuracy of the proposed method. The LOD values calculated are in the order of part per trillion (below 0.5 ng mL{sup −1} for all the FQs, except for enoxacin). It is noteworthy to mention that the method herein proposed, which does not include pre-concentration steps, allows reaching LOD values in the same order of magnitude than those achieved by more sophisticated methods based on SPE and UHPLC-MS/MS. - Highlights: • Highly sensitive method for the analysis of seven fluoroquinolones. • Coupling of yttrium-analyte complex and three-way modeling. • Complex or tedious sample treatments or enrichment processes are nor required. • Accuracy on the quantitation of fluoroquinolones in real water river samples.

  3. A comparative study of SrO and BaO doping to CeO{sub 2}-ZrO{sub 2}: Characteristic and its catalytic performance for three-way catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Jiaxiu, E-mail: guojiaxiu@scu.edu.cn [College of Architecture and Environment, Sichuan University, Chengdu 610065 (China); National Engineering Research Center for Flue Gas Desulfurization, Chengdu 610065 (China); Shi, Zhonghua, E-mail: shizhonghua@scu.edu.cn [College of Chemistry, Sichuan University, Chengdu 610064 (China); Wu, Dongdong [College of Chemistry, Sichuan University, Chengdu 610064 (China); Yin, Huaqiang [College of Architecture and Environment, Sichuan University, Chengdu 610065 (China); National Engineering Research Center for Flue Gas Desulfurization, Chengdu 610065 (China); Gong, Maochu [College of Chemistry, Sichuan University, Chengdu 610064 (China); Chen, Yaoqiang [College of Chemistry, Sichuan University, Chengdu 610064 (China); National Engineering Research Center for Flue Gas Desulfurization, Chengdu 610065 (China)

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ► The prepared materials have a face-centered cubic structure and nanosize particles. ►Comparing to CZB, aged CZS has 494 μmol/g of OSC and 30 m{sup 2}/g of surface area. ► CZS and CZB have similar NO sorption and reductive properties and different H{sub 2} uptake. ► T{sub 50} of Pt-Rh/CZS/LA is as low as 199 °C for CO, 228 °C for NO, and 252 °C for C{sub 3}H{sub 8}. ► Pt-Rh/CZS/LA has wider working-window at 320 °C under different λ value. -- Abstract: Ceria-zirconia-strontia (Ce{sub 0.35}Zr{sub 0.55}Sr{sub 0.10}O{sub 1.9}) and ceria-zirconia-baria (Ce{sub 0.35}Zr{sub 0.55}Ba{sub 0.10}O{sub 1.9}) were synthesized using an oxidation-co-precipitation method with hydrogen peroxide (H{sub 2}O{sub 2}) as oxidant. The physical and chemical properties of the prepared materials were investigated using Brunauer–Emmett–Teller surface area characterization, transmission electron microscopy, X-ray diffraction, Raman spectra, X-ray photoelectron spectroscopy, and oxygen pulse reaction. The prepared materials were used in preparing three-way catalysts with low Pt and Rh content. Moreover, catalytic activities were evaluated at a fixed bed under a simulated gaseous mixture. The results are as follows: (1) the prepared materials have a face-centered cubic structure and are nano-sized; (2) aged Ce{sub 0.35}Zr{sub 0.55}Sr{sub 0.10}O{sub 1.9} has higher oxygen storage capacity (494 μmol/g), better thermal stability (30 m{sup 2}/g), good low-temperature reducibility, and high hydrogen uptake after TPR-redox cycles; (3) the light-off temperature (T{sub 50}) of Pt-Rh/CZS/LA can be as low as 199 °C for CO, 228 °C for NO, and 252 °C for C{sub 3}H{sub 8}; and (4) Pt-Rh/CZS/LA has a fairly wide working-window.

  4. Effect of CeO2 and Al2O3 on the activity of Pd/Co3O4/cordierite catalyst in the three-way catalysis reactions (CO/NO/CnHm)

    Institute of Scientific and Technical Information of China (English)

    Sergiy O. Soloviev; Pavlo I. Kyriienko; Nataliia O. Popovych

    2012-01-01

    The present article studies the effect of CeO2 and Al2O3 on the activity of Pd/Co3O4/cordierite catalyst in conversion of NO,CO,CnHm.The catalysts were characterized by temperature programmed reduction with hydrogen,X-ray diffraction,X-ray photoelectron spectroscopy and transmission electron microscopy.It is shown that the effect of CeO2 on the properties of Pd/Co3O4/cordierite catalyst depends on preparation method.The catalyst obtained by co-deposition of cerium and cobalt oxides has higher activity in CO oxidation (CO + O2 and CO + NO) and total hexane oxidation (C6H14 + O2).Such phenomenon is probably caused by more than stoichiometric amount of formed oxygen vacancies,an increase in both mobility of surface oxygen and dispersity of components in the catalytic composition.It is demonstrated that CeO2 addition promotes the SO2 resistance of Pd/Co3O4/cordierite.The second support decreases the activity of Pd/Co3O4/cordierite catalyst in the reactions of CO and C6H14 with oxygen because of CoAl2O4 formation.

  5. THREE WAY DECOMPOSITION FOR THE BOLTZMANN EQUATION

    Institute of Scientific and Technical Information of China (English)

    Ilgis Ibragimov; Sergej Rjasanow

    2009-01-01

    The initial value problem for the spatially homogeneous Boltzmann equation is considered. A deterministic numerical scheme for this problem is developed by the use of the three way decomposition of the unknown function as well as of the collision integral. On this way, almost linear complexity of the algorithm is achieved. Some numerical examples are presented.

  6. THREE-WAY CATALYSTS: PAST, PRESENT AND FUTURE.

    Directory of Open Access Journals (Sweden)

    N. GUILLÉN-HURTADO

    2012-01-01

    Full Text Available En este artículo de revisión se discute el pasado, presente y futuro de los catalizadores de tres vías. Se presentan las principales reacciones químicas que tiene lugar en los motor de gasolina así como las reacciones que ocurren en los catalizadores de tres vías (CTV colocados en el escape, concretamente la oxidación de monóxido de carbonos e hidrocarburos y la reducción de los óxidos de nitrógeno a nitrógeno molecular. También se describen los principales componentes de un CTV (sustratos, metals nobles y óxidos de cerio. Por último se discute el problema del control de las emisiones en motores diesel, analizando la tecnología disponible en la actualidad para estos vehículos.

  7. The Influence of Deposition Methods of Support Layer on Cordierite Substrate on the Characteristics of a MnO2–NiO–Co3O4/Ce0.2Zr0.8O2/Cordierite Three Way Catalyst

    Directory of Open Access Journals (Sweden)

    Phuong Thi Mai Pham

    2014-09-01

    Full Text Available This paper compares different coating methods (in situ solid combustion, hybrid deposition, secondary growth on seed, suspension, double deposition of wet impregnation and suspension to deposit Ce0.2Zr0.8O2 mixed oxides on cordierite substrates, for use as a three way catalyst. Among them, the double deposition was proven to be the most efficient one. The coated sample shows a BET (Brunauer–Emmett–Teller surface area of 25 m2/g, combined with a dense and crack free surface. The catalyst with a layer of MnO2–NiO–Co3O4 mixed oxides on top of the Ce0.2Zr0.8O2/cordierite substrate prepared by this method exhibits good activity for the treatment of CO, NO and C3H6 in exhaust gases (CO conversion of 100% at 250 °C, C3H6 conversion of 100% at 400 °C and NO conversion of 40% at 400 °C.

  8. Decompositions and Biplots in Three-Way Correspondence Analysis.

    Science.gov (United States)

    Carlier, Andre; Kroonenberg, Pieter M.

    1996-01-01

    Correspondence analysis for three-way contingency tables is presented using three-way generalizations of the singular value decomposition. It is shown that, in combination with the additive decomposition of interactions in three-way tables proposed by H. O. Lancaster, a detailed analysis of decomposition of dependence is possible. (SLD)

  9. Persistent Memory Effects and the Mid- and Post-Brick Dynamic Behaviour of Three-Way Automotive Catalysts Effets mémoires persistants et comportement dynamique des briques médiane et postérieure de catalyseurs automobiles à trois voies

    Directory of Open Access Journals (Sweden)

    Peyton Jones J.C.

    2011-09-01

    Full Text Available This paper presents the results of an experimental study into the dynamic behaviour of a three-way automotive catalyst and its associated exhaust gas oxygen sensors. Motivated by issues of feedback sensor location, the study seeks to overlay the results of repeat experiments, with sensors and fast-response gas analyzers positioned at different locations, in order to obtain a detailed picture of system dynamics at different points within the catalyst. Initial results demonstrated that the dynamic response of the catalyst can be significantly affected by a persistent memory effect in addition to reversible deactivation dynamics and the familiar oxygen storage/release dynamics of the system. In particular, the effects of prior rich or stoichiometric operation are shown to persist even after extended periods of lean operation. This memory effect is important, not only because of its potential impact on conversion efficiency, but also because of its impact on the repeatability of experiments carried out under what would appear to be near-identical operating conditions. By pre-conditioning under rich conditions highly repeatable experiments were achieved. The results were combined to give a detailed picture of catalyst dynamics at pre-, mid- and post-catalyst locations, and provide insight into catalyst and (non-ideal exhaust gas oxygen sensor behavior. Cet article présente les résultats d’une étude expérimentale en matière de comportement dynamique d’un catalyseur automobile à trois voies et de ses capteurs d’oxygène de gaz d’échappement associés. Motivée par les problèmes de localisation des capteurs de retour d’information, l’étude cherche à corréler les résultats d’expériences répétées, capteurs et analyseurs de gaz à réponse rapide étant disposés en des emplacements différents afin d’obtenir une image détaillée des dynamiques de système en différents points à l’intérieur du catalyseur. Les r

  10. Three ways of assembling a house

    DEFF Research Database (Denmark)

    Beim, Anne; Nielsen, Jesper; Vibæk, Kasper Sánchez

    2010-01-01

    The Scandinavian construction industry is characterised by high quality craftsmanship, but also by an array of highly industrialised, but not always coordinated building systems. This book aims to shed some light on these systems and their underlying concepts. By looking at both the systems...... themselves, the way they are produced and the business models behind them, the systems and concepts are assessed in their broader organisational context and not just as physical manifestations of their design intentions. Acknowledging that there is more than one possible way of enhancing the application...... of industrialised solutions in building and architecture, the present work introduces a framework of several different strategies for industrialisation and assesses their viabilities....

  11. Temporal analysis of social networks using three-way DEDICOM.

    Energy Technology Data Exchange (ETDEWEB)

    Bader, Brett William; Harshman, Richard A. (University of Ontario, London, Ontario, Canada); Kolda, Tamara Gibson (Sandia National Laboratories, Livermore, CA)

    2006-06-01

    DEDICOM is an algebraic model for analyzing intrinsically asymmetric relationships, such as the balance of trade among nations or the flow of information among organizations or individuals. It provides information on latent components in the data that can be regarded as ''properties'' or ''aspects'' of the objects, and it finds a few patterns that can be combined to describe many relationships among these components. When we apply this technique to adjacency matrices arising from directed graphs, we obtain a smaller graph that gives an idealized description of its patterns. Three-way DEDICOM is a higher-order extension of the model that has certain uniqueness properties. It allows for a third mode of the data, such as time, and permits the analysis of semantic graphs. We present an improved algorithm for computing three-way DEDICOM on sparse data and demonstrate it by applying it to the adjacency tensor of a semantic graph with time-labeled edges. Our application uses the Enron email corpus, from which we construct a semantic graph corresponding to email exchanges among Enron personnel over a series of 44 months. Meaningful patterns are recovered in which the representation of asymmetries adds insight into the social networks at Enron.

  12. Catalyst Deactivation: Control Relevance of Model Assumptions

    Directory of Open Access Journals (Sweden)

    Bernt Lie

    2000-10-01

    Full Text Available Two principles for describing catalyst deactivation are discussed, one based on the deactivation mechanism, the other based on the activity and catalyst age distribution. When the model is based upon activity decay, it is common to use a mean activity developed from the steady-state residence time distribution. We compare control-relevant properties of such an approach with those of a model based upon the deactivation mechanism. Using a continuous stirred tank reactor as an example, we show that the mechanistic approach and the population balance approach lead to identical models. However, common additional assumptions used for activity-based models lead to model properties that may deviate considerably from the correct one.

  13. Some procedures for displaying results from three-way methods

    NARCIS (Netherlands)

    Kiers, Henk A.L.

    2000-01-01

    Three-way Tucker analysis and CANDECOMP/PARAFAC are popular methods for the analysis of three-way data (data pertaining to three sets of entities). To interpret the results from these methods, one can, in addition to inspecting the component matrices and the core array, inspect visual representation

  14. Three-way component analysis : Principles and illustrative application

    NARCIS (Netherlands)

    Kiers, Henk A.L.; Van Mechelen, Iven

    2001-01-01

    Three-way component analysis techniques are designed for descriptive analysis of 3-way data, for example, when data are collected on individuals, in different settings, and on different measures. Such techniques summarize all information in a 3-way data set by summarizing, for each way of the 3-way

  15. Three-way flexible cantilever probes for static contact

    DEFF Research Database (Denmark)

    Wang, Fei; Petersen, Dirch Hjorth; Jensen, Helle Vendelbo;

    2011-01-01

    In micro four-point probe measurements, three-way flexible L-shaped cantilever probes show significant advantages over conventional straight cantilever probes. The L-shaped cantilever allows static contact to the sample surface which reduces the frictional wear of the cantilever tips. We analyze...

  16. Charge Transport across DNA-Based Three-Way Junctions.

    Science.gov (United States)

    Young, Ryan M; Singh, Arunoday P N; Thazhathveetil, Arun K; Cho, Vincent Y; Zhang, Yuqi; Renaud, Nicolas; Grozema, Ferdinand C; Beratan, David N; Ratner, Mark A; Schatz, George C; Berlin, Yuri A; Lewis, Frederick D; Wasielewski, Michael R

    2015-04-22

    DNA-based molecular electronics will require charges to be transported from one site within a 2D or 3D architecture to another. While this has been shown previously in linear, π-stacked DNA sequences, the dynamics and efficiency of charge transport across DNA three-way junction (3WJ) have yet to be determined. Here, we present an investigation of hole transport and trapping across a DNA-based three-way junction systems by a combination of femtosecond transient absorption spectroscopy and molecular dynamics simulations. Hole transport across the junction is proposed to be gated by conformational fluctuations in the ground state which bring the transiently populated hole carrier nucleobases into better aligned geometries on the nanosecond time scale, thus modulating the π-π electronic coupling along the base pair sequence.

  17. 技能培训和情感承诺:一个三阶调节模型%Skill Training and Affective Commitment:A Three-way Moderating Model

    Institute of Scientific and Technical Information of China (English)

    柏帅蛟; 井润田

    2015-01-01

    Based on the social exchange theory and the theory of Maslow′s hierarchy of needs ,this paper constructs a three‐way moderating model to explore the relationship between skill training and affective commitment at individual level. The findings indicate as follows :skill train‐ing has positive effects on affective commitment ,which is moderated by the interaction between employment type(standard worker or temporary worker) and age ;in lower‐age group ,skill training has stronger effect on affective commitment for standard workers than for temporary work‐ers ;in higher‐age group ,the relationship between skill training and affective commitment is not moderated by employment type .%基于社会交换理论和需求层次理论,构建了一个三阶调节模型,在个体层次上探讨了技能培训与情感承诺的关系。结果表明:技能培训对情感承诺具有显著的正向影响;这种正向影响受到用工形式(正式工和非正式工)与年龄交互项的调节:在低年龄群体中,技能培训对正式员工的情感承诺具有更强的正向效应;在高年龄群体中,技能培训与情感承诺的关系没有受到用工形式的调节。

  18. MODELING STYRENE HYDROGENATION KINETICS USING PALLADIUM CATALYSTS

    Directory of Open Access Journals (Sweden)

    G. T. Justino

    Full Text Available Abstract The high octane number of pyrolysis gasoline (PYGAS explains its insertion in the gasoline pool. However, its use is troublesome due to the presence of gum-forming chemicals which, in turn, can be removed via hydrogenation. The use of Langmuir-Hinshelwood kinetic models was evaluated for hydrogenation of styrene, a typical gum monomer, using Pd/9%Nb2O5-Al2O3 as catalyst. Kinetic models accounting for hydrogen dissociative and non-dissociative adsorption were considered. The availability of one or two kinds of catalytic sites was analyzed. Experiments were carried out in a semi-batch reactor at constant temperature and pressure in the absence of transport limitations. The conditions used in each experiment varied between 16 - 56 bar and 60 - 100 ºC for pressure and temperature, respectively. The kinetic models were evaluated using MATLAB and EMSO software. Models using adsorption of hydrogen and organic molecules on the same type of site fitted the data best.

  19. Modeling of PEM fuel cell Pt/C catalyst degradation

    Science.gov (United States)

    Bi, Wu; Fuller, Thomas F.

    Pt/C catalyst degradation remains as one of the primary limitations for practical applications of proton exchange membrane (PEM) fuel cells. Pt catalyst degradation mechanisms with the typically observed Pt nanoparticle growth behaviors have not been completely understood and predicted. In this work, a physics-based Pt/C catalyst degradation model is proposed with a simplified bi-modal particle size distribution. The following catalyst degradation processes were considered: (1) dissolution of Pt and subsequent electrochemical deposition on Pt nanoparticles in cathode; (2) diffusion of Pt ions in the membrane electrode assembly (MEA); and (3) Pt ion chemical reduction in membrane by hydrogen permeating through the membrane from the negative electrode. Catalyst coarsening with Pt nanoparticle growth was clearly demonstrated by Pt mass exchange between small and large particles through Pt dissolution and Pt ion deposition. However, the model is not adequate to predict well the catalyst degradation rates including Pt nanoparticle growth, catalyst surface area loss and cathode Pt mass loss. Additional catalyst degradation processes such as new Pt cluster formation on carbon support and neighboring Pt clusters coarsening was proposed for further simulative investigation.

  20. Three-Way Complementarities: Performance Pay, Human Resource Analytics, and Information Technology

    OpenAIRE

    2010-01-01

    We test for three-way complementarities among information technology (IT), performance pay, and human resource (HR) analytics practices. We develop a principal-agent model examining how these practices work together as an incentive system that produces a larger productivity premium when the practices are implemented in concert rather than separately. We assess our model by combining fine-grained data on human capital management (HCM) software adoption over 11 years with detailed survey data o...

  1. Culture Three Ways: Culture and Subcultures Within Countries.

    Science.gov (United States)

    Oyserman, Daphna

    2017-01-03

    Culture can be thought of as a set of everyday practices and a core theme-individualism, collectivism, or honor-as well as the capacity to understand each of these themes. In one's own culture, it is easy to fail to see that a cultural lens exists and instead to think that there is no lens at all, only reality. Hence, studying culture requires stepping out of it. There are two main methods to do so: The first involves using between-group comparisons to highlight differences and the second involves using experimental methods to test the consequences of disruption to implicit cultural frames. These methods highlight three ways that culture organizes experience: (a) It shields reflexive processing by making everyday life feel predictable, (b) it scaffolds which cognitive procedure (connect, separate, or order) will be the default in ambiguous situations, and (c) it facilitates situation-specific accessibility of alternate cognitive procedures. Modern societal social-demographic trends reduce predictability and increase collectivism and honor-based go-to cognitive procedures.

  2. Modelling Catalyst Surfaces Using DFT Cluster Calculations

    Directory of Open Access Journals (Sweden)

    Oliver Kröcher

    2009-09-01

    Full Text Available We review our recent theoretical DFT cluster studies of a variety of industrially relevant catalysts such as TiO2, γ-Al2O3, V2O5-WO3-TiO2 and Ni/Al2O3. Aspects of the metal oxide surface structure and the stability and structure of metal clusters on the support are discussed as well as the reactivity of surfaces, including their behaviour upon poisoning. It is exemplarily demonstrated how such theoretical considerations can be combined with DRIFT and XPS results from experimental studies.

  3. Modelling catalyst surfaces using DFT cluster calculations.

    Science.gov (United States)

    Czekaj, Izabela; Wambach, Jörg; Kröcher, Oliver

    2009-11-20

    We review our recent theoretical DFT cluster studies of a variety of industrially relevant catalysts such as TiO(2), gamma-Al(2)O(3), V(2)O(5)-WO(3)-TiO(2) and Ni/Al(2)O(3). Aspects of the metal oxide surface structure and the stability and structure of metal clusters on the support are discussed as well as the reactivity of surfaces, including their behaviour upon poisoning. It is exemplarily demonstrated how such theoretical considerations can be combined with DRIFT and XPS results from experimental studies.

  4. Transient kinetic modeling of the ethylene and carbon monoxide oxidation over a commercial automotive exhaust gas catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Harmsen, J.M.A.; Hoebink, J.H.B.J.; Schouten, J.C.

    2000-03-01

    The transient kinetics of ethylene oxidation by oxygen over a commercial Pt/Rh/CeO{sub 2}/{gamma}-Al{sub 2}O{sub 3} three-way catalyst were modeled. Experiments were carried out in a fixed-bed microreactor with two separate inlets, enabling alternate feeding of ethylene and oxygen with frequencies up to {1/4} Hz. The experimental conditions resemble the cold-start period of an Otto engine in a car. Two types of adsorbed ethylene species seem to exist. A selective catalyst deactivation for oxygen adsorption, due to deposition of carbonaceous species, was found. A kinetic model was developed, based on elementary reaction steps, that allows one to describe the experiments quantitatively. Furthermore, this model was combined with the published model for transient carbon monoxide oxidation over the same catalyst, which enables one to predict the results of simultaneous ethylene and carbon monoxide oxidation. Both components react in rather distinct zones, with ethylene being converted only when carbon monoxide oxidation is almost complete.

  5. First-principles modeling of catalysts: novel algorithms and reaction mechanisms

    Science.gov (United States)

    Richard, Bryan Goldsmith

    that water present in aqueous solvents plays a critical rate-enhancing role in accelerating the formation of the active sites. In Chapter IV we study olefin epoxidation catalyzed by MTO, and the strong accelerating effects in the presence of H2O. DFT calculations and experiments both support that the primary origin of the acceleration of catalytic epoxidation arises from the water-dependence of the rates of generation of the peroxorhenium complexes. Modeling catalyst surfaces and active sites under realistic conditions is also a long-standing computational challenge due to the dynamic nature of catalytic processes. For example, catalyst surfaces can restructure under reaction conditions, nanoparticles can undergo Ostwald ripening or even disintegrate into adatom-reactant complexes, and active-site poisoning from reaction intermediates or side-products could occur. In Chapter V we focus on understanding the stability of supported nanoparticles under reaction conditions against disintegration into adatom-reactant complexes, as reactant-induced disintegration can lead to catalyst deactivation or be exploited to redisperse sintered catalysts. More specifically, to better understand the stability of TiO2(110) supported three-way catalysts rhodium, palladium, and platinum nanoparticles during NOx and CO reduction, we conducted an ab initio thermodynamics study of the feasibility for these noble metal nanoparticles to disintegrate across a large parameter space of operation temperatures, pressures of CO or NO gas, and nanoparticle sizes. Lastly, in Chapter VI, the status of DFT modeling of catalysts is briefly summarized and some remaining challenges are discussed. (Abstract shortened by UMI.).

  6. Kinetic modeling of ethylbenzene dehydrogenation over hydrotalcite catalysts

    KAUST Repository

    Atanda, Luqman

    2011-07-01

    Kinetics of ethylbenzene dehydrogenation to styrene was investigated over a series of quaternary mixed oxides of Mg3Fe0.25Me0.25Al0.5 (Me=Co, Mn and Ni) catalysts prepared by calcination of hydrotalcite-like compounds and compared with commercial catalyst. The study was carried out in the absence of steam using a riser simulator at 400, 450, 500 and 550°C for reaction times of 5, 10, 15 and 20s. Mg3Fe0.25Mn0.25Al0.5 afforded the highest ethylbenzene conversion of 19.7% at 550°C. Kinetic parameters for the dehydrogenation process were determined using the catalyst deactivation function based on reactant conversion model. The apparent activation energies for styrene production were found to decrease as follows: E1-Ni>E1-Co>E1-Mn. © 2011 Elsevier B.V.

  7. Estimation of Kinetic Parameters in an Automotive SCR Catalyst Model

    DEFF Research Database (Denmark)

    Åberg, Andreas; Widd, Anders; Abildskov, Jens;

    2016-01-01

    A challenge during the development of models for simulation of the automotive Selective Catalytic Reduction catalyst is the parameter estimation of the kinetic parameters, which can be time consuming and problematic. The parameter estimation is often carried out on small-scale reactor tests, or p...

  8. Regeneration of LOHC dehydrogenation catalysts: In-situ IR spectroscopy on single crystals, model catalysts, and real catalysts from UHV to near ambient pressure

    Energy Technology Data Exchange (ETDEWEB)

    Amende, Max, E-mail: max.amende@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Kaftan, Andre, E-mail: andre.kaftan@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Bachmann, Philipp, E-mail: philipp.bachmann@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Brehmer, Richard, E-mail: richard.brehmer@fau.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Preuster, Patrick, E-mail: patrick.preuster@fau.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Koch, Marcus, E-mail: marcus.koch@crt.cbi.uni-erlangen.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); and others

    2016-01-01

    Graphical abstract: - Highlights: • We examine the regeneration of Pt-based catalysts poisoned by LOHC degradation. • A microscopic mechanism of the removal of degradation products from Pt is proposed. • Results of our UHV studies on model catalysts are transferred to real catalysis. • Oxidative regeneration of Pt/alumina is possible under mild conditions (600 K). • The degree and temperature regime of regeneration depends on the catalyst morphology. - Abstract: 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/Al{sub 2}O{sub 3} model catalysts, and near-ambient pressure (NAP) measurements on real core–shell Pt/Al{sub 2}O{sub 3} 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/Al{sub 2}O{sub 3} model catalyst and

  9. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Grass, Michael Edward [Univ. of California, Berkeley, CA (United States)

    2008-09-01

    Model heterogeneous catalysts have been synthesized and studied to better understand how the surface structure of noble metal nanoparticles affects catalytic performance. In this project, monodisperse rhodium and platinum nanoparticles of controlled size and shape have been synthesized by solution phase polyol reduction, stabilized by polyvinylpyrrolidone (PVP). Model catalysts have been developed using these nanoparticles by two methods: synthesis of mesoporous silica (SBA-15) in the presence of nanoparticles (nanoparticle encapsulation, NE) to form a composite of metal nanoparticles supported on SBA-15 and by deposition of the particles onto a silicon wafer using Langmuir-Blodgett (LB) monolayer deposition. The particle shapes were analyzed by transmission electron microscopy (TEM) and high resolution TEM (HRTEM) and the sizes were determined by TEM, X-ray diffraction (XRD), and in the case of NE samples, room temperature H2 and CO adsorption isotherms. Catalytic studies were carried out in homebuilt gas-phase reactors. For the nanoparticles supported on SBA-15, the catalysts are in powder form and were studied using the homebuilt systems as plug-flow reactors. In the case of nanoparticles deposited on silicon wafers, the same systems were operated as batch reactors. This dissertation has focused on the synthesis, characterization, and reaction studies of model noble metal heterogeneous catalysts. Careful control of particle size and shape has been accomplished though solution phase synthesis of Pt and Rh nanoparticles in order to elucidate further structure-reactivity relationships in noble metal catalysis.

  10. Automotive Catalyst State Diagnosis Using Microwaves

    Directory of Open Access Journals (Sweden)

    Moos Ralf

    2015-01-01

    Full Text Available The state of catalysts plays a key role in automotive exhaust gas aftertreatment. The soot or ash loading of Diesel particulate filters, the oxygen loading degree in three-way catalysts, the amount of stored ammonia in SCR catalysts, or the NOx loading degree in NOx storage catalysts are important parameters that are today determined indirectly and in a model-based manner with gas sensors installed upstream and/or downstream of the catalysts. This contribution gives an overview on a novel approach to determine the catalyst state directly by a microwave-based technique. The method exploits the fact that the catalyst housing acts as a microwave cavity resonator. As “sensing” elements, one or two simple antennas are mounted inside the catalyst canning. The electrical properties of the catalyst device (ceramic honeycomb plus coating and storage material can be measured. Preferably, the resonance characteristics, e.g., the resonance frequencies, of selected cavity modes are observed. The information on the catalyst interior obtained in such a contactless manner is very well correlated with the catalyst state as will be demonstrated for different exhaust gas aftertreatment systems.

  11. Formation of Three-Way Scanning Electron Microscope Moiré on Micro/Nanostructures

    Directory of Open Access Journals (Sweden)

    Qinghua Wang

    2014-01-01

    Full Text Available Three-way scanning electron microscope (SEM moiré was first generated using a designed three-way electron beam (EB in an SEM. The spot-type three-way SEM moiré comes from the interference between the three-way EB and the specimen grating in which the periodic cells are arranged in a triangular manner. The deformation and the structure information of the specimen grating in three directions can be simultaneously obtained from the three-way SEM moiré. The design considerations of the three-way EB were discussed. As an illustration, the three-way SEM moiré spots produced on a silicon slide were presented. The proposed three-way SEM moiré method is expected to characterize micro/nanostructures in triangular or hexagonal arrangements in three directions at the same time.

  12. Three-way analysis of the UPLC-PDA dataset for the multicomponent quantitation of hydrochlorothiazide and olmesartan medoxomil in tablets by parallel factor analysis and three-way partial least squares.

    Science.gov (United States)

    Dinç, Erdal; Ertekin, Zehra Ceren

    2016-01-01

    An application of parallel factor analysis (PARAFAC) and three-way partial least squares (3W-PLS1) regression models to ultra-performance liquid chromatography-photodiode array detection (UPLC-PDA) data with co-eluted peaks in the same wavelength and time regions was described for the multicomponent quantitation of hydrochlorothiazide (HCT) and olmesartan medoxomil (OLM) in tablets. Three-way dataset of HCT and OLM in their binary mixtures containing telmisartan (IS) as an internal standard was recorded with a UPLC-PDA instrument. Firstly, the PARAFAC algorithm was applied for the decomposition of three-way UPLC-PDA data into the chromatographic, spectral and concentration profiles to quantify the concerned compounds. Secondly, 3W-PLS1 approach was subjected to the decomposition of a tensor consisting of three-way UPLC-PDA data into a set of triads to build 3W-PLS1 regression for the analysis of the same compounds in samples. For the proposed three-way analysis methods in the regression and prediction steps, the applicability and validity of PARAFAC and 3W-PLS1 models were checked by analyzing the synthetic mixture samples, inter-day and intra-day samples, and standard addition samples containing HCT and OLM. Two different three-way analysis methods, PARAFAC and 3W-PLS1, were successfully applied to the quantitative estimation of the solid dosage form containing HCT and OLM. Regression and prediction results provided from three-way analysis were compared with those obtained by traditional UPLC method.

  13. The cluster beam route to model catalysts and beyond.

    Science.gov (United States)

    Ellis, Peter R; Brown, Christopher M; Bishop, Peter T; Yin, Jinlong; Cooke, Kevin; Terry, William D; Liu, Jian; Yin, Feng; Palmer, Richard E

    2016-07-01

    The generation of beams of atomic clusters in the gas phase and their subsequent deposition (in vacuum) onto suitable catalyst supports, possibly after an intermediate mass filtering step, represents a new and attractive approach for the preparation of model catalyst particles. Compared with the colloidal route to the production of pre-formed catalytic nanoparticles, the nanocluster beam approach offers several advantages: the clusters produced in the beam have no ligands, their size can be selected to arbitrarily high precision by the mass filter, and metal particles containing challenging combinations of metals can be readily produced. However, until now the cluster approach has been held back by the extremely low rates of metal particle production, of the order of 1 microgram per hour. This is more than sufficient for surface science studies but several orders of magnitude below what is desirable even for research-level reaction studies under realistic conditions. In this paper we describe solutions to this scaling problem, specifically, the development of two new generations of cluster beam sources, which suggest that cluster beam yields of grams per hour may ultimately be feasible. Moreover, we illustrate the effectiveness of model catalysts prepared by cluster beam deposition onto agitated powders in the selective hydrogenation of 1-pentyne (a gas phase reaction) and 3-hexyn-1-ol (a liquid phase reaction). Our results for elemental Pd and binary PdSn and PdTi cluster catalysts demonstrate favourable combinations of yield and selectivity compared with reference materials synthesised by conventional methods.

  14. Direct reduction of nickel catalyst with model bio-compounds

    OpenAIRE

    Cheng, F; Dupont, V; Twigg, MV

    2017-01-01

    The effects of temperature and S/C on the reduction extent and kinetics of a steam reforming NiO/α-Al₂O₃ catalyst were systematically investigated using five bio-compounds commonly produced during the fermentation, pyrolysis and gasification processes of biomass (acetic acid, ethanol, acetone, furfural and glucose). Reduction was also performed with methane and hydrogen for comparison. Kinetic modelling was applied to the NiO conversion range of 0–50% using the Handcock and Sharp method. The ...

  15. Three Ways.

    Science.gov (United States)

    Lisitano, Larry F.; And Others

    1983-01-01

    Three student projects using clay are discussed. These include a ceramic wall panel with an eagle motif, clay vessels formed by coiling clay, and clay puppets made with light bulbs as armatures. Instructions on materials, forming techniques, and finishing are given. (IS)

  16. Sulfur Deactivation of NOx Storage Catalysts: A Multiscale Modeling Approach

    Directory of Open Access Journals (Sweden)

    Rankovic N.

    2013-09-01

    Full Text Available Lean NOx Trap (LNT catalysts, a promising solution for reducing the noxious nitrogen oxide emissions from the lean burn and Diesel engines, are technologically limited by the presence of sulfur in the exhaust gas stream. Sulfur stemming from both fuels and lubricating oils is oxidized during the combustion event and mainly exists as SOx (SO2 and SO3 in the exhaust. Sulfur oxides interact strongly with the NOx trapping material of a LNT to form thermodynamically favored sulfate species, consequently leading to the blockage of NOx sorption sites and altering the catalyst operation. Molecular and kinetic modeling represent a valuable tool for predicting system behavior and evaluating catalytic performances. The present paper demonstrates how fundamental ab initio calculations can be used as a valuable source for designing kinetic models developed in the IFP Exhaust library, intended for vehicle simulations. The concrete example we chose to illustrate our approach was SO3 adsorption on the model NOx storage material, BaO. SO3 adsorption was described for various sites (terraces, surface steps and kinks and bulk for a closer description of a real storage material. Additional rate and sensitivity analyses provided a deeper understanding of the poisoning phenomena.

  17. On the degradation of fuel cell catalyst. From model systems to high surface area catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Arenz, M. [Copenhagen Univ. (Denmark). Dept. of Chemistry

    2010-07-01

    In the presented work, as an alternative accelerated degradation tests in the form of half-cell measurements combined with identical location transmission electron microscopy (IL-TEM){sup 10,} {sup 11} are presented. It is demonstrated that for different catalysts the degradation mechanism can be scrutinized in detail. Thus this approach enables the systematic investigation of fuel cell catalyst degradation in a reduced period of time. (orig.)

  18. Bond Energies in Models of the Schrock Metathesis Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Vasiliu, Monica; Li, Shenggang; Arduengo, Anthony J.; Dixon, David A.

    2011-06-23

    Heats of formation, adiabatic and diabatic bond dissociation energies (BDEs) of the model Schrock-type metal complexes M(NH)(CRR)(OH)₂ (M = Cr, Mo, W; CRR = CH₂, CHF, CF₂) and MO₂(OH)₂ compounds, and Brønsted acidities and fluoride affinities for the M(NH)(CH₂)(OH) ₂ transition metal complexes are predicted using high level CCSD(T) calculations. The metallacycle intermediates formed by reaction of C₂H4 with M(NH)-(CH₂)(OH)2 and MO₂(OH)₂ are investigated at the same level of theory. Additional corrections were added to the complete basis set limit to obtain near chemical accuracy ((1 kcal/mol). A comparison between adiabatic and diabatic BDEs is made and provides an explanation of trends in the BDEs. Electronegative groups bonded on the carbenic carbon lead to less stable Schrock-type complexes as the adiabatic BDEs ofMdCF₂ andMdCHF bonds are much lower than theMdCH₂ bonds. The Cr compounds have smaller BDEs than theWorMo complexes and should be less stable. Different M(NH)(OH)₂(C₃H₆) and MO(OH)₂(OC₂H4) metallacycle intermediates are investigated, and the lowest-energy metallacycles have a square pyramidal geometry. The results show that consideration of the singlet_triplet splitting in the carbene in the initial catalyst as well as in the metal product formed by the retro [2+2] cycloaddition is a critical component in the design of an effective olefin metathesis catalyst in terms of the parent catalyst and the groups being transferred.

  19. INVESTIGATION ON THE DYNAMIC RESPONSE PERFORMANCE OF A NOVEL THREE-WAY SOLENOID VALVE

    Institute of Scientific and Technical Information of China (English)

    Li Wei; Su Ling; Wang Ying; Zhou Longbao; Liu Quanbing

    2006-01-01

    Objective A novel high-speed three-way solenoid valve is developed, which is used for the common-rail injection system equipped on DME powered engine. In order to improve the dynamic response performance of the three-way solenoid. Methods Experimental studies have been conducted to investigate the effects of spool stroke, drive voltage, negative demagnetizing pulse and two drive schemes on the dynamic response performance of the three-way solenoid valve. Results The results show that the dynamic response performance of the three-way solenoid valve can be remarkably improved by shortening the spool stroke and increasing the drive voltage. Simultaneously, the difference between the response time of closing valve and that of opening valve decreases. At each different drive voltage, there exists an optimal negative demagnetizing pulse corresponding to the same positive exciting pulse. At this optimal pulse,the dynamic response performance of the three-way solenoid valve is the best. In addition, the high drive voltage can lead to the smaller optimal negative demagnetizing pulse. It is also indicated from the experiments that the dynamic response performance of the three-way solenoid valve is better when the NO. 1 drive scheme is adopted. The lower drive voltage results in the larger difference between the dynamic response performances for the two drive schemes.Conclusion The dynamic response performance of a novel three-way solenoid valve is good.

  20. PEM fuel cell catalyst degradation mechanism and mathematical modeling

    Science.gov (United States)

    Bi, Wu

    orders of magnitude higher under the air condition than in a non-reacting nitrogen environment. However, the difference was less than 100% between the nitrogen and air environments at a holding potential of 0.8 V (vs. RHE). Hence we believed that at an open-circuit condition, platinum was oxidized by oxygen molecule and further dissolved in acidic electrolyte. While at closed-circuit conditions, both chemical and electrochemical oxidation and dissolution might be involved. Platinum electrochemical oxidation kinetics was studied and simulated by cyclic voltammetry. In a simplified cathode degradation model, overall Pt particle growth by Pt mass exchange between small and large particles was clearly demonstrated through a favored Pt dissolution from small particles and Pt ion deposition onto large particles due to the particle size effect. The model also predicted the cycling upper potential and cycle frequency as the major positive effects on catalyst degradation, in an agreement with other literature results. We recommended further study of catalyst degradation especially on dissolution processes, and more durable electrode materials and an effective management of cell potentials will be needed to prolong cathode lifetime.

  1. A modular LHC built on the DNA three-way junction.

    Science.gov (United States)

    Probst, Markus; Langenegger, Simon M; Häner, Robert

    2014-01-07

    A light-harvesting complex composed of a π-stacked multichromophoric array in a DNA three-way junction is described. The modular design allows for a ready exchange of non-covalently attached energy acceptors.

  2. Modeling Deactivation of Catalysts for Selective Catalytic Reduction of NOx by KCl Aerosols

    DEFF Research Database (Denmark)

    Olsen, Brian Kjærgaard; Castellino, Francesco; Jensen, Anker Degn

    2017-01-01

    with the catalyst at the surface of the monolith wall, the transport and accumulation of potassium, bound to Brønsted acid sites, throughout the catalyst wall, and the resulting loss in SCR activity. Using an experimentally measured KCl aerosol size distribution as input, the model can replicate the observed...... if the particle size of the incoming aerosol is increased. The model provides, for the first time, a mechanistic framework for understanding and modeling SCR catalyst deactivation by KCl that may be applicable also for deactivation by other salts and at different operating conditions.......A detailed model for the deactivation of a V2O5–WO3/TiO2-based SCR monolith catalyst by potassium poisoning has been developed and validated. The model accounts for deposition of KCl aerosol particles present in the flue gas on the external catalyst surface, the reaction of the deposited particles...

  3. Mathematical Model of Synthesis Catalyst with Local Reaction Centers

    Directory of Open Access Journals (Sweden)

    I. V. Derevich

    2017-01-01

    Full Text Available The article considers a catalyst granule with a porous ceramic passive substrate and point active centers on which an exothermic synthesis reaction occurs. A rate of the chemical reaction depends on the temperature according to the Arrhenius law. Heat is removed from the pellet surface in products of synthesis due to heat transfer. In our work we first proposed a model for calculating the steady-state temperature of a catalyst pellet with local reaction centers. Calculation of active centers temperature is based on the idea of self-consistent field (mean-field theory. At first, it is considered that powers of the reaction heat release at the centers are known. On the basis of the found analytical solution, which describes temperature distribution inside the granule, the average temperature of the reaction centers is calculated, which then is inserted in the formula for heat release. The resulting system of transcendental algebraic equations is transformed into a system of ordinary differential equations of relaxation type and solved numerically to achieve a steady-state value. As a practical application, the article considers a Fischer-Tropsch synthesis catalyst granule with active cobalt metallic micro-particles. Cobalt micro-particles are the centers of the exothermic reaction of hydrocarbons macromolecular synthesis. Synthesis occurs as a result of absorption of the components of the synthesis gas on metallic cobalt. The temperature distribution inside the granule for a single local center and reaction centers located on the same granule diameter is found. It was found that there is a critical temperature of reactor exceeding of which leads to significant local overheating of the centers - thermal explosion. The temperature distribution with the local reaction centers is qualitatively different from the granule temperature, calculated in the homogeneous approximation. It is shown that, in contrast to the homogeneous approximation, the

  4. Model studies with gold: a versatile oxidation and hydrogenation catalyst.

    Science.gov (United States)

    Pan, Ming; Gong, Jinlong; Dong, Guangbin; Mullins, C Buddie

    2014-03-18

    Historically, scientists have considered gold an inert catalyst constituent. However, in recent decades, chemists have discovered that nanoscale gold shows exceptional activity for many chemical reactions. They have investigated model gold surfaces in order to obtain fundamental understanding of catalytic properties. In this Account, we present our current understanding of oxidation and hydrogenation reactions on the Au(111) single crystal as a planar representative of gold catalysts, revealing the interesting surface chemistry of gold. We begin by comparing two inverse reactions, alcohol oxidation and aldehyde hydrogenation, on a Au(111) surface. Beyond the expected different chemistry, we observe intriguing similarities since the same surface is employed. First, both molecular oxygen and hydrogen have high barriers to dissociation on Au(111), and frequently chemists study reactions here by using atomic O and H to populate the surfaces. Recombinative desorption features of oxygen and hydrogen are apparent at ∼500 and ∼110 K, lower than other transition metals. These results indicate that oxygen and hydrogen have low desorption activation energies and weakly chemisorb on the surface, likely leading to selective reactions. On the oxygen-precovered Au(111) surface, alcohols are selectively oxidized to aldehydes. Similarly, weakly bound hydrogen atoms on Au(111) also show chemoselective reactivity for hydrogenation of propionaldehyde and acetone. The second similarity is that the gold surface activates self-coupling of alcohol or aldehyde with oxygen or hydrogen, resulting in the formation of esters and ethers, respectively, in alcohol oxidation and aldehyde hydrogenation. During these two reactions, both alkoxy groups and alcohol-like species show up as intermediates, which likely play a key role in the formation of coupling products. In addition, the cross coupling reaction between alcohol and aldehyde occurs on both O- and H-modified surfaces, yielding the

  5. Analytical solution and meaning of feasible regions in two-component three-way arrays.

    Science.gov (United States)

    Omidikia, Nematollah; Abdollahi, Hamid; Kompany-Zareh, Mohsen; Rajkó, Róbert

    2016-10-01

    Although many efforts have been directed to the development of approximation methods for determining the extent of feasible regions in two- and three-way data sets; analytical determination (i.e. using only finite-step direct calculation(s) instead of the less exact numerical ones) of feasible regions in three-way arrays has remained unexplored. In this contribution, an analytical solution of trilinear decomposition is introduced which can be considered as a new direct method for the resolution of three-way two-component systems. The proposed analytical calculation method is applied to the full rank three-way data array and arrays with rank overlap (a type of rank deficiency) loadings in a mode. Close inspections of the analytically calculated feasible regions of rank deficient cases help us to make clearer the information gathered from multi-way problems frequently emerged in physics, chemistry, biology, agricultural, environmental and clinical sciences, etc. These examinations can also help to answer, e.g., the following practical question: "Is two-component three-way data with proportional loading in a mode actually a three-way data array?" By the aid of the additional information resulted from the investigated feasible regions of two-component three-way data arrays with proportional profile in a mode, reasons for the inadequacy of the seemingly trilinear data treatment methods published in the literature (e.g., U-PLS/RBL-LD that was used for extraction of quantitative and qualitative information reported by Olivieri et al. (Anal. Chem. 82 (2010) 4510-4519)) could be completely understood.

  6. Three-Way Channels With Multiple Unicast Sessions: Capacity Approximation via Network Transformation

    KAUST Repository

    Chaaban, Anas

    2016-09-28

    A network of three nodes mutually communicating with each other is studied. This multi-way network is a suitable model for three-user device-to-device communications. The main goal of this paper is to characterize the capacity region of the underlying Gaussian three-way channel (3WC) within a constant gap. To this end, a capacity outer bound is derived using cut-set bounds and genie-aided bounds. For achievability, the 3WC is first transformed into an equivalent star channel. This latter is then decomposed into a set of “successive” sub-channels, leading to a sub-channel allocation problem. Using backward decoding, interference neutralization, and known results on the capacity of the star-channel relying of physical-layer network coding, an achievable rate region for the 3WC is obtained. It is then shown that the achievable rate region is within a constant gap of the developed outer bound, leading to the desired capacity approximation. Interestingly, in contrast to the Gaussian two-way channel (TWC), adaptation is necessary in the 3WC. Furthermore, message splitting is another ingredient of the developed scheme for the 3WC, which is not required in the TWC. The two setups are, however, similar in terms of their sum-capacity pre-log, which is equal to 2. Finally, some interesting networks and their approximate capacities are recovered as special cases of the 3WC, such as the cooperative broadcast channel and multiple access channel.

  7. In-situ Spectroscopic Studies and Modelling of Crystallization Processes of Sulphuric Acid Catalysts

    DEFF Research Database (Denmark)

    Oehlers, C.; Fehrmann, Rasmus; Masters, Stephen Grenville

    1996-01-01

    Deactivation of commercial and prototype sulphuric acid catalysts has been investigated in-situ by ESR spectroscopy. The influence of support pore structure,and the chemical composition of the catalyst and the gas phase was dicussed.A statistical lattice model was applied to describe...

  8. Active Gold-Ceria and Gold-Ceria/titania Catalysts for CO Oxidation. From Single-Crystal Model Catalysts to Powder Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, Jose A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Si, Rui [Brookhaven National Lab. (BNL), Upton, NY (United States); Evans, Jaime [Central Univ. of Venezuela, Caracas (Venezuela); Xu, Wenqian [Brookhaven National Lab. (BNL), Upton, NY (United States); Hanson, Jonathan C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Tao, Jing [Brookhaven National Lab. (BNL), Upton, NY (United States); Zhu, Yimei [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2014-07-23

    We studied CO oxidation on model and powder catalysts of Au-CeO2 and Au-CeOx/TiO2. Phenomena observed in Au-CeO2(1 1 1) and Au-CeO2/TiO2(1 1 0) provided useful concepts for designing and preparing highly active and stable Au-CeOx/TiO2 powder catalysts for CO oxidation. Small particles of Au dispersed on CeO2(1 1 1) displayed high catalytic activity, making Au-CeO2(1 1 1) a better CO oxidation catalyst than Au-TiO2(1 1 0) or Au-MgO(1 0 0). An excellent support for gold was found after depositing nanoparticles of ceria on TiO2(1 1 0). The CeOx nanoparticles act as nucleation centers for gold, improving dispersion of the supported metal and helping in the creation of reaction sites efficient for the adsorption of CO and the dissociation of the O2 molecule. High-surface area catalysts were prepared by depositing gold on ceria nanorods and CeOx/TiO2 powders. The samples were tested for the low-temperature (10–70 °C) oxygen-rich (1%CO/4%O2/He) CO oxidation reaction after pre-oxidation (20%O2/He, 300 °C) and pre-reduction (5%H2/He, 300 °C) treatments. Moreover, synchrotron-based operando X-ray diffraction (XRD) and X-ray absorption (XAS) spectroscopy were used to study the Au-CeO2 and Au-CeOx/TiO2 catalysts under reaction conditions. Our operando findings indicate that the most active phase of these catalysts for low-temperature CO oxidation consist of small particles of metallic Au dispersed on CeO2 or CeOx/TiO2.

  9. Structure and chemistry of model catalysts in ultrahigh vacuum

    Science.gov (United States)

    Walker, Joshua D.

    The study of catalysis is a key area of focus not only in the industrial sector but also in the nature and biological systems. The market for catalysis is a multi-billion dollar industry. Many of the materials and products we use on a daily basis are formed through a catalytic process. The quest to understanding and improving catalytic mechanisms is ongoing. Many model catalysts use transition metals as a support for chemical reactions to take place due to their selectivity and activity. Palladium, gold, and copper metals are studied in this work and show the ability to be catalytically reactive. It is important to understand the characteristics and properties of these surfaces. A well-known example of catalysis is the conversion of carbon monoxide (CO), a very harmful gas to carbon dioxide (CO2) which is less harmful. This reaction is mainly seen in the automotive industry. This reaction is investigated in this work on a Au(111) single crystal, which is normally inert but becomes reactivity with the adsorption of oxygen on the surface. Temperature Programmed Desorption (TPD) is used to understand some of the chemistry and effects with and without the addition of H2O. The oxidation of CO is shown to be enhanced by the addition of water, but warrants further analysis too fully understand the different mechanisms and reaction pathways existing. The field of nano-electronics is rapidly growing as technology continues to challenge scientists to create innovative ideas. The trend to produce smaller electronic products is increasing as consumer demands persist. It has been shown previously that 1,4-phenlyene diisocyanobenzene (1,4-PDI) on Au(111) react to form one-dimensional oligomer chains comprising alternating gold and 1,4-PDI units on the Au(111) surface. A similar compound 1,3-phenlyene diisocyanobenzene (1,3-PDI) was studied in order to investigate whether the oligomerization found for 1,4-PDI is a general phenomenon and to ultimately explore the effect of

  10. Shape Optimization of Three-Way Reversing Valve for Cavitation Reduction

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Myeong Gon; Han, Seung Ho [Donga Univ., Busan (Korea, Republic of); Lim, Cha Suk [Baek San Hi-Tech Co., Ltd., Seoul (Korea, Republic of)

    2015-11-15

    A pair of two-way valves typically is used in automotive washing machines, where the water flow direction is frequently reversed and highly pressurized clean water is sprayed to remove the oil and dirt remaining on machined engine and transmission blocks. Although this valve system has been widely used because of its competitive price, its application is sometimes restricted by surging effects, such as pressure ripples occurring in rapid changes in water flow caused by inaccurate valve control. As an alternative, one three-way reversing valve can replace the valve system because it provides rapid and accurate changes to the water flow direction without any precise control device. However, a cavitation effect occurs because of the complicated bottom plug shape of the valve. In this study, the cavitation index and percent of cavitation (POC) were introduced to numerically evaluate fluid flows via computational fluid dynamics (CFD) analysis. To reduce the cavitation effect generated by the bottom plug, the optimal shape design was carried out through a parametric study, in which a simple computer-aided engineering (CAE) model was applied to avoid time consuming CFD analysis and difficulties in achieving convergence. The optimal shape design process using full factorial design of experiments (DOEs) and an artificial neural network meta-model yielded the optimal waist and tail length of the bottom plug with a POC value of less than 30%, which meets the requirement of no cavitation occurrence. The optimal waist length, tail length and POC value were found to 6.42 mm, 6.96 mm and 27%, respectively.

  11. Shape optimization of three-way reversing valve for cavitation reduction

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Myeong Gon; Han, Seung Ho [Dept. of Mechanical Engineering, Dong-A University, Busan (Korea, Republic of); Lim, Cha Suk [Baek San Hi-Tech Co., Ltd., Yangsan(Korea, Republic of)

    2015-11-15

    A pair of two-way valves typically is used in automotive washing machines, where the water flow direction is frequently reversed and highly pressurized clean water is sprayed to remove the oil and dirt remaining on machined engine and transmission blocks. Although this valve system has been widely used because of its competitive price, its application is sometimes restricted by surging effects, such as pressure ripples occurring in rapid changes in water flow caused by inaccurate valve control. As an alternative, one three-way reversing valve can replace the valve system because it provides rapid and accurate changes to the water flow direction without any precise control device. However, a cavitation effect occurs because of the complicated bottom plug shape of the valve. In this study, the cavitation index and percent of cavitation (POC) were introduced to numerically evaluate fluid flows via computational fluid dynamics (CFD) analysis. To reduce the cavitation effect generated by the bottom plug, the optimal shape design was carried out through a parametric study, in which a simple computer-aided engineering (CAE) model was applied to avoid time-consuming CFD analysis and difficulties in achieving convergence. The optimal shape design process using full factorial design of experiments (DOEs) and an artificial neural network meta-model yielded the optimal waist and tail length of the bottom plug with a POC value of less than 30%, which meets the requirement of no cavitation occurrence. The optimal waist length, tail length and POC value were found to 6.42 mm, 6.96 mm and 27%, respectively.

  12. Thermodynamically stable RNA three-way junction for constructing multifunctional nanoparticles for delivery of therapeutics

    Science.gov (United States)

    Shu, Dan; Shu, Yi; Haque, Farzin; Abdelmawla, Sherine; Guo, Peixuan

    2011-10-01

    RNA nanoparticles have applications in the treatment of cancers and viral infection; however, the instability of RNA nanoparticles has hindered their development for therapeutic applications. The lack of covalent linkage or crosslinking in nanoparticles causes dissociation in vivo. Here we show that the packaging RNA of bacteriophage phi29 DNA packaging motor can be assembled from 3-6 pieces of RNA oligomers without the use of metal salts. Each RNA oligomer contains a functional module that can be a receptor-binding ligand, aptamer, short interfering RNA or ribozyme. When mixed together, they self-assemble into thermodynamically stable tri-star nanoparticles with a three-way junction core. These nanoparticles are resistant to 8 M urea denaturation, are stable in serum and remain intact at extremely low concentrations. The modules remain functional in vitro and in vivo, suggesting that the three-way junction core can be used as a platform for building a variety of multifunctional nanoparticles. We studied 25 different three-way junction motifs in biological RNA and found only one other motif that shares characteristics similar to the three-way junction of phi29 pRNA.

  13. Uniqueness conditions for constrained three-way factor decompositions with linearly dependent loadings

    NARCIS (Netherlands)

    Stegeman, Alwin; De Almeida, Andre L. F.

    2009-01-01

    In this paper, we derive uniqueness conditions for a constrained version of the parallel factor (Parafac) decomposition, also known as canonical decomposition (Candecomp). Candecomp/Parafac (CP) decomposes a three-way array into a prespecified number of outer product arrays. The constraint is that

  14. Parabolic Anderson model with a finite number of moving catalysts

    CERN Document Server

    Castell, Fabienne; Maillard, Grégory

    2010-01-01

    We consider the parabolic Anderson model (PAM) which is given by the equation $\\partial u/\\partial t = \\kappa\\Delta u + \\xi u$ with $u\\colon\\, \\Z^d\\times [0,\\infty)\\to \\R$, where $\\kappa \\in [0,\\infty)$ is the diffusion constant, $\\Delta$ is the discrete Laplacian, and $\\xi\\colon\\,\\Z^d\\times [0,\\infty)\\to\\R$ is a space-time random environment that drives the equation. The solution of this equation describes the evolution of a ``reactant'' $u$ under the influence of a ``catalyst'' $\\xi$. In the present paper we focus on the case where $\\xi$ is a system of $n$ independent simple random walks each with step rate $2d\\rho$ and starting from the origin. We study the \\emph{annealed} Lyapunov exponents, i.e., the exponential growth rates of the successive moments of $u$ w.r.t.\\ $\\xi$ and show that these exponents, as a function of the diffusion constant $\\kappa$ and the rate constant $\\rho$, behave differently depending on the dimension $d$. In particular, we give a description of the intermittent behavior of the sys...

  15. Direct dimethyl-ether (DME) synthesis by spatial patterned catalyst arrangement. A modeling and simulation study

    Energy Technology Data Exchange (ETDEWEB)

    McBride, K.; Turek, T.; Guettel, R. [Clausthal Univ. of Technology (Germany). Inst. of Chemical Process Engineering

    2011-07-01

    The effect of spatially patterned catalyst beds was investigated for direct DME synthesis from synthesis gas as an example. A layered arrangement of methanol synthesis and dehydration catalyst was chosen and studied by numerical simulation under typical operating conditions for single-step DME synthesis. It was revealed that catalyst layers significantly influence the DME productivity. With an increasing number of layers from 2 to 40, an increase in DME productivity was observed approaching the performance of a physical catalyst mixture for an infinite number of layers. The results prove that a physical mixture of methanol synthesis and dehydration catalyst achieves the highest DME productivity under operating conditions chosen in this study. This can be explained by the higher average methanol concentration for the layered catalyst arrangement and thus stronger equilibrium constraints for the methanol synthesis reaction. Essentially, the layered catalyst arrangement is comparable to a cascade model of the two-step process, which is less efficient in terms of DME yield than the single-step process. However, since a significant effect was found, the layered catalyst arrangement could be beneficial for other reaction systems. (orig.)

  16. Generation of Nano-Catalyst Particles by Spinodal Nano-Decomposition in Perovskite

    Science.gov (United States)

    Kizaki, Hidetoshi; Kusakabe, Koichi; Nogami, Soichiro; Katayama-Yoshida, Hiroshi

    2008-10-01

    A new mechanism of nano-catalyst generation based on the spinodal nano-decomposition in self-regenerating perovskite catalysts for automotive-emissions control is proposed. To demonstrate existence of the spinodal nano-decomposition in real perovskite catalysts, we performed first-principles calculations to evaluate the free energy of La(Fe1-xPdx)O3 and La(Fe1-xRhx)O3. The result indicates appearance of a spinodal region in the phase diagram of each material. Formation of nano-catalyst particles in the perovskite host matrix is crucial for the self-regeneration of perovskite catalyst. Based on the spinodal nano-decomposition model, possible materials are designed for new three-way catalyst with no contents of precious metal.

  17. Modeling of Isobutane/Butene Alkylation Using Solid Acid Catalysts in a Fixed Bed Reactor

    Institute of Scientific and Technical Information of China (English)

    Liu Zheng; Tang Xiaojin; Hu Lifeng; Hou Shuandi

    2016-01-01

    A dynamic mass transfer model of isobutane/butene alkylation over solid acid catalysts in a ifxed bed reactor was established. In the model, a modiifed equation for the relationship between point activity and effective diffusion coefifcient was proposed. It is found that the simulation results ift the experimental data well and the breakthrough time of the bed layer is predicted accurately. By modeling the alkylation process, the time-space distribution of butene and point activity proifles of catalysts can be obtained. Furthermore, the reasons for the deactivation of solid acid catalysts were investigated. It indicates that the main reason for the deactivation of catalysts is the site coverage near the inlet of the reactor, while it is ascribed to the steric effect in the region far away from the inlet.

  18. Perspective: On the active site model in computational catalyst screening

    Science.gov (United States)

    Reuter, Karsten; Plaisance, Craig P.; Oberhofer, Harald; Andersen, Mie

    2017-01-01

    First-principles screening approaches exploiting energy trends in surface adsorption represent an unparalleled success story in recent computational catalysis research. Here we argue that our still limited understanding of the structure of active sites is one of the major bottlenecks towards an ever extended and reliable use of such computational screening for catalyst discovery. For low-index transition metal surfaces, the prevalently chosen high-symmetry (terrace and step) sites offered by the nominal bulk-truncated crystal lattice might be justified. For more complex surfaces and composite catalyst materials, computational screening studies will need to actively embrace a considerable uncertainty with respect to what truly are the active sites. By systematically exploring the space of possible active site motifs, such studies might eventually contribute towards a targeted design of optimized sites in future catalysts.

  19. Refinement of the solution structure of a branched DNA three-way junction.

    Science.gov (United States)

    Ouporov, I V; Leontis, N B

    1995-01-01

    We have refined the structure of the DNA Three-Way Junction complex, TWJ-TC, described in the companion paper by quantitative analysis of two 2D NOESY spectra (mixing times 60 and 200 ms) obtained in D2O solution. NOESY crosspeak intensities extracted from these spectra were used in two kinds of refinement procedure: 1) distance-restrained energy minimization (EM) and molecular dynamics (MD) and 2) full relaxation matrix back calculation refinement. The global geometry of the refined model is very similar to that of a published, preliminary model (Leontis, 1993). Two of the helical arms of the junction are stacked. These are Helix 1, defined by basepairs S1-G1/S3-C12 through S1-C5/S3-G8 and Helix 2, which comprises basepairs S1-C6/S2-G5 through S1-G10/S2-G1. The third helical arm (Helix 3), comprised of basepairs S2-C6/S3-G5 through S2-C10/S3-G1 extends almost perpendicularly from the axis defined by Helices 1 and 2. The bases S1-C5 and S1-C6 of Strand 1 are continuously stacked across the junction region. The conformation of this strand is close to that of B-form DNA along its entire length, including the S1-C5 to S1-C6 dinucleotide step at the junction. The two unpaired bases S3-T6 and S3-C7 lie outside of the junction along the minor groove of Helix 1 and largely exposed to solvent. Analysis of the refined structure reveals that the glycosidic bond of S3-T6 exists in the syn conformation, allowing the methyl group of this residue to contact the hydrophobic surface of the minor groove of Helix 1, at S3-G11. The helical parameters of the three helical arms of the structure exhibit only weak deviations from typical values for right-handed B-form DNA. Unusual dihedral angles are only observed for the sugarphosphate backbone joining the "hinge" residues, S2-G5 and S2-C6, and S3-G5 through S3-G8. The glycosidic bond of S3-G8also lies within the syn range, allowing favorable Watson-Crick base-pairing interactions with Si -C5. The stability of this structure was checked

  20. TRAP: A Three-Way Handshake Server for TCP Connection Establishment

    Directory of Open Access Journals (Sweden)

    Fu-Hau Hsu

    2016-11-01

    Full Text Available Distributed denial of service attacks have become more and more frequent nowadays. In 2013, a massive distributed denial of service (DDoS attack was launched against Spamhaus causing the service to shut down. In this paper, we present a three-way handshaking server for Transmission Control Protocol (TCP connection redirection utilizing TCP header options. When a legitimate client attempted to connect to a server undergoing an SYN-flood DDoS attack, it will try to initiate a three-way handshake. After it has successfully established a connection, the server will reply with a reset (RST packet, in which a new server address and a secret is embedded. The client can, thus, connect to the new server that only accepts SYN packets with the corrected secret using the supplied secret.

  1. Filter Connected with Three-way Cock in Remove of the Vehicle in Triamcinolone Acetonide

    Institute of Scientific and Technical Information of China (English)

    Lei Du; Yiqiao Xing; Changzheng Chen

    2006-01-01

    Purpose: To evaluate the clinical effect of 5-μm pore filter connected with three-way cock by removing the vehicle in triamcinolone acetonide (TA) suspension.Methods: Through 5-μm pore filter connected with three-way cock, TA suspension was replaced by intraocular irrigating solution. The new suspension has been applied to 60 cases of diabetic branch retinal vein occlusion, diabetic macular edema and agerelated macular degeneration patients through intravitreal injection. It was also been applied to 41 cases of diabetic retinopathy, epimacular membrane, proliferative vitreoretinopathy and idiopathic macular hole patients to assist pas plana vitrectomy (PPV). Whether TA particles can adhere to posterior hyaloid cortex, epiretinal membrane and internal limiting membrane during the surgery have been observed.During follow up, corrected visual acuity and intraocular pressure were recorded.Results: Fiveμm pore filter connected with three-way cock can remove the vehicle in TA suspension successfully and retain TA particles. When the new suspension was applied to assist PPV, it can adhere to posterior hyaloid cortex, epiretinal membrane, internal limiting membrane and visualized them clearly. In all the 41 cases that underwent PPV surgery, visual acuity of 30 cases increased or remained stable.Intraocular hypertension happened in 4 cases. Two cases of the 41 patients had cataract formation during follow up. In the 60 cases that underwent TA intravitreal injection,45 cases increased their visual acuity at least 2 lines. Intraocular hypertension happened in 17 cases and 4 patients had cataract formation. None of the 101 patients caught endophthalmitis or other serious complications.Conclusion: Filter connected with three-way cock can remove the vehicle in TA suspension effectively and this procedure can be applied to intravitreal injection or PPV. This manipulation is so simple that it deserves to be popularized for clinical use.

  2. Optimum prediction of three-way crosses from single crosses in forage maize (Zea mays L.).

    Science.gov (United States)

    Melchinger, A E; Geiger, H H; Seitz, G; Schmidt, G A

    1987-07-01

    Three-way cross means were predicted with formulae involving linear functions of general (GCA) and specific combining ability (SCA) effects estimated from single-cross factorials between genetically divergent populations. Data from an experiment with 66 single-cross and 66 three-way cross forage maize (Zea mays L.) hybrids was used for comparing the prediction formulae. The genotypic correlation (r) between observed and predicted three-way crosses increased with increasing χ, the weighting factor of SCA effects, for plant height and ear dry matter (DM) content. It displayed slightly convex curves for total and stover DM yield, ear percentage, and metabolizable energy content of stover. For Jenkins' method B, r was considerably less than 1.0 for all traits, indicating the presence of epistasis. The square root of heritability (hĜ) of the predicted means decreased with increasing χ, the reduction being small with a greater number of test environments. Using the product r·hĜ as a criterion of efficiency, none of the prediction methods was consistently superior and the differences among them were rather small (< 7.5%) for all traits, irrespective of the number of test environments. We recommend evaluating the GCA of a greater number of lines from each parent population in testcrosses with a small number of elite lines from the opposite population. All possible three-way or double crosses between both sets of lines should be predicted by Jenkins's method C. This procedure allows one to select with a higher intensity among the predicted hybrids and thus should increase the genetic gain.

  3. Three-way analysis of spectrospatial electromyography data: classification and interpretation.

    Directory of Open Access Journals (Sweden)

    Jukka-Pekka Kauppi

    Full Text Available Classifying multivariate electromyography (EMG data is an important problem in prosthesis control as well as in neurophysiological studies and diagnosis. With modern high-density EMG sensor technology, it is possible to capture the rich spectrospatial structure of the myoelectric activity. We hypothesize that multi-way machine learning methods can efficiently utilize this structure in classification as well as reveal interesting patterns in it. To this end, we investigate the suitability of existing three-way classification methods to EMG-based hand movement classification in spectrospatial domain, as well as extend these methods by sparsification and regularization. We propose to use Fourier-domain independent component analysis as preprocessing to improve classification and interpretability of the results. In high-density EMG experiments on hand movements across 10 subjects, three-way classification yielded higher average performance compared with state-of-the art classification based on temporal features, suggesting that the three-way analysis approach can efficiently utilize detailed spectrospatial information of high-density EMG. Phase and amplitude patterns of features selected by the classifier in finger-movement data were found to be consistent with known physiology. Thus, our approach can accurately resolve hand and finger movements on the basis of detailed spectrospatial information, and at the same time allows for physiological interpretation of the results.

  4. Three-way analysis of spectrospatial electromyography data: classification and interpretation.

    Science.gov (United States)

    Kauppi, Jukka-Pekka; Hahne, Janne; Müller, Klaus-Robert; Hyvärinen, Aapo

    2015-01-01

    Classifying multivariate electromyography (EMG) data is an important problem in prosthesis control as well as in neurophysiological studies and diagnosis. With modern high-density EMG sensor technology, it is possible to capture the rich spectrospatial structure of the myoelectric activity. We hypothesize that multi-way machine learning methods can efficiently utilize this structure in classification as well as reveal interesting patterns in it. To this end, we investigate the suitability of existing three-way classification methods to EMG-based hand movement classification in spectrospatial domain, as well as extend these methods by sparsification and regularization. We propose to use Fourier-domain independent component analysis as preprocessing to improve classification and interpretability of the results. In high-density EMG experiments on hand movements across 10 subjects, three-way classification yielded higher average performance compared with state-of-the art classification based on temporal features, suggesting that the three-way analysis approach can efficiently utilize detailed spectrospatial information of high-density EMG. Phase and amplitude patterns of features selected by the classifier in finger-movement data were found to be consistent with known physiology. Thus, our approach can accurately resolve hand and finger movements on the basis of detailed spectrospatial information, and at the same time allows for physiological interpretation of the results.

  5. Ordered mesoporous materials as model supports to study catalyst preparation

    NARCIS (Netherlands)

    Sietsma, J.R.A.

    2007-01-01

    Catalysts are indispensable to modern-day society because of their prominent role in petroleum refining, chemical processing, and the reduction of environmental pollution. The catalytically active component often consists of small metal (oxide) particles that are supported on a carrier such as silic

  6. Real catalysis on single crystalline model catalysts with in-situ reactivity measurement

    OpenAIRE

    O. Shekhah; Ranke, W.; Schlögl, R.

    2003-01-01

    The pressure and materials gap between reactivity studies in UHV and real catalysis can only be overcome by application of in-situ methods for catalyst characterization and/or activity measurements under realistic pressure and temperature conditions. As a model reaction we study the economically important catalytic dehydrogenation of ethylbenzene (EB) to styrene (St) [1]. The technical catalyst consists of potassium-promoted iron oxides. We use single crystalline epitaxial layers of Fe2O3, Fe...

  7. Research on Integration of an Automotive Exhaust-Based Thermoelectric Generator and a Three-Way Catalytic Converter

    Science.gov (United States)

    Deng, Y. D.; Chen, Y. L.; Chen, S.; Xianyu, W. D.; Su, C. Q.

    2015-06-01

    A key research topic related to thermoelectric generators (TEGs) for automotive applications is to improve their compatibility with the original vehicle exhaust system, which determines the quality of the exhaust gas treatment and the realization of energy conservation and emission reduction. A new TEG integrated with a three-way catalytic converter (CTEG) by reshaping the converter as the heat exchanger is proposed. A heat-flux coupling simulation model of the integrated TEG is established at the light-off stage of the original three-way catalytic converter (TWC). Temperature distribution maps of the integrated heat exchanger, thermoelectric modules, and cooling-water tank are obtained to present the process of energy flow among the parts of the CTEG. Based on the simulation results, the output power of the CTEG is calculated by a mathematical model. A minimum output power of 31.93 W can be obtained by conversion when the TWC starts working at steady conditions. Theoretically, this case study demonstrates the great potential for use of CTEGs in vehicles.

  8. Energetic Mapping of Ni Catalysts by Detailed Kinetic Modeling

    DEFF Research Database (Denmark)

    Bjørgum, Erlend; Chen, De; Bakken, Mari G.

    2005-01-01

    was found to be 119 kJ/mol, and the binding energy of C to the Ni(111) surface of the crystal was 703 kJ/mol. The supported catalysts consist of nickel supported on hydrotalcite-like compounds with three different Mg2+/Al3+ ratios. The experimental results show that for the supported Ni catalysts TPD of CO...... leads to desorption of both CO and CO2, with the latter being dominant. Dissociation of CO takes place, and considerable amounts of residue C are left on the surface. The residue C is removed by temperature-programmed oxidation (TPO). The results show that a low Mg2+/Al3+ ratio in the hydrotalcite...

  9. Towards a general growth model for graphene CVD on transition metal catalysts

    Science.gov (United States)

    Cabrero-Vilatela, Andrea; Weatherup, Robert S.; Braeuninger-Weimer, Philipp; Caneva, Sabina; Hofmann, Stephan

    2016-01-01

    The chemical vapour deposition (CVD) of graphene on three polycrystalline transition metal catalysts, Co, Ni and Cu, is systematically compared and a first-order growth model is proposed which can serve as a reference to optimize graphene growth on any elemental or alloy catalyst system. Simple thermodynamic considerations of carbon solubility are insufficient to capture even basic growth behaviour on these most commonly used catalyst materials, and it is shown that kinetic aspects such as carbon permeation have to be taken into account. Key CVD process parameters are discussed in this context and the results are anticipated to be highly useful for the design of future strategies for integrated graphene manufacture.The chemical vapour deposition (CVD) of graphene on three polycrystalline transition metal catalysts, Co, Ni and Cu, is systematically compared and a first-order growth model is proposed which can serve as a reference to optimize graphene growth on any elemental or alloy catalyst system. Simple thermodynamic considerations of carbon solubility are insufficient to capture even basic growth behaviour on these most commonly used catalyst materials, and it is shown that kinetic aspects such as carbon permeation have to be taken into account. Key CVD process parameters are discussed in this context and the results are anticipated to be highly useful for the design of future strategies for integrated graphene manufacture. Electronic supplementary information (ESI) available: Fig. S1. See DOI: 10.1039/c5nr06873h

  10. Model heterogeneous acid catalysts and metal-support interactions: A combined surface science and catalysis study

    Energy Technology Data Exchange (ETDEWEB)

    Boszormenyi, I.

    1991-05-01

    This (<100 [Angstrom]) silica-alumina layers were tested as potential model heterogeneous acid catalysts for combined surface science and catalysis studies. Three preparation methods were used: oxidation of r3 [times] r3 R30 Al/Si(111) structure in UHV; deposition on Si(lll) from aqueous solution; and argon ion beam sputter deposition in UHV. The homogeneous thin layers are amorphous, and the chemical environment of surface atoms is similar to that of Si, Al and oxygen atoms on high surface area acid catalysts. Since the ion beam-deposited thin layer of silica-alumina has the same composition as the target zeolite this deposition method is a promising tool to prepare model catalysts using practical catalyst targets. The silica-alumina layers are active in cumene cracking, a typical acid catalyzed reaction. In order to clearly distinguish background reactions and the acid catalyzed reaction at least 20 cm[sup 2] catalyst surface area is needed. Two series of model platinum-alumina catalysts were prepared in a combined UHV -- high pressure reactor cell apparatus by depositing alumina on polycrystalline Pt foil and by vapor depositing Pt on a thin alumina layer on Au. Both model surfaces have been prepared with and without chlorine. AES, CO desorption as well as methyl cyclopentane (MCP) hydrogenolysis studies indicate that the Pt surface area is always higher if a chlorination step is involved. Selectivity patterns in MCP ring opening on Pt-on-alumina'' and on alumina-on-Pt'' are different; only the former is a linear combination of selective and statistical ring opening. Product distribution, however, changes with coverage and reaction time. The properties of the two model catalyst systems and role of chlorine in MCP hydrogenolysis are also discussed.

  11. Model heterogeneous acid catalysts and metal-support interactions: A combined surface science and catalysis study

    Energy Technology Data Exchange (ETDEWEB)

    Boszormenyi, I.

    1991-05-01

    This (<100 {Angstrom}) silica-alumina layers were tested as potential model heterogeneous acid catalysts for combined surface science and catalysis studies. Three preparation methods were used: oxidation of r3 {times} r3 R30 Al/Si(111) structure in UHV; deposition on Si(lll) from aqueous solution; and argon ion beam sputter deposition in UHV. The homogeneous thin layers are amorphous, and the chemical environment of surface atoms is similar to that of Si, Al and oxygen atoms on high surface area acid catalysts. Since the ion beam-deposited thin layer of silica-alumina has the same composition as the target zeolite this deposition method is a promising tool to prepare model catalysts using practical catalyst targets. The silica-alumina layers are active in cumene cracking, a typical acid catalyzed reaction. In order to clearly distinguish background reactions and the acid catalyzed reaction at least 20 cm{sup 2} catalyst surface area is needed. Two series of model platinum-alumina catalysts were prepared in a combined UHV -- high pressure reactor cell apparatus by depositing alumina on polycrystalline Pt foil and by vapor depositing Pt on a thin alumina layer on Au. Both model surfaces have been prepared with and without chlorine. AES, CO desorption as well as methyl cyclopentane (MCP) hydrogenolysis studies indicate that the Pt surface area is always higher if a chlorination step is involved. Selectivity patterns in MCP ring opening on ``Pt-on-alumina`` and on ``alumina-on-Pt`` are different; only the former is a linear combination of selective and statistical ring opening. Product distribution, however, changes with coverage and reaction time. The properties of the two model catalyst systems and role of chlorine in MCP hydrogenolysis are also discussed.

  12. Aromatization of light naphtha fractions on zeolites: 2. Model of catalyst deactivation

    Directory of Open Access Journals (Sweden)

    Ostrovski Nikolaj M.

    2004-01-01

    Full Text Available A model of catalyst deactivation in the "Zeoforming" process was developed. The deactivation rate constants and activation energies were estimated. The role of adsorbed oligomers in the reaction and the deactivation kinetics were examined. The model is intended for further modeling and optimization of the process.

  13. An information-gain approach to detecting three-way epistatic interactions in genetic association studies

    DEFF Research Database (Denmark)

    Hu, Ting; Chen, Yuanzhu; Kiralis, Jeff W;

    2013-01-01

    Background Epistasis has been historically used to describe the phenomenon that the effect of a given gene on a phenotype can be dependent on one or more other genes, and is an essential element for understanding the association between genetic and phenotypic variations. Quantifying epistasis....... In the tuberculosis data, we found a statistically significant pure three-way epistatic interaction effect that was stronger than any lower-order associations. Conclusion Our study provides a methodological basis for detecting and characterizing high-order gene-gene interactions in genetic association studies....

  14. Steiner minimal trees—the final destinations for lipid nanotube networks with three-way junctions

    Science.gov (United States)

    Yin, YaJun; Wu, JiYe; Yin, Jie; Fan, QinShan

    2011-04-01

    Through the combination of the minimum energy principle in physics and the Steiner minimal tree (SMT) theory in geometry, this paper proves a universal law for lipid nanotube networks (LNNs): at stable equilibrium state, the network of three-way lipid nanotube junctions is equivalent to a SMT. Besides, an arbitrary (usually non-equilibrium) network of lipid nanotube junctions may fission into a SMT through diffusions and dynamic self-organizations of lipid molecules. Potential applications of the law to the micromanipulations of LNNs are presented.

  15. DNA Three Way Junction Core Decorated with Amino Acids-Like Residues-Synthesis and Characterization

    Directory of Open Access Journals (Sweden)

    Claudia Addamiano

    2016-08-01

    Full Text Available Construction and physico-chemical behavior of DNA three way junction (3WJ functionalized by protein-like residues (imidazole, alcohol and carboxylic acid at unpaired positions at the core is described. One 5′-C(S-propargyl-thymidine nucleotide was specifically incorporated on each strand to react through a post synthetic CuACC reaction with either protected imidazolyl-, hydroxyl- or carboxyl-azide. Structural impacts of 5′-C(S-functionalization were investigated to evaluate how 3WJ flexibility/stability is affected.

  16. An analytical model of hydrogen evolution and oxidation reactions on electrodes partially covered with a catalyst.

    Science.gov (United States)

    Kemppainen, Erno; Halme, Janne; Lund, Peter D

    2016-05-11

    Our previous theoretical study on the performance limits of the platinum (Pt) nanoparticle catalyst for the hydrogen evolution reaction (HER) had shown that the mass transport losses at a partially catalyst-covered planar electrode are independent of the catalyst loading. This suggests that the two-dimensional (2D) numerical model used could be simplified to a one-dimensional (1D) model to provide an easier but equally accurate description of the operation of these HER electrodes. In this article, we derive an analytical 1D model and show that it indeed gives results that are practically identical to the 2D numerical simulations. We discuss the general principles of the model and how it can be used to extend the applicability of existing electrochemical models of planar electrodes to low catalyst loadings suitable for operating photoelectrochemical devices under unconcentrated sunlight. Since the mass transport losses of the HER are often very sensitive to the H2 concentration, we also discuss the limiting current density of the hydrogen oxidation reaction (HOR) and how it is not necessarily independent of the reaction kinetics. The results give insight into the interplay of kinetic and mass-transport limitations at HER/HOR electrodes with implications for the design of kinetic experiments and the optimization of catalyst loadings in the photoelectrochemical cells.

  17. Nanostructured, mesoporous Au/TiO2 model catalysts – structure, stability and catalytic properties

    Directory of Open Access Journals (Sweden)

    Matthias Roos

    2011-09-01

    Full Text Available Aiming at model systems with close-to-realistic transport properties, we have prepared and studied planar Au/TiO2 thin-film model catalysts consisting of a thin mesoporous TiO2 film of 200–400 nm thickness with Au nanoparticles, with a mean particle size of ~2 nm diameter, homogeneously distributed therein. The systems were prepared by spin-coating of a mesoporous TiO2 film from solutions of ethanolic titanium tetraisopropoxide and Pluronic P123 on planar Si(100 substrates, calcination at 350 °C and subsequent Au loading by a deposition–precipitation procedure, followed by a final calcination step for catalyst activation. The structural and chemical properties of these model systems were characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, N2 adsorption, inductively coupled plasma ionization spectroscopy (ICP–OES and X-ray photoelectron spectroscopy (XPS. The catalytic properties were evaluated through the oxidation of CO as a test reaction, and reactivities were measured directly above the film with a scanning mass spectrometer. We can demonstrate that the thin-film model catalysts closely resemble dispersed Au/TiO2 supported catalysts in their characteristic structural and catalytic properties, and hence can be considered as suitable for catalytic model studies. The linear increase of the catalytic activity with film thickness indicates that transport limitations inside the Au/TiO2 film catalyst are negligible, i.e., below the detection limit.

  18. XPS/STM study of model bimetallic Pd–Au/HOPG catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Bukhtiyarov, Andrey V., E-mail: avb@catalysis.ru [Boreskov Institute of Catalysis, Lavrentieva Ave. 5, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Prosvirin, Igor P., E-mail: prosvirin@catalysis.ru [Boreskov Institute of Catalysis, Lavrentieva Ave. 5, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Bukhtiyarov, Valerii I., E-mail: vib@catalysis.ru [Boreskov Institute of Catalysis, Lavrentieva Ave. 5, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation)

    2016-03-30

    Graphical abstract: - Highlights: • The model Pd–Au/HOPG catalysts preparation has been studied by XPS and STM. • Model “core–shell” type Pd–Au/HOPG catalysts with different Pd/Au ratios were prepared. • Heating of the “core–shell” Pd–Au/HOPG samples up to 400 °C leads to alloy formation. • Contribution of parameters controlling the properties of Pd–Au alloyed particles has been discussed. - Abstract: The preparation of model bimetallic Pd–Au/HOPG catalysts has been investigated using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) techniques. Initially, model “core–shell” type Pd–Au/HOPG catalysts with similar particle size distribution (5–8 nm), but with different densities of particle locations on the HOPG surface and Pd/Au atomic ratios are prepared. Further, their thermal stability is studied within a temperature range of 50–500 °C at UHV conditions. It has been shown that annealing the model catalysts at a temperature range of 300–400 °C leads to formation of Pd–Au alloyed particles. Enhancement of heating temperature up to 500 °C results in sintering of bimetallic nanoparticles. Contribution of different parameters controlling the properties of Pd–Au alloyed particles has been discussed.

  19. Surface reaction network of CO oxidation on CeO2/Au(110) inverse model catalysts.

    Science.gov (United States)

    Ding, Liangbing; Xiong, Feng; Jin, Yuekang; Wang, Zhengming; Sun, Guanghui; Huang, Weixin

    2016-11-30

    CeO2/Au(110) inverse model catalysts were prepared and their activity toward the adsorption and co-adsorption of O2, CO, CO2 and water was studied by means of X-ray photoelectron spectroscopy, low energy electron diffraction, thermal desorption spectra and temperature-programmed reaction spectra. The Au surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs CO, CO2 and water, and the polycrystalline CeO2 surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs O2, and molecularly and reactively adsorbs CO, CO2 and water. By controllably preparing co-adsorbed surface species on CeO2/Au(110) inverse model catalysts, we successfully identified various surface reaction pathways of CO oxidation to produce CO2 with different barriers both on the CeO2 surface and at the Au-CeO2 interface, including CO oxidation by various oxygen species, and water/hydroxyl group-involved CO oxidation. These results establish a surface reaction network of CO oxidation catalyzed by Au/CeO2 catalysts, greatly advancing the fundamental understandings of catalytic CO oxidation reactions.

  20. Modeling Species Inhibition and Competitive Adsorption in Urea-SCR Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Devarakonda, Maruthi N.; Tonkyn, Russell G.; Lee, Jong H.

    2012-04-16

    Although the urea-SCR technology exhibits high NOx reduction efficiency over a wide range of temperatures among the lean NOx reduction technologies, further improvement in low-temperature performance is required to meet the future emission standards and to lower the system cost. In order to improve the catalyst technologies and optimize the system performance, it is critical to understand the reaction mechanisms and catalyst behaviors with respect to operating conditions. Urea-SCR catalysts exhibit poor NOx reduction performance at low temperature operating conditions (T < 150 C). We postulate that the poor performance is either due to NH3 storage inhibition by species like hydrocarbons or due to competitive adsorption between NH3 and other adsorbates such as H2O and hydrocarbons in the exhaust stream. In this paper we attempt to develop one-dimensional models to characterize inhibition and competitive adsorption in Fe-zeolite based urea-SCR catalysts based on bench reactor experiments. We further use the competitive adsorption (CA) model to develop a standard SCR model based on previously identified kinetics. Simulation results indicate that the CA model predicts catalyst outlet NO and NH3 concentrations with minimal root mean square error.

  1. Optimization of alkali catalyst for transesterification of jatropha curcus using adaptive neuro-fuzzy modeling

    Directory of Open Access Journals (Sweden)

    Vipan K Sohpal

    2014-06-01

    Full Text Available Transesterification of Jatropha curcus for biodiesel production is a kinetic control process, which is complex in nature and controlled by temperature, the molar ratio, mixing intensity and catalyst process parameters. A precise choice of catalyst is required to improve the rate of transesterification and to simulate the kinetic study in a batch reactor. The present paper uses an Adaptive Neuro-Fuzzy Inference System (ANFIS approach to model and simulate the butyl ester production using alkaline catalyst (NaOH. The amounts of catalyst and time for reaction have been used as the model’s input parameters. The model is a combination of fuzzy inference and artificial neural network, including a set of fuzzy rules which have been developed directly from experimental data. The proposed modeling approach has been verified by comparing the expected results with the practical results which were observed and obtained through a batch reactor operation. The application of the ANFIS test shows which amount of catalyst predicted by the proposed model is suitable and in compliance with the experimental values at 0.5% level of significance.

  2. Three-Way Tucker2 Component Analysis Solutions of Stimuli x Responses x Individuals Data with Simple Structure and the Fewest Core Differences

    Science.gov (United States)

    Adachi, Kohei

    2011-01-01

    Multivariate stimulus-response designs can be described by a three-way array of stimuli by responses by individuals. Its underlying structure can be represented by a network based on the Tucker2 component model in which stimulus components are connected with response components by means of the links that differ between individuals. For each…

  3. A Stochastic Multidimensional Scaling Procedure for the Spatial Representation of Three-Mode, Three-Way Pick Any/"J" Data.

    Science.gov (United States)

    Jedidi, Kamel; DeSarbo, Wayne S.

    1991-01-01

    A stochastic multidimensional scaling procedure is presented for analysis of three-mode, three-way pick any/"J" data. The procedure fits both vector and ideal-point models and characterizes the effect of situations by a set of dimension weights. An application in the area of consumer psychology is discussed. (SLD)

  4. Session 4: Atr catalyst for natural gas conversion to hydrogen: performance, simulation, and modeling

    Energy Technology Data Exchange (ETDEWEB)

    Baumann, F.; Duisberg, M.; Sextl, G.; Wieland, S. [Umicore AG and Co. KG, Hanau (Germany); Deutschmann, O. [Karlsruhe Univ., Institute for Chemical Technology (Germany); Maier, L. [Heidelberg Univ., IWR (Germany); Schmidt, L.D. [Minnesota Univ., Chem. Engineering and Mat. Sciences Minneapolis (United States)

    2004-07-01

    A non-pyrophoric precious metal based auto-thermal reforming catalyst was developed and, the performance of the catalyst at different operational conditions was measured. Additionally, the physical properties of the catalytic layer such as precious metal loading, the BET surface, and the dispersion were determined. A profound knowledge of the ATR process is required to improve the performance of the catalyst. Therefore, a detailed reaction mechanism consisting of 42 reactions among six stable gas-phase and further 23 adsorbed species was developed for the simultaneous description of the partial oxidation, heated steam reforming, water-gas shift reactions and the undesired methanation. A variety of numerical simulations of the ATR process at various conditions were performed using the CFD code DETCHEM(CHANNEL), which models the flow field in monolithic channels and the chemical processes in the gas phase and on the surface including diffusion and reactions in the wash coat structure. The results demonstrate the applicability of the developed mechanism for Umicore's ATR catalyst. The simulation offers an insight into the processes occurring in the catalytic reactor. The figure, for instance, reveals the surface coverage of the reacting species along the catalytic channel wall. In the first centimetre of the catalyst the concentrations vary drastically. The initially high oxygen coverage, leading to total oxidation and heat release, decreases rapidly. Farther downstream the processes on the catalyst are predominated by steam reforming; oxygen on the surface now comes from re-adsorbed water. Thus, the verified model allows the localization of different reaction zones. This information can be generated for different operation conditions such as start up or load alternation. Thus the model is a valuable tool for further improvement of the catalyst performance by 'designing' new formulations. (authors)

  5. Heteroepitaxial praseodymium sesquioxide films on Si(1 1 1): A new model catalyst system for praseodymium oxide based catalysts

    Science.gov (United States)

    Schaefer, A.; Schroeder, T.; Lupina, G.; Borchert, Y.; Dabrowski, J.; Wenger, Ch.; Bäumer, M.

    2007-03-01

    The structure, growth and stoichiometry of heteroepitaxial Pr 2O 3 films on Si(1 1 1) were characterized by a combined RHEED, XRD, XPS and UPS study in view of future applications as a surface science model catalyst system. RHEED and XRD confirm the growth of a (0 0 0 1) oriented hexagonal Pr 2O 3 phase on Si(1 1 1), matching the surface symmetry by aligning the oxide in-plane direction along the Si azimuth. After an initial nucleation stage RHEED growth oscillation studies point to a Frank-van der Merwe growth mode up to a thickness of approximately 12 nm. XPS and UPS prove that the initial growth of the Pr 2O 3 layer on Si up to ˜1 nm thickness is characterized by an interface reaction with Si. Nevertheless stoichiometric Pr 2O 3 films of high crystalline quality form on top of these Pr-silicate containing interlayers.

  6. SO2 oxidation catalyst model systems characterized by thermal methods

    DEFF Research Database (Denmark)

    Hatem, G; Eriksen, Kim Michael; Gaune-Escard, M;

    2002-01-01

    The molten salts M2S2O7 and MHSO4, the binary molten salt Systems M2S2O7-MHSO4 and the molten salt-gas systems M2S2O7 V2O5 and M2S2O7-M2SO4 V2O5 (M = Na, K, Rb, Cs) in O-2, SO2 and At atmospheres have been investigated by thermal methods like calorimetry, Differential Enthalpic Analysis (DEA) and...... to the mechanism Of SO2 oxidation by V2O5 based industrial catalysts....

  7. Three ways to minimise professionals’ resistance to governmental change using the policy alienation model

    NARCIS (Netherlands)

    L.G. Tummers (Lars)

    2013-01-01

    textabstractWhy do public service professionals resist some changes, while embracing others? Lars Tummers is an expert on the analysis of ‘policy alienation’. He has studied problems that professionals working in a range of sectors – including healthcare, social security and education – face in

  8. Successful three-way kidney paired donation transplantation: The first Indian report.

    Science.gov (United States)

    Kute, V B; Gumber, M R; Shah, P R; Patel, H V; Vanikar, A V; Modi, P R; Shah, V R; Trivedi, H L

    2014-01-01

    Providing transplantation opportunities for patients with incompatible live donors through kidney paired donation (KPD) is an important strategy for easing the crisis in organ availability. KPD is can overcome the barriers when the only living potential donors are deemed unsuitable owing to an incompatibility of blood type, of human leukocyte antigen cross-match, or both. In KPD, the incompatibility problems with two donor recipient pairs can be solved by exchanging donors. In the absence of well-organized deceased donor program, or transplantation with desensitization protocol and ABO incompatible transplantation, living donor KPD promises hope to the growing number of patients suffering from end-stage renal disease in India. We report our first successful three-way KPD transplantation from India. In an era of organ shortage, this approach is relevant to encourage wider participation from KPD donors and transplant centers to prevent commercial transplantation.

  9. Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization

    Directory of Open Access Journals (Sweden)

    Sonali Sengupta

    2013-12-01

    Full Text Available The oxidation of catechol was studied in an eco-friendly process with commercial titanium silicate-1 (TS-1 catalyst and hydrogen peroxide as oxidant in absence of all mass transfer effects. The process was opti-mized by Box-Behnken design in terms of three independent process variables such as reaction tempera-ture, moles of hydrogen peroxide per mole of catechol and catalyst amount whose optimum values of the process variables were found to be 60 °C, 13.2 and 1.24 g respectively for maximum conversion of 75.8 %. The effects of different process parameters such as mole ratio of hydrogen peroxide to catechol, catalyst par-ticle size, catalyst amount, temperature and reaction time were studied. A pseudo first order kinetic model was fitted with the experimental rate data. The apparent activation energy for the reaction was found to be 11.37 kJ/mole.  © 2013 BCREC UNDIP. All rights reservedReceived: 22nd April 2013; Revised: 25th October 2013; Accepted: 1st November 2013[How to Cite: Sengupta, S., Ghosal, D., Basu, J.K. (2013. Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (2: 167-177. (doi:10.9767/bcrec.8.2.4759.167-177][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.2.4759.167-177

  10. Experimental Study and Kinetic Modeling of Decoking of Pacol Process Dehydrogenation Catalyst

    Directory of Open Access Journals (Sweden)

    M. Toghyani

    2015-07-01

    Full Text Available The Pt/γ-Al2O3 catalyst life time was limited by the formation of coke on the external and internal surfaces of catalyst in dehydrogenation reactors. The kinetics of decoking of dehydrogenation catalyst was studied in a pilot scale fixed bed reactor experimentally. The effects of temperature, oxygen concentration and other operating conditions on decoking process were investigated. A kinetic model was deve-loped to describe the decoking of mentioned catalyst. An objective function was defined as the sum of squares of the deviations among the calculated and plant data. Accordingly the appropriate values were found in order to minimize this function. It was concluded that there was a good agreement between simulation results and experimental data.  © 2015 BCREC UNDIP. All rights reservedReceived: 18th September 2014; Revised: 28th February 2015; Accepted: 9th March 2015How to Cite: Toghyani, M., Rahimi, A., Mamanpoush, M., Kazemian, R., Harandizadeh, A.H. (2015. Experimental Study and Kinetic Modeling of Decoking of Pacol Process Dehydrogenation Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (2: 155-161. (doi:10.9767/bcrec.10.2.7357.155-161 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.7357.155-161  

  11. The model thin film alumina catalyst support suitable for catalysis-oriented surface science studies

    Energy Technology Data Exchange (ETDEWEB)

    Nartova, Anna V., E-mail: avnartova@gmail.com [Boreskov Institute of Catalysis SB RAS, Lavrentieva Ave., 5, Novosibirsk, 630090 (Russian Federation); Novosibirsk State University, Pirogova St., 2, Novosibirsk, 630090 (Russian Federation); Bukhtiyarov, Andrey V., E-mail: avb@catalysis.ru [Boreskov Institute of Catalysis SB RAS, Lavrentieva Ave., 5, Novosibirsk, 630090 (Russian Federation); Kvon, Ren I., E-mail: kvon@catalysis.ru [Boreskov Institute of Catalysis SB RAS, Lavrentieva Ave., 5, Novosibirsk, 630090 (Russian Federation); Bukhtiyarov, Valerii I., E-mail: vib@catalysis.ru [Boreskov Institute of Catalysis SB RAS, Lavrentieva Ave., 5, Novosibirsk, 630090 (Russian Federation); Novosibirsk State University, Pirogova St., 2, Novosibirsk, 630090 (Russian Federation)

    2015-09-15

    Graphical abstract: - Highlights: • New model catalyst on “AlOx-thin film/FeCrAl” support is presented. • Metal substrate minimizes sample charging, allows fast and uniform heating. • Surface is rough to model the catalyst support's morphology. • Planar alumina is stable in air/gases/solutions and similar to γ-Al{sub 2}O{sub 3}. • New model support is suitable for in situ XPS, STM, TPD, TPR, etc. - Abstract: The preparation of thin continuous alumina film at the surface of metal substrate in UHV (ultra high vacuum) conditions is described. The peculiarities of the obtained films studied by XPS (X-ray photoelectron spectroscopy) and STM (scanning tunneling microscopy) are discussed. The long-term durability of the oxide film was tested and proved both under ambient conditions and in acidic aqueous solutions. The stability of the planar alumina samples toward oxidation by oxygen was checked in the wide ranges of gas pressure and sample temperature. The suggested procedure ensures the controlled and reproducible preparation of thin alumina films – model support appropriate for wet chemistry catalyst preparation, suitable for STM and for other Surface Science techniques studies of alumina supported metal catalysts.

  12. Monolayer Iron Carbide Films on Au(111) as a Fischer–Tropsch Model Catalyst

    DEFF Research Database (Denmark)

    Mannie, Gilbère; Lammich, Lutz; Li, Yong-Wang;

    2014-01-01

    Using scanning tunneling microscopy (STM), we characterize the atomic-scale details of ultrathin films of iron carbide (FexCy) on Au(111) synthesized as a potential model system for the active iron carbide phase in iron Fischer–Tropsch synthesis (FTS) catalysts. The experiments show that room...

  13. Hydrodeoxygenation of waste fat for diesel production: Study on model feed with Pt/alumina catalyst

    DEFF Research Database (Denmark)

    Madsen, Anders Theilgaard; Ahmed, El Hadi; Christensen, Claus H.

    2011-01-01

    Hydrodeoxygenation of waste fats and oils is a viable method for producing renewable diesel oil. In this study a model feed consisting of oleic acid and tripalmitin in molar ratio 1:3 was hydrotreated at 325°C with 20bars H2 in a stirred batch autoclave with a 5wt% Pt/γ-Al2O3 catalyst, and samples...

  14. Effect of cobalt doping on ceria-zirconia mixed oxide: Structural characteristics,oxygen storage/release capacity and three-way catalytic performance

    Institute of Scientific and Technical Information of China (English)

    WANG Jianqiang; SHEN Meiqing; WANG Jun; GAO Jidong; MA Jie; LIU Shuangxi

    2012-01-01

    The effect of Co doping on ceria-zirconia mixed oxides was investigated for Co0.1Ce0.6Zr0.3Ox sample prepared by sol-gel method.The Pd-only three-way catalyst (TWC) was obtained by incipient wetness impregnation with 0.5 wt.% Pd loading.The structural and oxygen handling properties were analyzed by X-ray diffraction (XRD),H2-temperature programmed reduction (H2-TPR) and the dynamic oxygen storage capacity (DOSC).The introduction of Co into ceria-zirconia lattice strongly modified the mobility of oxygen and enhanced the DOSC performance.Pd-only TWC based on the Co0.1Ce0.6Zr0.3Ox support exhibited superior activity for water-gas shift and steam reforming and amplified amplitude of stoichiometric window.

  15. Fresh tar (from biomass gasification) destruction with downstream catalysts: comparison of their intrinsic activity with a realistic kinetic model

    Energy Technology Data Exchange (ETDEWEB)

    Corella, J.; Narvaez, I.; Orio, A. [Complutense Univ. of Madrid (Spain). Dept. of Chemical Engineering

    1996-12-31

    A model for fresh tar destruction over catalysts placed downstream a biomass gasifier is presented. It includes the stoichio-metry and the calculation of the kinetic constants for the tar destruction. Catalysts studied include commercial Ni steam reforming catalysts and calcinated dolomites. Kinetic constants for tar destruction are calculated for several particle sizes, times- on-stream and temperatures of the catalyst and equivalence ratios in the gasifier. Such intrinsic kinetic constants allow a rigorous or scientific comparison of solids and conditions to be used in an advanced gasification process. (orig.) 4 refs.

  16. Non-parametric three-way mixed ANOVA with aligned rank tests.

    Science.gov (United States)

    Oliver-Rodríguez, Juan C; Wang, X T

    2015-02-01

    Research problems that require a non-parametric analysis of multifactor designs with repeated measures arise in the behavioural sciences. There is, however, a lack of available procedures in commonly used statistical packages. In the present study, a generalization of the aligned rank test for the two-way interaction is proposed for the analysis of the typical sources of variation in a three-way analysis of variance (ANOVA) with repeated measures. It can be implemented in the usual statistical packages. Its statistical properties are tested by using simulation methods with two sample sizes (n = 30 and n = 10) and three distributions (normal, exponential and double exponential). Results indicate substantial increases in power for non-normal distributions in comparison with the usual parametric tests. Similar levels of Type I error for both parametric and aligned rank ANOVA were obtained with non-normal distributions and large sample sizes. Degrees-of-freedom adjustments for Type I error control in small samples are proposed. The procedure is applied to a case study with 30 participants per group where it detects gender differences in linguistic abilities in blind children not shown previously by other methods.

  17. Thermodynamic stabilities of three-way junction nanomotifs in prohead RNA

    Science.gov (United States)

    Hill, Alyssa C.; Schroeder, Susan J.

    2017-01-01

    The thermodynamic stabilities of four natural prohead or packaging RNA (pRNA) three-way junction (3WJ) nanomotifs and seven phi29 pRNA 3WJ deletion mutant nanomotifs were investigated using UV optical melting on a three-component RNA system. Our data reveal that some pRNA 3WJs are more stable than the phi29 pRNA 3WJ. The stability of the 3WJ contributes to the unique self-assembly properties of pRNA. Thus, ultrastable pRNA 3WJ motifs suggest new scaffolds for pRNA-based nanotechnology. We present data demonstrating that pRNA 3WJs differentially respond to the presence of metal ions. A comparison of our data with free energies predicted by currently available RNA secondary structure prediction programs shows that these programs do not accurately predict multibranch loop stabilities. These results will expand the existing parameters used for RNA secondary structure prediction from sequence in order to better inform RNA structure–function hypotheses and guide the rational design of functional RNA supramolecular assemblies. PMID:28069889

  18. Size-segregated aerosol in a hot-spot pollution urban area: Chemical composition and three-way source apportionment.

    Science.gov (United States)

    Bernardoni, V; Elser, M; Valli, G; Valentini, S; Bigi, A; Fermo, P; Piazzalunga, A; Vecchi, R

    2017-08-24

    In this work, a comprehensive characterisation and source apportionment of size-segregated aerosol collected using a multistage cascade impactor was performed. The samples were collected during wintertime in Milan (Italy), which is located in the Po Valley, one of the main pollution hot-spot areas in Europe. For every sampling, size-segregated mass concentration, elemental and ionic composition, and levoglucosan concentration were determined. Size-segregated data were inverted using the program MICRON to identify and quantify modal contributions of all the measured components. The detailed chemical characterisation allowed the application of a three-way (3-D) receptor model (implemented using Multilinear Engine) for size-segregated source apportionment and chemical profiles identification. It is noteworthy that - as far as we know - this is the first time that three-way source apportionment is attempted using data of aerosol collected by traditional cascade impactors. Seven factors were identified: wood burning, industry, resuspended dust, regional aerosol, construction works, traffic 1, and traffic 2. Further insights into size-segregated factor profiles suggested that the traffic 1 factor can be associated to diesel vehicles and traffic 2 to gasoline vehicles. The regional aerosol factor resulted to be the main contributor (nearly 50%) to the droplet mode (accumulation sub-mode with modal diameter in the range 0.5-1 μm), whereas the overall contribution from the two factors related to traffic was the most important one in the other size modes (34-41%). The results showed that applying a 3-D receptor model to size-segregated samples allows identifying factors of local and regional origin while receptor modelling on integrated PM fractions usually singles out factors characterised by primary (e.g. industry, traffic, soil dust) and secondary (e.g. ammonium sulphate and nitrate) origin. Furthermore, the results suggested that the information on size

  19. Multiple serial picture presentation with millisecond resolution using a three-way LC-shutter-tachistoscope.

    Science.gov (United States)

    Fischmeister, Florian Ph S; Leodolter, Ulrich; Windischberger, Christian; Kasess, Christian H; Schöpf, Veronika; Moser, Ewald; Bauer, Herbert

    2010-03-30

    Throughout recent years there has been an increasing interest in studying unconscious visual processes. Such conditions of unawareness are typically achieved by either a sufficient reduction of the stimulus presentation time or visual masking. However, there are growing concerns about the reliability of the presentation devices used. As all these devices show great variability in presentation parameters, the processing of visual stimuli becomes dependent on the display-device, e.g. minimal changes in the physical stimulus properties may have an enormous impact on stimulus processing by the sensory system and on the actual experience of the stimulus. Here we present a custom-built three-way LC-shutter-tachistoscope which allows experimental setups with both, precise and reliable stimulus delivery, and millisecond resolution. This tachistoscope consists of three LCD-projectors equipped with zoom lenses to enable stimulus presentation via a built-in mirror-system onto a back projection screen from an adjacent room. Two high-speed liquid crystal shutters are mounted serially in front of each projector to control the stimulus duration. To verify the intended properties empirically, different sequences of presentation times were performed while changes in optical power were measured using a photoreceiver. The obtained results demonstrate that interfering variabilities in stimulus parameters and stimulus rendering are markedly reduced. Together with the possibility to collect external signals and to send trigger-signals to other devices, this tachistoscope represents a highly flexible and easy to set up research tool not only for the study of unconscious processing in the brain but for vision research in general.

  20. Screening of Catalysts for Hydrodeoxygenation of Phenol as Model Compound for Bio-oil

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard; Grunwaldt, Jan-Dierk; Jensen, Peter Arendt

    2013-01-01

    in that order. Nickel was the only active non-noble metal catalyst. For nickel, also the effect of support was investigated and ZrO2 was found to perform best. Pt/C, Ni/CeO2, and Ni/CeO2-ZrO2 were the most active catalysts for the initial hydrogenation of phenol to cyclohexanol, but were not very active...... effectively be described by a kinetic model involving a two-step reaction were phenol initially was hydrogenated to cyclohexanol and then subsequently deoxygenated to cyclohexane. Among reduced noble metal catalysts ruthenium, palladium, and platinum were all found to be active, with decreasing activity...... for the subsequent deoxygenation step. Overall, the order of activity of the best performing HDO catalysts was: Ni/ZrO2 > Ni-V2O5/ZrO2 > Ni-V2O5/SiO2 > Ru/C > Ni/Al2O3 > Ni/SiO2 >> Pd/C > Pt/C. The choice of support influenced the activity significantly. Nickel was found to be practically inactive for HDO of phenol...

  1. Biomimetic Catalysts for Oxidation of Veratryl Alcohol, a Lignin Model Compound

    Directory of Open Access Journals (Sweden)

    Marcelino Maneiro

    2013-03-01

    Full Text Available Kraft pulp has to be bleached to eliminate the chromophoric structures, which cause a darkening of the pulp. In Nature, an equivalent role is assumed by ligninolytic enzymes such as lignin peroxidases, manganese peroxidases and laccases. The development of low molecular weight manganese peroxidase mimics may achieve environmentally-safe bleaching catalysts for the industry. Herein we report the synthesis and characterization of six manganese(III complexes 1–6, incorporating dianionic hexadentate Schiff base ligands (H2L1-H2L4 and different anions. Complex 4, Mn2L22(H2O2(DCA2 was crystallographically characterized. Complexes 1–4 behave as more efficient mimics of peroxidase in contrast to 5–6. We have studied the use of these complexes as catalysts for the degradation of the lignin model compound veratryl alcohol. The biomimetic catalysts were used in conjunction with chlorine-free inexpensive co-oxidants as dioxygen or hydrogen peroxide. Yields up to 30% of veratryl alcohol conversion to veratraldehyde have been achieved at room temperature in presence of air flow using 0.5% of catalyst.

  2. The relationship between CO2 emission, energy consumption and economic growth in Malaysia: a three-way linkage approach.

    Science.gov (United States)

    Sulaiman, Chindo; Abdul-Rahim, A S

    2017-09-19

    This study examines the three-way linkage relationships between CO2 emission, energy consumption and economic growth in Malaysia, covering the 1975-2015 period. An autoregressive distributed lag approach was employed to achieve the objective of the study and gauged by dynamic ordinary least squares. Additionally, vector error correction model, variance decompositions and impulse response functions were employed to further examine the relationship between the interest variables. The findings show that economic growth is neither influenced by energy consumption nor by CO2 emission. Energy consumption is revealed to be an increasing function of CO2 emission. Whereas, CO2 emission positively and significantly depends on energy consumption and economic growth. This implies that CO2 emission increases with an increase in both energy consumption and economic growth. Conclusively, the main drivers of CO2 emission in Malaysia are proven to be energy consumption and economic growth. Therefore, renewable energy sources ought to be considered by policy makers to curb emission from the current non-renewable sources. Wind and biomass can be explored as they are viable sources. Energy efficiency and savings should equally be emphasised and encouraged by policy makers. Lastly, growth-related policies that target emission reduction are also recommended.

  3. Reaction selectivity studies on nanolithographically-fabricated platinum model catalyst arrays

    Energy Technology Data Exchange (ETDEWEB)

    Grunes, Jeffrey Benjamin

    2004-05-15

    In an effort to understand the molecular ingredients of catalytic activity and selectivity toward the end of tuning a catalyst for 100% selectivity, advanced nanolithography techniques were developed and utilized to fabricate well-ordered two-dimensional model catalyst arrays of metal nanostructures on an oxide support for the investigation of reaction selectivity. In-situ and ex-situ surface science techniques were coupled with catalytic reaction data to characterize the molecular structure of the catalyst systems and gain insight into hydrocarbon conversion in heterogeneous catalysis. Through systematic variation of catalyst parameters (size, spacing, structure, and oxide support) and catalytic reaction conditions (hydrocarbon chain length, temperature, pressures, and gas composition), the data presented in this dissertation demonstrate the ability to direct a reaction by rationally adjusting, through precise control, the design of the catalyst system. Electron beam lithography (EBL) was employed to create platinum nanoparticles on an alumina (Al{sub 2}O{sub 3}) support. The Pt nanoparticle spacing (100-150-nm interparticle distance) was varied in these samples, and they were characterized using x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM), both before and after reactions. The TEM studies showed the 28-nm Pt nanoparticles with 100 and 150-nm interparticle spacing on alumina to be polycrystalline in nature, with crystalline sizes of 3-5 nm. The nanoparticle crystallites increased significantly after heat treatment. The nanoparticles were still mostly polycrystalline in nature, with 2-3 domains. The 28-nm Pt nanoparticles deposited on alumina were removed by the AFM tip in contact mode with a normal force of approximately 30 nN. After heat treatment at 500 C in vacuum for 3 hours, the AFM tip, even at 4000 nN, could not remove the platinum nanoparticles. The

  4. Reaction selectivity studies on nanolithographically-fabricated platinum model catalyst arrays

    Energy Technology Data Exchange (ETDEWEB)

    Grunes, Jeffrey Benjamin [Univ. of California, Berkeley, CA (United States)

    2004-05-01

    In an effort to understand the molecular ingredients of catalytic activity and selectivity toward the end of tuning a catalyst for 100% selectivity, advanced nanolithography techniques were developed and utilized to fabricate well-ordered two-dimensional model catalyst arrays of metal nanostructures on an oxide support for the investigation of reaction selectivity. In-situ and ex-situ surface science techniques were coupled with catalytic reaction data to characterize the molecular structure of the catalyst systems and gain insight into hydrocarbon conversion in heterogeneous catalysis. Through systematic variation of catalyst parameters (size, spacing, structure, and oxide support) and catalytic reaction conditions (hydrocarbon chain length, temperature, pressures, and gas composition), the data presented in this dissertation demonstrate the ability to direct a reaction by rationally adjusting, through precise control, the design of the catalyst system. Electron beam lithography (EBL) was employed to create platinum nanoparticles on an alumina (Al2O3) support. The Pt nanoparticle spacing (100-150-nm interparticle distance) was varied in these samples, and they were characterized using x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM), both before and after reactions. The TEM studies showed the 28-nm Pt nanoparticles with 100 and 150-nm interparticle spacing on alumina to be polycrystalline in nature, with crystalline sizes of 3-5 nm. The nanoparticle crystallites increased significantly after heat treatment. The nanoparticles were still mostly polycrystalline in nature, with 2-3 domains. The 28-nm Pt nanoparticles deposited on alumina were removed by the AFM tip in contact mode with a normal force of approximately 30 nN. After heat treatment at 500 C in vacuum for 3 hours, the AFM tip, even at 4000 nN, could not remove the platinum

  5. Modeling Low-Platinum-Loading Effects in Fuel-Cell Catalyst Layers

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Wonseok; Weber, Adam Z.

    2011-01-20

    The cathode catalyst layer within a proton-exchange-membrane fuel cell is the most complex and critical, yet least understood, layer within the cell. The exact method and equations for modeling this layer are still being revised and will be discussed in this paper, including a 0.8 reaction order, existence of Pt oxides, possible non-isopotential agglomerates, and the impact of a film resistance towards oxygen transport. While the former assumptions are relatively straightforward to understand and implement, the latter film resistance is shown to be critically important in explaining increased mass-transport limitations with low Pt-loading catalyst layers. Model results demonstrate agreement with experimental data that the increased oxygen flux and/or diffusion pathway through the film can substantially decrease performance. Also, some scale-up concepts from the agglomerate scale to the more macroscopic porous-electrode scale are discussed and the resulting optimization scenarios investigated.

  6. A Systematic Modelling Framework for Phase Transfer Catalyst Systems

    DEFF Research Database (Denmark)

    Anantpinijwatna, Amata; Sales-Cruz, Mauricio; Hyung Kim, Sun

    2016-01-01

    in an aqueous phase. These reacting systems are receiving increased attention as novel organic synthesis options due to their flexible operation, higher product yields, and ability to avoid hazardous or expensive solvents. Major considerations in the design and analysis of PTC systems are physical and chemical...... equilibria, as well as kinetic mechanisms and rates. This paper presents a modelling framework for design and analysis of PTC systems that requires a minimum amount of experimental data to develop and employ the necessary thermodynamic and reaction models and embeds them into a reactor model for simulation....... The application of the framework is made to two cases in order to highlight the performance and issues of activity coefficient models for predicting design and operation and the effects when different organic solvents are employed....

  7. Mechanisms and modeling development of water transport/phase change in catalyst layers of portion exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Yexiang [Dept. of Thermal Engineering, Tsinghua University Beijing (China)], email: Yexiang.Xiao@energy.lth.se; Yuan, Jinliang; Sunden, Bengt [Dept. of Energy Sciences, Faculty of Engineering, Lund University (Sweden)], email: Jinliang.yuan@energy.lth.se, email: bengt.sunden@energy.lth.se

    2011-07-01

    Research on proton exchange membrane fuel cells has shown that incorporation of nanosized catalysts can effectively increase active areas and catalyst activity and make a great contribution to development in performance and catalyst utilization. Multiphase transport processes are as significant and complicated as water generation/transfer processes which occur in nano-structured catalyst layers. A review project has been launched aimed at gaining a comprehensive understanding of the mechanisms of water generation or transport phenomena. It covers catalytic reactions and water-phase change within the catalyst layers. The review proceeds in three main stages: Firstly, it characterizes and reconstructs the nano/micro-structured pores and solid-phases; secondly, it emphasises the importance of sensitive and consistent analysis of various water-phase change and transport schemes; and thirdly, it recommends development of microscopic models for multi-phase transport processes in the pores and the solid phases.

  8. Mathematical modeling taking into account of intrinsic kinetic properties of cylinder-type vanadium catalyst

    Institute of Scientific and Technical Information of China (English)

    陈振兴; 李洪桂; 王零森

    2004-01-01

    The method to calculate internal surface effective factor of cylinder-type vanadium catalyst Ls-9 was given. Based on hypothesis of subjunctive one dimension diffusion and combined shape adjustment factor with threestep catalytic mechanism model, the macroscopic kinetic model equation about SO2 oxidation on Ls-9 was deduced.With fixed-bed integral reactor and under the conditions of temperature 350 - 410 ℃, space velocity 1 800 - 5 000h-1, SO2 inlet content 7 %- 12%, the macroscopic kinetic data were detected. Through model parameter estimation,the macroscopic kinetic model equation was obtained.

  9. Kinetic modeling of the SWNT growth by CO disproportionation on CoMo catalysts.

    Science.gov (United States)

    Monzon, A; Lolli, G; Cosma, S; Mohamed, S B; Resasco, D E

    2008-11-01

    A kinetic model has been developed to describe the growth of single-walled carbon nanotubes (SWNT) in the CoMoCAT method, which is based on the disproportionation of CO on supported CoMo catalysts. The model attempts to capture mathematically the different stages involved in this method: (i) catalyst activation or in-situ creation of active sites, i.e., reduced Co clusters by transformation of CoMoOx precursor species, or oxidized sites; (ii) CO decomposition over active sites, which increases the surface fugacity of carbon until reaching a certain threshold; (iii) nucleation of ordered forms of carbon; (iv) C diffusion (both across the surface and into the metal particle); (v) SWNT growth; (vi) termination, by either deactivation of the catalyst active sites or by increase in the carbon concentration at the metal/SWNT interface, approaching that of the metal/gas interface and eliminating the driving force for diffusion. Previous investigations have only explained the growth termination by the former. Here, we emphasize the possible contribution of the later and propose a novel "hindrance factor" to quantify the effect of nanotube interaction with its surroundings on the growth termination. To test the kinetic model and obtain typical values of the physical parameters, experiments have been conducted on a CoMo/SiO2 catalyst in a laboratory flow reactor, in which the rate of carbon deposition was continuously evaluated by the direct measurement of the CO2 evolution as a function of time. The experimental data are fitted very well with model.

  10. UV-Raman spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption studies of model and bulk heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Tewell, Craig R.

    2002-08-19

    X-ray photoelectron spectroscopy (XPS) and Temperature Programmed Desorption (TPD) have been used to investigate the surface structure of model heterogeneous catalysts in ultra-high vacuum (UHV). UV-Raman spectroscopy has been used to probe the structure of bulk model catalysts in ambient and reaction conditions. The structural information obtained through UV-Raman spectroscopy has been correlated with both the UHV surface analysis and reaction results. The present day propylene and ethylene polymerization catalysts (Ziegler-Natta catalysts) are prepared by deposition of TiCl{sub 4} and a Al(Et){sub 3} co-catalyst on a microporous Mg-ethoxide support that is prepared from MgCl{sub 2} and ethanol. A model thin film catalyst is prepared by depositing metallic Mg on a Au foil in a UHV chamber in a background of TiCl{sub 4} in the gas phase. XPS results indicate that the Mg is completely oxidized to MgCl{sub 2} by TiCl{sub 4} resulting in a thin film of MgCl{sub 2}/TiCl{sub x}, where x = 2, 3, and 4. To prepare an active catalyst, the thin film of MgCl{sub 2}/TiCl{sub x} on Au foil is enclosed in a high pressure cell contained within the UHV chamber and exposed to {approx}1 Torr of Al(Et){sub 3}.

  11. UV-Raman spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption studies of model and bulk heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Tewell, Craig Richmond [Univ. of California, Berkeley, CA (United States)

    2002-01-01

    X-ray photoelectron spectroscopy (XPS) and Temperature Programmed Desorption (TPD) have been used to investigate the surface structure of model heterogeneous catalysts in ultra-high vacuum (UHV). UV-Raman spectroscopy has been used to probe the structure of bulk model catalysts in ambient and reaction conditions. The structural information obtained through UV-Raman spectroscopy has been correlated with both the UHV surface analysis and reaction results. The present day propylene and ethylene polymerization catalysts (Ziegler-Natta catalysts) are prepared by deposition of TiCl4 and a Al(Et)3 co-catalyst on a microporous Mg-ethoxide support that is prepared from MgCl2 and ethanol. A model thin film catalyst is prepared by depositing metallic Mg on a Au foil in a UHV chamber in a background of TiCl4 in the gas phase. XPS results indicate that the Mg is completely oxidized to MgCl2 by TiCl4 resulting in a thin film of MgCl2/TiClx, where x = 2, 3, and 4. To prepare an active catalyst, the thin film of MgCl2/TiClx on Au foil is enclosed in a high pressure cell contained within the UHV chamber and exposed to ~1 Torr of Al(Et)3.

  12. Kinetics modeling of ethylbenzene dehydrogenation to styrene over a mesoporous alumina supported iron catalyst

    KAUST Repository

    Hossain, Mohammad M.

    2012-10-01

    The kinetics of ethylbenzene (EB) dehydrogenation over a FeO x-meso-Al 2O 3 catalyst is studied. The models were developed based on physicochemical characterization and a CREC fluidized Riser Simulator data. N 2 adsorption shows that the synthesized FeO x-meso-Al 2O 3 catalyst is mesoporous with pore size between 9 and 35nm. TPR profile indicates that iron on meso-Al 2O 3 forms easily reducible nanostructured crystals which is confirmed by TEM image. NH 3- and CO-TPD analysis, respectively reveals the availability of both acidic and basic sites. The dehydrogenation of ethylbenzene on FeO x-meso-Al 2O 3 catalyst mainly gives styrene (∼99%) while a small amount of benzene, toluene and coke are also detected. Based on the experimental observations two Langmuir-Hinshelwood type kinetics models are formulated. The possible catalyst deactivation is expressed as function of EB conversion. Parameters are estimated by fitting of the experimental data implemented in MATLAB. Results show that one type site Langmuir-Hinshelwood model appropriately describes the experimental data, with adequate statistical fitting indicators and also satisfied the physical constraints. The activation energy for the formation of styrene (80kJ/mol) found to be significantly lower than that of the undesired products benzene (144kJ/mol) and toluene (164kJ/mol). The estimated heat of adsorptions of EB and ST are found to be 55kJ/mol and 19kJ/mol, respectively. © 2012 Elsevier B.V.

  13. Application of New Electrolyte Model to Phase Transfer Catalyst (PTC) Systems

    DEFF Research Database (Denmark)

    2015-01-01

    Abstract Phase transfer catalyst (PTC) is used to transfer the desirable active form of an anion from the aqueous phase to organic phase where the reaction occurs. One of major challenges for process design of the PTC system is to establish a reliable thermodynamic model capable of describing phase...... in PTC systems, thereby, extending the application range of the PTC-system model. The solubility of PTC in organic solvents, which is a key factor for strategy of PTC and solvent selection, has been calculated using the e-NRTL-SAC model....

  14. Modeling the Kinetics of Deactivation of Catalysts during the Upgrading of Bio-Oil

    Energy Technology Data Exchange (ETDEWEB)

    Weber, Robert S.; Olarte, Mariefel V.; Wang, Huamin

    2015-01-25

    The fouling of catalysts for the upgrading of bio-oils appears to be very different from the fouling of catalysts for the hydroprocessing of petroleum-derived streams. There are two reasons for the differences: a) bio-oil contains polarizable components and phases that can stabilize reaction intermediates exhibiting charge separation and b) bio-oil components contain functional groups that contain O, notably carbonyls (>C=O). Aldol condensation of carbonyls affords very different pathways for the production of oligomeric, refractory deposits than does dehydrogenation/polymerization of petroleum-derived hydrocarbons. Colloquially, we refer to the bio-oil derived deposits as “gunk” to discriminate them from coke, the carbonaceous deposits encountered in petroleum refining. Classical gelation, appears to be a suitable model for the “gunking” reaction. Our work has helped explain the temperature range at which bio-oil should be pre-processed (“stabilized”) to confer longer lifetimes on the catalysts used for more severe processing. Stochastic modeling (kinetic Monte Carlo simulations) appears suitable to capture the rates of oligomerization of bio-oil. This work was supported by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

  15. Growth of transition metals on cerium tungstate model catalyst layers

    Science.gov (United States)

    Skála, T.; Tsud, N.; Stetsovych, V.; Mysliveček, J.; Matolín, V.

    2016-10-01

    Two model catalytic metal/oxide systems were investigated by photoelectron spectroscopy and scanning tunneling microscopy. The mixed-oxide support was a cerium tungstate epitaxial thin layer grown in situ on the W(1 1 0) single crystal. Active particles consisted of palladium and platinum 3D islands deposited on the tungstate surface at 300 K. Both metals were found to interact weakly with the oxide support and the original chemical state of both support and metals was mostly preserved. Electronic and morphological changes are discussed during the metal growth and after post-annealing at temperatures up to 700 K. Partial transition-metal coalescence and self-cleaning from the CO and carbon impurities were observed.

  16. KINETIC MODELING OF TRANSESTERFICATION REACTION FOR BIODIESEL PRODUCTION USING HETEROGENEOUS CATALYST

    Directory of Open Access Journals (Sweden)

    N. JAYA,

    2011-04-01

    Full Text Available Biodiesel derived from renewable plant sources is monoalkyl esters of long chain fatty acids which fall in the carbon range of C12-C22. It has similar properties as mineral diesel. Various processes exist to convert vegetable oils into biodiesel. Transesterification of such vegetable oils using alcohol in the catalytic environment is most commonly used method for producing biodiesel. The equilibrium conversion of triglycerides is affected by various factors namely feed Quality (like free fatty acid content, water content etc.,type of alcohol used, molar ratio of alcohol to triglycerides, type of catalyst, amount of catalyst, reaction temperature, reaction time and stirring rates. The present work reports on the characterization of cotton seed oil and production of biodiesel. This study also reports on the optimal operating parameter for cotton seed oil inbatch reactor. The main thrust of present work was to study the kinetics, modeling and simulation of anionic ion exchange resin catalyzed transesterification of cotton seed oil. Experiments were carried out in batch reactor to generate kinetic data and a kinetic model was developed. The effect of temperature, catalyst concentration and molar ratio of methanol to triglycerides and stirring rates were investigated. A few fuel properties were alsomeasured for biodiesel to observe its competitiveness with onventional diesel fuel. The equilibrium conversions of triglycerides were observed to be in the range of 85%. It was also observed that higher conversion was achieved at 6:1 molar ratio of ethanol to oil, 2 wt.% of anionic resin catalyst ,temperature at 338 K, reaction time of 180 minutes with stirring speed 10 Hz. Model parameters such as order, activation energy and rate constants were calculated, the overall activation energy was also estimated. The rate constants werefound to increase with an increase in temperature and catalyst concentration. Various simulations were also carried out at

  17. First-principles approach to heat and mass transfer effects in model catalyst studies

    OpenAIRE

    Matera, S.; Reuter, K.

    2009-01-01

    We assess heat and mass transfer limitations in in situ studies of model catalysts with a first-principles based multiscale modeling approach that integrates a detailed description of the surface reaction chemistry and the macro-scale flow structures. Using the CO oxidation at RuO2(110) as a prototypical example we demonstrate that factors like a suppressed heat conduction at the backside of the thin single-crystal, and the build-up of a product boundary layer above the flat-faced surface pla...

  18. Ammonia synthesis and decomposition on a Ru-based catalyst modeled by first-principles

    DEFF Research Database (Denmark)

    Hellman, A.; Honkala, Johanna Karoliina; Remediakis, Ioannis

    2009-01-01

    A recently published first-principles model for the ammonia synthesis on an unpromoted Ru-based catalyst is extended to also describe ammonia decomposition. In addition, further analysis concerning trends in ammonia productivity, surface conditions during the reaction, and macro......-properties, such as apparent activation energies and reaction orders are provided. All observed trends in activity are captured by the model and the absolute value of ammonia synthesis/decomposition productivity is predicted to within a factor of 1-100 depending on the experimental conditions. Moreover it is shown: (i...

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

    Energy Technology Data Exchange (ETDEWEB)

    Contreras, Anthony Marshall [Univ. of California, Berkeley, CA (United States)

    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. Handling ordinal variables in three-way analysis of quantification matrices for variables of mixed measurement levels

    NARCIS (Netherlands)

    Kiers, Henk A.L.

    1993-01-01

    For the analysis of variables of mixed measurement levels a class of methods can be used that is based on three-way analysis of quantification matrices for nominal or quantitative variables. This class of methods incorporates some well-known techniques but also offers a series of interesting new alt

  1. Handling ordinal variables in three-way analysis of quantification matrices for variables of mixed measurement levels

    NARCIS (Netherlands)

    Kiers, Henk A.L.

    For the analysis of variables of mixed measurement levels a class of methods can be used that is based on three-way analysis of quantification matrices for nominal or quantitative variables. This class of methods incorporates some well-known techniques but also offers a series of interesting new

  2. Steam reforming of tar model compound using Pd catalyst on alumina tube.

    Science.gov (United States)

    Nisamaneenate, Jurarat; Atong, Duangduen; Sricharoenchaikul, Viboon

    2012-12-01

    Gasification processing of biomass as a renewable energy source generates tar in the product gas. Tar leads to foul-up of the process equipment by corrosion and deposit formation. Catalytic elimination of tars is a crucial step to improve fuel gas quality from the process. In this study, a palladium catalyst on alumina (Pd/Al2O3) was used in steam reforming of benzene as a biomass gasification tar model compound. The reaction was carried out in a laboratory-scale tube reactor made of stainless steel to study the effect of reaction temperature, catalyst loading, quantity of palladium catalyst tubes, steam to carbon ratio (S/C), and residence time on catalytic performance and stability. Pd/Al2O3 showed high efficiency ofbenzene decomposition and enhanced the formation of fuel gas. Hydrogen and carbon conversions increased with reaction temperature. Although the benzene concentration increased from 2000 to 5000 mg/l, the catalytic performance at 600 degrees C and 800 degrees C was similar. 1.0 wt% Pd/Al2O3 showed excellent catalytic activity with the highest hydrogen and carbon conversions of 83% and 81%, respectively at 800 degrees C. This result is attributed to the smooth surface of the palladium, as noted from scanning electron microscopy imaging. An S/C of 2 provided the highest conversion. The addition of catalyst from four and seven tubes did not result in any great difference in terms of benzene cracking efficiency. The fourth cyclic usage of 1.0 wt% Pd/Al2O3 exhibited a higher conversion than that of 0.5 wt%.

  3. Atomic structure of graphene supported heterogeneous model catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Franz, Dirk

    2017-04-15

    Graphene on Ir(111) forms a moire structure with well defined nucleation centres. Therefore it can be utilized to create hexagonal metal cluster lattices with outstanding structural quality. At diffraction experiments these 2D surface lattices cause a coherent superposition of the moire cell structure factor, so that the measured signal intensity scales with the square of coherently scattering unit cells. This artificial signal enhancement enables the opportunity for X-ray diffraction to determine the atomic structure of small nano-objects, which are hardly accessible with any experimental technique. The uniform environment of every metal cluster makes the described metal cluster lattices on graphene/Ir(111) an attractive model system for the investigation of catalytic, magnetic and quantum size properties of ultra-small nano-objects. In this context the use of x-rays provides a maximum of flexibility concerning the possible sample environments (vacuum, selected gases, liquids, sample temperature) and allows in-situ/operando measurements. In the framework of the present thesis the structure of different metal clusters grown by physical vapor deposition in an UHV environment and after gas exposure have been investigated. On the one hand the obtained results will explore many aspects of the atomic structure of these small metal clusters and on the other hand the presented results will proof the capabilities of the described technique (SXRD on cluster lattices). For iridium, platinum, iridium/palladium and platinum/rhodium the growth on graphene/Ir(111) of epitaxial, crystalline clusters with an ordered hexagonal lattice arrangement has been confirmed using SXRD. The clusters nucleate at the hcp sites of the moire cell and bind via rehybridization of the carbon atoms (sp{sup 2} → sp{sup 3}) to the Ir(111) substrate. This causes small displacements of the substrate atoms, which is revealed by the diffraction experiments. All metal clusters exhibit a fcc structure

  4. Model studies of secondary hydrogenation in Fischer-Tropsch synthesis studied by cobalt catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Aaserud, Christian

    2003-07-01

    Mass transfer effects are very important in Fischer-Tropsch (FT) synthesis. In order to study the FT synthesis without the influence of any transport limitations, cobalt foils have been used as model catalysts. The effect of pretreatment (number of calcinations and different reduction times) for cobalt foil catalysts at 220 {sup o}C, 1 bar and H{sub 2}/CO = 3 has been studied in a microreactor. The foils were examined by Scanning electron microscopy (SEM). It was found that the catalytic activity of the cobalt foil increases with the number of pretreatments possibly due to an increase in the surface area of the cobalt foil. The SEM results support the assumption that the surface area of the cobalt foil increases with the number of pretreatments. The reduction time was also found to influence the catalytic activity of the cobalt foil. Highest activity was obtained using a reduction time of only five min (compared to one and thirty min). The decrease in activity after reduction for thirty min compared to five min was suggested to be due to restructuring of the surface of the cobalt foil and a reduction time of only 1 min was not enough to reduce the cobalt foil sufficiently. Time of reduction did also influence the product distribution. Increased reduction time resulted in a lower selectivity to light products and increased selectivity to heavier components. The paraffin/olefin ratio increased with increasing CO-conversion also for cobalt foils. The paraffin/olefin ratio also increased when the reduction period of the cobalt foil was increased at a given CO-conversion. Hydrogenation of propene to propane has been studied as a model reaction for secondary hydrogenation of olefins in the FT synthesis. The study has involved promoted and unpromoted cobalt FT catalysts supported on different types of supports and also unsupported cobalt. Hydrogenation of propene was carried out at 120 {sup o}C, 1.8 bar and H{sub 2}/C{sub 3}H{sub 6} 6 in a fixed bed microreactor. The rate

  5. Kinetic Modeling of C3H6 Inhibition on NO Oxidation over Pt Catalyst

    Directory of Open Access Journals (Sweden)

    Muhammad Mufti Azis

    2016-03-01

    Full Text Available Exhaust after treatment for lean burn and diesel engine is a complex catalytic system that consists of a number of catalytic units. Pt/Al2O3 is often used as a model Diesel Oxidation Catalyst (DOC that plays an important role to facilitate oxidation of NO to NO2. In the present study, we proposed a detailed kinetic model of NO oxidation as well as low temperature C3H6 inhibition to simulate temperature-programmed reaction (TPR data for NO oxidation over Pt/Al2O3. A steady-state microkinetic model based on Langmuir-Hinshelwood mechanism for NO oxidation was proposed. In addition, low temperature C3H6 inhibition was proposed as a result of site blocking as well as surface nitrite consumption. The model can explain the experimental data well over the studied temperature range. Copyright © 2016 BCREC GROUP. All rights reserved Received: 10th November 2015; Revised: 1st February 2016; Accepted: 1st February 2016 How to Cite: Azis, M.M., Creaser, D. (2016. Kinetic Modeling of C3H6 Inhibition on NO Oxidation over Pt Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 27-33. (doi:10.9767/bcrec.11.1.403.27-33 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.403.27-33

  6. Modeling Species Inhibition of NO Oxidation in Urea-SCR Catalysts for Diesel Engine NOx Control

    Energy Technology Data Exchange (ETDEWEB)

    Devarakonda, Maruthi N.; Tonkyn, Russell G.; Tran, Diana N.; Lee, Jong H.; Herling, Darrell R.

    2011-04-20

    Urea-selective catalytic reduction (SCR) catalysts are regarded as the leading NOx aftertreatment technology to meet the 2010 NOx emission standards for on-highway vehicles running on heavy-duty diesel engines. However, issues such as low NOx conversion at low temperature conditions still exist due to various factors, including incomplete urea thermolysis, inhibition of SCR reactions by hydrocarbons and H2O. We have observed a noticeable reduction in the standard SCR reaction efficiency at low temperature with increasing water content. We observed a similar effect when hydrocarbons are present in the stream. This effect is absent under fast SCR conditions where NO ~ NO2 in the feed gas. As a first step in understanding the effects of such inhibition on SCR reaction steps, kinetic models that predict the inhibition behavior of H2O and hydrocarbons on NO oxidation are presented in the paper. A one-dimensional SCR model was developed based on conservation of species equations and was coded as a C-language S-function and implemented in Matlab/Simulink environment. NO oxidation and NO2 dissociation kinetics were defined as a function of the respective adsorbate’s storage in the Fe-zeolite SCR catalyst. The corresponding kinetic models were then validated on temperature ramp tests that showed good match with the test data. Such inhibition models will improve the accuracy of model based control design for integrated DPF-SCR aftertreatment systems.

  7. Oxidation catalyst

    Science.gov (United States)

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

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

  8. Global structure of a three-way junction in a phi29 packaging RNA dimer determined using site-directed spin labeling.

    Science.gov (United States)

    Zhang, Xiaojun; Tung, Chang-Shung; Sowa, Glenna Z; Hatmal, Ma'mon M; Haworth, Ian S; Qin, Peter Z

    2012-02-08

    The condensation of bacteriophage phi29 genomic DNA into its preformed procapsid requires the DNA packaging motor, which is the strongest known biological motor. The packaging motor is an intricate ring-shaped protein/RNA complex, and its function requires an RNA component called packaging RNA (pRNA). Current structural information on pRNA is limited, which hinders studies of motor function. Here, we used site-directed spin labeling to map the conformation of a pRNA three-way junction that bridges binding sites for the motor ATPase and the procapsid. The studies were carried out on a pRNA dimer, which is the simplest ring-shaped pRNA complex and serves as a functional intermediate during motor assembly. Using a nucleotide-independent labeling scheme, stable nitroxide radicals were attached to eight specific pRNA sites without perturbing RNA folding and dimer formation, and a total of 17 internitroxide distances spanning the three-way junction were measured using Double Electron-Electron Resonance spectroscopy. The measured distances, together with steric chemical constraints, were used to select 3662 viable three-way junction models from a pool of 65 billion. The results reveal a similar conformation among the viable models, with two of the helices (H(T) and H(L)) adopting an acute bend. This is in contrast to a recently reported pRNA tetramer crystal structure, in which H(T) and H(L) stack onto each other linearly. The studies establish a new method for mapping global structures of complex RNA molecules, and provide information on pRNA conformation that aids investigations of phi29 packaging motor and developments of pRNA-based nanomedicine and nanomaterial.

  9. Global Structure of a Three-Way Junction in a Phi29 Packaging RNA Dimer Determined Using Site-Directed Spin Labeling

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xiaojun; Tung, Chang-Shung; Sowa, Glenna; Hatmal, Ma' mon M.; Haworth, Ian S.; Qin, Peter Z.

    2012-02-08

    The condensation of bacteriophage phi29 genomic DNA into its preformed procapsid requires the DNA packaging motor, which is the strongest known biological motor. The packaging motor is an intricate ring-shaped protein/RNA complex, and its function requires an RNA component called packaging RNA (pRNA). Current structural information on pRNA is limited, which hinders studies of motor function. Here, we used site-directed spin labeling to map the conformation of a pRNA three-way junction that bridges binding sites for the motor ATPase and the procapsid. The studies were carried out on a pRNA dimer, which is the simplest ring-shaped pRNA complex and serves as a functional intermediate during motor assembly. Using a nucleotide-independent labeling scheme, stable nitroxide radicals were attached to eight specific pRNA sites without perturbing RNA folding and dimer formation, and a total of 17 internitroxide distances spanning the three-way junction were measured using Double Electron-Electron Resonance spectroscopy. The measured distances, together with steric chemical constraints, were used to select 3662 viable three-way junction models from a pool of 65 billion. The results reveal a similar conformation among the viable models, with two of the helices (HT and HL) adopting an acute bend. This is in contrast to a recently reported pRNA tetramer crystal structure, in which HT and HL stack onto each other linearly. The studies establish a new method for mapping global structures of complex RNA molecules, and provide information on pRNA conformation that aids investigations of phi29 packaging motor and developments of pRNA-based nanomedicine and nanomaterial.

  10. Modeling hydrodynamic flows in plasma fluxes when depositing metal layer on the surface of catalyst converters

    Science.gov (United States)

    Chinakhov, D. A.; Sarychev, V. D.; Granovsky, A. Yu; Solodsky, S. A.; Nevsky, S. A.; Konovalov, S. V.

    2017-01-01

    Air pollution with harmful substances resulting from combustion of liquid hydrocarbons and emitted into atmosphere became one of the global environmental problems in the late 20th century. The systems of neutralization capable to reduce toxicity of exhaust gases several times are very important for making environmentally safer combustion products discharged into the atmosphere. As revealed in the literature review, one of the most promising purification procedures is neutralization of burnt gases by catalyst converter systems. The principal working element in the converter is a catalytic layer of metals deposited on ceramics, with thickness 20-60 micron and a well-developed micro-relief. The paper presents a thoroughly substantiated new procedure of deposing a nano-scale surface layer of metal-catalyst particles, furthering the utilization of catalysts on a new level. The paper provides description of mathematical models and computational researches into plasma fluxes under high-frequency impulse input delivered to electrode material, explorations of developing Kelvin-Helmholtz, Marangoni and magnetic hydrodynamic instabilities on the surface of liquid electrode metal droplet in the nano-scale range of wavelengths to obtain a flow of nano-meter particles of cathode material. The authors have outlined a physical and mathematical model of magnetic and hydrodynamic instability for the case of melt flowing on the boundary with the molten metal with the purpose to predict the interphase shape and mutual effect of formed plasma jet and liquid metal droplet on the electrode in the nano-scale range of wavelengths at high-frequency impact on the boundary “electrode-liquid layer”.

  11. Effect of the Sequence of the Thermoelectric Generator and the Three-Way Catalytic Converter on Exhaust Gas Conversion Efficiency

    Science.gov (United States)

    Su, Chuqi; Tong, Naiqiang; Xu, Yuman; Chen, Shan; Liu, Xun

    2013-07-01

    The potential for thermoelectric exhaust heat recovery in vehicles has increased with recent improvements in the efficiency of thermoelectric generators (TEGs). The problem with using thermoelectric generators for vehicle applications is whether the device is compatible with the original vehicle exhaust system, which determines the quality of the exhaust gas treatment and the realization of energy conservation and emission reduction. Based on ANSYS CFX simulation analysis of the impact of two positional relationships between the TEG and three-way catalytic converter in the exhaust system on the working efficiency of both elements, it is concluded that the layout with the front three-way catalytic converter has an advantage over the other layout mode under current conditions. New ideas for an improvement program are proposed to provide the basis for further research.

  12. MECHANISTIC KINETIC MODELS FOR STEAM REFORMING OF CONCENTRATED CRUDE ETHANOL ON NI/AL2O3 CATALYST

    Directory of Open Access Journals (Sweden)

    O. A. OLAFADEHAN

    2015-05-01

    Full Text Available Mechanistic kinetic models were postulated for the catalytic steam reforming of concentrated crude ethanol on a Ni-based commercial catalyst at atmosphere pressure in the temperature range of 673-863 K, and at different catalyst weight to the crude ethanol molar flow rate ratio (in the range 0.9645-9.6451 kg catalyst h/kg mole crude ethanol in a stainless steel packed bed tubular microreactor. The models were based on Langmuir-Hinshelwood-Hougen-Watson (LHHW and Eley-Rideal (ER mechanisms. The optimization routine of Nelder-Mead simplex algorithm was used to estimate the inherent kinetic parameters in the proposed models. The selection of the best kinetic model amongst the rival kinetic models was based on physicochemical, statistical and thermodynamic scrutinies. The rate determining step for the steam reforming of concentrated crude ethanol on Ni/Al2O3 catalyst was found to be surface reaction between chemisorbed CH3O and O when hydrogen and oxygen were adsorbed as monomolecular species on the catalyst surface. Excellent agreement was obtained between the experimental rate of reaction and conversion of crude ethanol, and the simulated results, with ADD% being ±0.46.

  13. A comprehensive model for the supported vanadium oxide catalyst: The umbrella model

    NARCIS (Netherlands)

    Lingen, J.N.J. van

    2006-01-01

    Supported vanadium oxide catalysts are widely used in industry. However, the molecular structure of the active species, responsible for the actual catalysis, is for a large part still unknown. This thesis describes four years study on the elucidation of this molecular structure. It mainly focuses on

  14. Steam reforming of biomass gasification tar using benzene as a model compound over various Ni supported metal oxide catalysts.

    Science.gov (United States)

    Park, Hyun Ju; Park, Sung Hoon; Sohn, Jung Min; Park, Junhong; Jeon, Jong-Ki; Kim, Seung-Soo; Park, Young-Kwon

    2010-01-01

    The steam reforming of benzene as a model compound of biomass gasification tar was carried out over various Ni/metal oxide catalysts. The effects of the support, temperature, Ni-precursor, Ni loading and reaction time were examined, and their catalytic performance was compared with that of a commercial Ni catalyst. Among the Ni/metal oxide catalysts used, 15 wt% Ni/CeO(2)(75%)-ZrO(2)(25%) showed the highest catalytic performance owing to its greater redox characteristics and increased surface area, irrespective of the reaction temperature. The catalytic activity of 15 wt% Ni/CeO(2)(75%)-ZrO(2)(25%) was higher than that of the commercial Ni catalyst. Moreover, the catalyst activity was retained due to its excellent resistance to coke deposition even after 5h. The Ni-precursor played a critical role in the catalytic activity. With the exception of nickel nitrate, all the Ni-precursors (chloride and sulfate) caused deactivation of the catalyst.

  15. Optimization of polymer electrolyte fuel cell cathode catalyst layers via direct numerical simulation modeling

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Guoqing; Mukherjee, Partha P.; Wang, Chao-Yang [Electrochemical Engine Center (ECEC), Department of Mechanical and Nuclear Engineering, The Pennsylvania State University, University Park, PA 16802 (United States)

    2007-06-30

    The cathode catalyst layer (CL), due to sluggish oxygen reduction reaction and several transport losses therein, plays an important role in the overall performance of polymer electrolyte fuel cells (PEFCs). The relative volume fractions of the constituent phases, i.e. the electronic, electrolyte and void phases, of the cathode CL need to be selected appropriately in order to achieve an optimal balance between oxygen diffusion and proton conduction. In this work, the influence of electrolyte and void phase fractions of the cathode CL on the cell performance is investigated based on a pore-level description of species and charge transport through a random CL microstructure via the direct numerical simulation (DNS) model. Additionally, the effects of inlet relative humidity and net water transport from the anode on the cathode performance have been studied which indicate the interdependence between the CL composition and the cell operating conditions. The results indicate that the low humidity operation benefits the performance by enhancing the oxygen transport especially under high current densities. Finally, the DNS model predicts the volume fractions of 0.4 and 0.26 for the void and electrolyte phases, respectively, as the optimal composition of the catalyst layer for the best performance. (author)

  16. Predictive Modelling of Phase-Transfer Catalyst Systems for Improved and Innovative Design

    DEFF Research Database (Denmark)

    Anantpinijwatna, Amata; Hyung Kim, Sun; Sales-Cruz, Mauricio

    2016-01-01

    increasing attention as a novel organic synthesis option due to its flexible and easier operation, higher production yield, and ability to eliminate expensive solvents, although, not eliminating the use of solvents. New mathematical models of the PTC system, which includes physical and chemical equilibrium......Phase-transfer catalyst (PTC) systems contain two immiscible liquid phases with a heterogeneous PTC transferring active ion from one phase to the other for converting the reactant to the desired product, and in the process generating the inactive ion. This type of reacting systems is receiving......, reaction mechanism and unit operation has been developed. In the developed model, the PTC system is divided into four sub-systems of aqueous-organic solvent partition, inorganic salt in aqueous phase, PTC in aqueous phase, and PTC in aqueous phase. Each subsystem requires an appropriate thermodynamic model...

  17. Novel Oxygen Storage Components Promoted Palladium Catalysts for Emission Control in Natural Gas Powered Engines

    Institute of Scientific and Technical Information of China (English)

    Bin ZHAO; Mao Chu GONG; Xue Song FENG; Yong Yue LUO; Yao Qiang CHEN

    2005-01-01

    A three-way catalyst comprised novel oxygen storage components for emission control in natural gas powered engines was prepared. The addition of novel oxygen storage components to the Pd/γ-A12O3 catalysts resulted in improved activities of the fresh and aged catalyst by lowering the light-off temperature for methane in natural gas engines exhaust.

  18. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts; A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    Energy Technology Data Exchange (ETDEWEB)

    Manos Mavrikakis; James Dumesic; Rahul Nabar; Calvin Bartholonew; Hu Zou; Uchenna Paul

    2008-09-29

    This work focuses on (1) searching/summarizing published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) preparation and characterization of unsupported iron catalysts with/without potassium/platinum promoters; (3) measurement of H{sub 2} and CO adsorption/dissociation kinetics on iron catalysts using transient methods; (3) analysis of the transient rate data to calculate kinetic parameters of early elementary steps in FTS; (4) construction of a microkinetic model of FTS on iron, and (5) validation of the model from collection of steady-state rate data for FTS on iron catalysts. Three unsupported iron catalysts and three alumina-supported iron catalysts were prepared by non-aqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, temperature-programmed reduction (TPR), extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2} and thus ideal for kinetic and mechanistic studies. Kinetic parameters for CO adsorption, CO dissociation, and surface carbon hydrogenation on these catalysts were determined from temperature-programmed desorption (TPD) of CO and temperature programmed surface hydrogenation (TPSR), temperature-programmed hydrogenation (TPH), and isothermal, transient hydrogenation (ITH). A microkinetic model was constructed for the early steps in FTS on polycrystalline iron from the kinetic parameters of elementary steps determined experimentally in this work and from literature values. Steady-state rate data were collected in a Berty reactor and used for validation of the microkinetic model. These rate data were fitted to 'smart' Langmuir-Hinshelwood rate expressions derived from a sequence of elementary steps and using a combination of fitted steady-state parameters and parameters specified from the transient

  19. The selective oxidation of ammonia over alumina supported catalysts. Experiments and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Jones, J.M.; Pourkashanian, M.; Williams, A.; Backreedy, R.I.; Darvell, L.I. [Energy and Resources Research Institute, School of Process Environmental and Materials Engineering, University of Leeds, Leeds LS29JT (United Kingdom); Simell, P.; Heiskanen, K. [VTT Processes, P.O. Box 1601, FIN-02044 VTT (Finland); Kilpinen, P. [AAbo Akademi Process Chemistry Centre, Laboratory for Industrial Chemistry, Turku (Finland)

    2005-09-01

    Hot gas-clean up will improve the efficiency of emerging gasification technologies. Selective catalytic oxidation (SCO) of ammonia is a promising approach for dealing with the main fixed nitrogen species. The work presented here comprises both laboratory scale experimental measurements of potential SCO catalysts, as well as the development of a simple four-step reaction model to describe the behaviour of one of the more promising catalysts. A range of transition metal oxides supported on {gamma}-alumina were studied for their activity in the SCO of ammonia in a simulated gasification gas mixture containing CO, H{sub 2}O, H{sub 2}, CO{sub 2}, CH{sub 4}, H{sub 2}S and toluene as model tar species. Both copper and chromium based catalysts demonstrated a window of operating temperature over which they were resistant to poisoning by H{sub 2}S; Cu/Al{sub 2}O{sub 3} was in fact promoted by this gas for the SCO reaction. The ammonia conversion over 7% Cu/Al{sub 2}O{sub 3} was studied in more detail, and this data was further used to develop a kinetic model for the reactions taking place over the temperature range 723-906K. Excellent conversion and selectivity to N{sub 2} was found in the temperature window 973-1173K and 2.6vol% O{sub 2}. However, it also catalyses a rapid H{sub 2}-O{sub 2} reaction. This reaction consumes all remaining available oxygen so that no other oxidation reactions take place (e.g. of methane or 'tar'). The four-step reaction model was developed using the PLUG application of Chemkin and Surface Chemkin software coupled with the gas-phase mechanism. Rates for the heterogeneous oxidation of ammonia and hydrogen are included as well as forward and reverse reactions of the water gas shift. Over the temperature range in question, the surface reaction rates are much faster than the gas-phase reactions. The model is applicable for the 723-906K temperature range using a gas mixture containing 0.4vol% ammonia and 0.01vol% H{sub 2}S in the presence

  20. Two-way and three-way approaches to ultra high performance liquid chromatography-photodiode array dataset for the quantitative resolution of a two-component mixture containing ciprofloxacin and ornidazole.

    Science.gov (United States)

    Dinç, Erdal; Ertekin, Zehra Ceren; Büker, Eda

    2016-09-01

    Two-way and three-way calibration models were applied to ultra high performance liquid chromatography with photodiode array data with coeluted peaks in the same wavelength and time regions for the simultaneous quantitation of ciprofloxacin and ornidazole in tablets. The chromatographic data cube (tensor) was obtained by recording chromatographic spectra of the standard and sample solutions containing ciprofloxacin and ornidazole with sulfadiazine as an internal standard as a function of time and wavelength. Parallel factor analysis and trilinear partial least squares were used as three-way calibrations for the decomposition of the tensor, whereas three-way unfolded partial least squares was applied as a two-way calibration to the unfolded dataset obtained from the data array of ultra high performance liquid chromatography with photodiode array detection. The validity and ability of two-way and three-way analysis methods were tested by analyzing validation samples: synthetic mixture, interday and intraday samples, and standard addition samples. Results obtained from two-way and three-way calibrations were compared to those provided by traditional ultra high performance liquid chromatography. The proposed methods, parallel factor analysis, trilinear partial least squares, unfolded partial least squares, and traditional ultra high performance liquid chromatography were successfully applied to the quantitative estimation of the solid dosage form containing ciprofloxacin and ornidazole.

  1. Catalytic Hydrodeoxygenation of Bio-oil Model Compounds over Pt/HY Catalyst

    Science.gov (United States)

    Lee, Heejin; Kim, Hannah; Yu, Mi Jin; Ko, Chang Hyun; Jeon, Jong-Ki; Jae, Jungho; Park, Sung Hoon; Jung, Sang-Chul; Park, Young-Kwon

    2016-06-01

    The hydrodeoxygenation of a model compound of lignin-derived bio-oil, guaiacol, which can be obtained from the pyrolysis of biomass to bio-oil, has attracted considerable research attention because of its huge potential as a substitute for conventional fuels. In this study, platinum-loaded HY zeolites (Pt/HY) with different Si/Al molar ratios were used as catalysts for the hydrodeoxygenation of guaiacol, anisole, veratrole, and phenol to a range of hydrocarbons, such as cyclohexane. The cyclohexane (major product) yield increased with increasing number of acid sites. To produce bio-oil with the maximum level of cyclohexane and alkylated cyclohexanes, which would be suitable as a substitute for conventional transportation fuels, the Si/Al molar ratio should be optimized to balance the Pt particle-induced hydrogenation with acid site-induced methyl group transfer. The fuel properties of real bio-oil derived from the fast pyrolysis of cork oak was improved using the Pt/HY catalyst.

  2. Shake-Rattle-and-Roll: A Model of Dynamic Structural Disorder in Supported Nanoscale Catalysts

    CERN Document Server

    Rehr, J J

    2013-01-01

    We investigate the effects of "dynamic structural disorder" (DSD) on the behavior of supported nano-scale catalysts. DSD refers to the intrinsic fluctuating, inhomogeneous structure of such nano-scale systems. In contrast to bulk materials, nano-scale systems exhibit substantial fluctuations in energy, charge, and other extensive quantities as well as large surface effects. The DSD is driven by the stochastic librational motion of the center of mass and fluxional bonding at the nanoparticle surface due to thermal coupling with the substrate. Our approach for calculating DSD is based on a combination of statistical mechanics, transient coupled-oscillator models, and real-time DFT/MD simulations. This approach treats thermal and dynamic effects over multiple time-scales, including bond-stretching and -bending vibrations, DSD, and transient tethering to the substrate at longer ps time-scales. Model calculations of molecule-cluster interactions and molecular dissociation reaction paths are presented in which the ...

  3. Catalytic pyrolysis of model compounds and waste cooking oil for production of light olefins over La/ZSM-5 catalysts

    Science.gov (United States)

    Li, F. W.; Ding, S. L.; Li, L.; Gao, C.; Zhong, Z.; Wang, S. X.; Li, Z. X.

    2016-08-01

    Waste cooking oil (WCO) and its model compounds (oleic acid and methyl laurate) are catalytically pyrolyzed in a fixed-bed reactor over La modified ZSM-5 catalysts (La/ZSM-5) aiming for production of C2-C4 light olefins. The LaO content in catalysts was set at 0, 2, 6, 10 and 14 wt%. The gas and liquid products are analyzed. The La/ZSM-5 catalyst with 6% LaO showed higher selectivity to light olefins when WCO and methyl laurate were pyrolyzed, and olefin content was 26% for WCO and 21% for methyl laurate. The catalyst with 10% LaO showed high selectivity to light olefins (28.5%) when oleic acid was pyrolyzed. The liquid products from WCO and model compounds mainly contain esters and aromatic hydrocarbons. More esters were observed in liquid products from methyl laurate and WCO pyrolysis, indicating that it is more difficult to pyrolyze esters and WCO than oleic acid. The coked catalysts were analyzed by temperature-programmed oxidation. The result shows that graphite is the main component of coke. The conversion of WCO to light olefins potentially provides an alternative and sustainable route for production of the key petrochemicals.

  4. Application of a Coated Film Catalyst Layer Model to a High Temperature Polymer Electrolyte Membrane Fuel Cell with Low Catalyst Loading Produced by Reactive Spray Deposition Technology

    Directory of Open Access Journals (Sweden)

    Timothy D. Myles

    2015-10-01

    Full Text Available In this study, a semi-empirical model is presented that correlates to previously obtained experimental overpotential data for a high temperature polymer electrolyte membrane fuel cell (HT-PEMFC. The goal is to reinforce the understanding of the performance of the cell from a modeling perspective. The HT-PEMFC membrane electrode assemblies (MEAs were constructed utilizing an 85 wt. % phosphoric acid doped Advent TPS® membranes for the electrolyte and gas diffusion electrodes (GDEs manufactured by Reactive Spray Deposition Technology (RSDT. MEAs with varying ratios of PTFE binder to carbon support material (I/C ratio were manufactured and their performance at various operating temperatures was recorded. The semi-empirical model derivation was based on the coated film catalyst layer approach and was calibrated to the experimental data by a least squares method. The behavior of important physical parameters as a function of I/C ratio and operating temperature were explored.

  5. Modeling of methanol decomposition on Pt/CeO2/ZrO2 catalyst in a packed bed microreactor

    Science.gov (United States)

    Pohar, Andrej; Belavič, Darko; Dolanc, Gregor; Hočevar, Stanko

    2014-06-01

    Methanol decomposition on Pt/CeO2/ZrO2 catalyst is studied inside a packed bed microreactor in the temperature range of 300-380 °C. The microreactor is fabricated using low-temperature co-fired ceramic (LTCC) technology, which is well suited for the production of relatively complex three-dimensional structures. It is packed with 2 wt% Pt-CeO2 catalyst, which is deposited onto ZrO2 spherical particles. A 1D mathematical model, which incorporates diffusion, convection and mass transfer through the boundary layer to the catalyst particles, as well as a 3D computational fluid dynamics model, are developed to describe the methanol decomposition process inside the packed bed. The microreactor exhibits reliable operation and no catalyst deactivation was observed during three months of experimentation. A comparison between the 1D mathematical model and the 3D model, considering the full 3D geometry of the microreactor is made and the differences between the models are identified and evaluated.

  6. Dry (CO2) reforming of methane over Pt catalysts studied by DFT and kinetic modeling

    Science.gov (United States)

    Niu, Juntian; Du, Xuesen; Ran, Jingyu; Wang, Ruirui

    2016-07-01

    Dry reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial importance. In order to design catalysts that minimize the deactivation and improve the selectivity and activity for a high H2/CO yield, it is necessary to understand the elementary reaction steps involved in activation and conversion of CO2 and CH4. In our present work, a microkinetic model based on density functional theory (DFT) calculations is applied to explore the reaction mechanism for methane dry reforming on Pt catalysts. The adsorption energies of the reactants, intermediates and products, and the activation barriers for the elementary reactions involved in the DRM process are calculated over the Pt(1 1 1) surface. In the process of CH4 direct dissociation, the kinetic results show that CH dissociative adsorption on Pt(1 1 1) surface is the rate-determining step. CH appears to be the most abundant species on the Pt(1 1 1) surface, suggesting that carbon deposition is not easy to form in CH4 dehydrogenation on Pt(1 1 1) surface. In the process of CO2 activation, three possible reaction pathways are considered to contribute to the CO2 decomposition: (I) CO2* + * → CO* + O*; (II) CO2* + H* → COOH* + * → CO* + OH*; (III) CO2* + H* → mono-HCOO* + * → bi-HCOO* + * [CO2* + H* → bi-HCOO* + *] → CHO* + O*. Path I requires process to overcome the activation barrier of 1.809 eV and the forward reaction is calculated to be strongly endothermic by 1.430 eV. In addition, the kinetic results also indicate this process is not easy to proceed on Pt(1 1 1) surface. While the CO2 activation by H adsorbed over the catalyst surface to form COOH intermediate (Path II) is much easier to be carried out with the lower activation barrier of 0.746 eV. The Csbnd O bond scission is the rate-determining step along this pathway and the process needs to overcome the activation barrier of 1.522 eV. Path III reveals the CO2 activation through H adsorbed over the catalyst

  7. Alternative Models of Iron and Cobalt Catalysts for Ethylene Oligomerization and Polymerization

    Institute of Scientific and Technical Information of China (English)

    Katrin; Wedeking; Sherrif; Adewuyi; Maliha; Asma; Igor; Vystorop; Saliu; Amolegbe; Elena; Novikova

    2007-01-01

    1 Results Great progresses have been made in the field of transition metal-based complexes as catalytic precursors for olefin oligomerization and polymerization,in which the core subjects will remain as "know and how" to develop novel catalysts both in academic and industrial consideration.The key advantage of iron and cobalt catalyst for ethylene polymerization is to produce vinyl-type polyethylenes.Therefore following the pioneering works of bis(imino) pyridyl iron and cobalt catalyst by Brookhart[1] ...

  8. The CO methanation on Rh/CeO 2 and CeO 2/Rh model catalysts: a comparative study

    Science.gov (United States)

    Jenewein, B.; Fuchs, M.; Hayek, K.

    2003-06-01

    Like other reducible oxides, ceria promotes the CO methanation reaction on noble metals, but after high-temperature reduction the promotion is usually reduced and limited to transient conditions. We studied the effect of low- and high-temperature reduction on two types of Rh/ceria model catalysts: "thin film catalysts" consisting of well-defined regular Rh nanoparticles partly embedded in the crystalline ceria support, and "inverse catalysts", i.e. UHV grown ceria submonolayers on polycrystalline Rh surfaces. The turnover rates on either catalyst were related to the free Rh surface area and to the dimensions of the metal-oxide boundary. On thin film catalysts the rates decrease strongly with reduction temperature up to 723 K while no significant structural changes are detectable by ex situ electron microscopy. On ceria-modified surfaces the reaction is initially favoured after reduction below 573 K, but promotion converts to inhibition with increasing reduction temperature. The changing number of Ce III/Ce IV ions on the surface, the oxygen transport to and from the interface, and changes in the free Rh surface area resulting from spreading and reordering of the ceria overlayer are discussed as possible reasons for the observed effects.

  9. Jacobsen Catalyst as a Cytochrome P450 Biomimetic Model for the Metabolism of Monensin A

    Directory of Open Access Journals (Sweden)

    Bruno Alves Rocha

    2014-01-01

    Full Text Available Monensin A is a commercially important natural product isolated from Streptomyces cinnamonensins that is primarily employed to treat coccidiosis. Monensin A selectively complexes and transports sodium cations across lipid membranes and displays a variety of biological properties. In this study, we evaluated the Jacobsen catalyst as a cytochrome P450 biomimetic model to investigate the oxidation of monensin A. Mass spectrometry analysis of the products from these model systems revealed the formation of two products: 3-O-demethyl monensin A and 12-hydroxy monensin A, which are the same ones found in in vivo models. Monensin A and products obtained in biomimetic model were tested in a mitochondrial toxicity model assessment and an antimicrobial bioassay against Staphylococcus aureus, S. aureus methicillin-resistant, Staphylococcus epidermidis, Pseudomonas aeruginosa, and Escherichia coli. Our results demonstrated the toxicological effects of monensin A in isolated rat liver mitochondria but not its products, showing that the metabolism of monensin A is a detoxification metabolism. In addition, the antimicrobial bioassay showed that monensin A and its products possessed activity against Gram-positive microorganisms but not for Gram-negative microorganisms. The results revealed the potential of application of this biomimetic chemical model in the synthesis of drug metabolites, providing metabolites for biological tests and other purposes.

  10. The potential of model studies for the understanding of catalyst poisoning and temperature effects in polymer electrolyte fuel cell reactions

    Science.gov (United States)

    Behm, R. J.; Jusys, Z.

    In this contribution we demonstrate the potential of model studies for the understanding of electrocatalytic reactions in low-temperature polymer electrolyte fuel cells (PEFCs) operated by H 2-rich anode feed gas, in particular of the role of temperature effects and catalyst poisoning. Reviewing previous work from our laboratory and, for better comparison, focussing on carbon-supported Pt catalysts, the important role of using fuel cell relevant reaction and mass transport conditions will be outlined. The latter conditions include continuous reaction, elevated temperatures, realistic supported catalyst materials and controlled mass transport. The data show the importance of combining electrochemical techniques such as rotating disc electrode (RDE), wall-jet and flow cell measurements, and on-line differential electrochemical mass spectrometry (DEMS) under controlled mass transport conditions.

  11. ATOMIC-SCALE DESIGN OF IRON FISCHER-TROPSCH CATALYSTS: A COMBINED COMPUTATIONAL CHEMISTRY, EXPERIMENTAL, AND MICROKINETIC MODELING APPROACH

    Energy Technology Data Exchange (ETDEWEB)

    Manos Mavrikakis; James A. Dumesic; Amit A. Gokhale; Rahul P. Nabar; Calvin H. Bartholomew; Hu Zou; Brian Critchfield

    2005-03-22

    Efforts during this first year focused on four areas: (1) searching/summarizing published FTS mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) construction of mass spectrometer-TPD and Berty CSTR reactor systems; (3) preparation and characterization of unsupported iron and alumina-supported iron catalysts at various iron loadings (4) Determination of thermochemical parameters such as binding energies of reactive intermediates, heat of FTS elementary reaction steps, and kinetic parameters such as activation energies, and frequency factors of FTS elementary reaction steps on a number of model surfaces. Literature describing mechanistic and kinetic studies of Fischer-Tropsch synthesis on iron catalysts was compiled in a draft review. Construction of the mass spectrometer-TPD system is 90% complete and of a Berty CSTR reactor system 98% complete. Three unsupported iron catalysts and three alumina-supported iron catalysts were prepared by nonaqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2}, thus ideal for kinetic and mechanistic studies. The alumina-supported iron catalysts will be used for kinetic and mechanistic studies. In the coming year, adsorption/desorption properties, rates of elementary steps, and global reaction rates will be measured for these catalysts, with and without promoters, providing a database for understanding effects of dispersion, metal loading, and support on elementary kinetic parameters and for validation of computational models that incorporate effects of surface structure and promoters. Furthermore, using state-of-the-art self-consistent Density Functional Theory (DFT) methods, we have extensively studied the thermochemistry and kinetics of various elementary steps on

  12. High-pressure study on the adsorption and oxidation of CO on gold/titania model catalysts

    Science.gov (United States)

    Diemant, Thomas; Zhao, Zhong; Rauscher, Hubert; Bansmann, Joachim; Behm, R. Jürgen

    2007-09-01

    The results of an IR study on the interaction of CO/O 2 gas mixtures with planar Au/TiO 2 model catalysts at elevated pressures and at room temperature are presented. The model catalysts were prepared by deposition of a flat titania film on a Ru(0 0 0 1) substrate and subsequent evaporation of gold on the titania film. In the presence of the gas mixtures, an IR band in the CO stretching region was formed, pointing to linearly adsorbed CO. The position of this band is nearly independent of the Au coverage employed. Compared to pure CO, the IR band is shifted to higher wave numbers when CO/O 2 gas mixtures are used. Although the production of CO 2 was detected in the CO oxidation reaction on the model catalysts, the formation of other IR bands, revealing the build-up of carbonates or other side-products which is usually observed for Au/TiO 2 real powder catalysts, was very weak.

  13. A Continuum Model for Water Transport in the Ionomer-Phase of Catalyst Coated Membranes for PEMFCs

    Directory of Open Access Journals (Sweden)

    Vladimir Gurau

    2010-01-01

    Full Text Available We study the problem of water transport in the ionomer-phase of catalyst coated membranes (CCMs for proton exchange membrane fuel cells (PEMFCs, where microscopic-scale phenomena at the distributed interfaces between structural components control the water management. Existing models for water transport in CCMs describe the transport in systems which consist exclusively of an ionomer-phase. Interfacial water fluxes across distributed interfaces representing various mechanisms of water transfer between ionomer and catalyst layer pores are not captured properly in these models. Here we develop a continuum model for water transport in CCMs using the method of volume averaging. Water is exchanged between ionomer and the catalyst layer pores by electro-osmotic discharge (EOD through the three-phase boundary (TPB regions and by sorption and desorption across the ionomer-pore interfaces. While the former mechanism does not affect directly the water content in the ionomer-phase, it represents an effective mechanism for water transfer during fuel cell operation and controls directly the water saturation in the catalyst pores.

  14. Direct determination of reserpine in urine using excitationemission fluorescence combined with three-way chemometric calibration methodologies

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The concentration of reserpine in urine was directly and quantitatively measured by using the excitation-emission fluorescence (EEM) combined with threeway calibration methodologies.Two calibration methods are based on the alternating trilinear decomposition (ATLD) and the self-weighted alternating trilinear decomposition (SWATLD) algorithms,respectively.These chemometric methodologies have the second-order advantage,which is the ability to get accurate concentration estimates of interested analyte(s) even in the presence of uncalibrated interferences.The satisfactory results on spiked urine samples are obtained,when the component number was chosen to 3 (N=3) for both the methods.This experiment is easily carried out without time-consuming and complicated pretreatment.It has proved that the three-way calibration methodologies based on ATLD and SWATLD can be feasible to directly quantify the medical content of reserpine in urine.

  15. CLV3W : A clustering around latent variables approach to detect panel disagreement in three-way conventional sensory profiling data

    NARCIS (Netherlands)

    Wilderjans, T.F.; Cariou, V.

    2016-01-01

    To detect panel disagreement, we propose the clustering around latent variables for three-way data (CLV3W) approach which extends the clustering of variables around latent components (CLV) approach to three-way data typically obtained from a conventional sensory profiling procedure (i.e., assessors

  16. CLV3W : A clustering around latent variables approach to detect panel disagreement in three-way conventional sensory profiling data

    NARCIS (Netherlands)

    Wilderjans, T.F.; Cariou, V.

    2016-01-01

    To detect panel disagreement, we propose the clustering around latent variables for three-way data (CLV3W) approach which extends the clustering of variables around latent components (CLV) approach to three-way data typically obtained from a conventional sensory profiling procedure (i.e., assessors

  17. 高等教育的三种理解方式%Three Ways of Understanding Higher Education

    Institute of Scientific and Technical Information of China (English)

    李海龙

    2015-01-01

    The understanding is the human survival way,people continue to construct their own spirit and the real world by understanding. For higher education,its own shape and value of property can become different because of the way people understand. By understanding,people shape the history,now and in the future of higher education. Generally speaking,people tend to understand higher education from three ways that shape the perception of life,knowledge of intellectual activities,entity organizational university. Although it is not the only expression way for human understanding and the expression higher education,through these three ways that people can be more intuitive insight into the feelings of the people brought to higher education.%理解是人的生存方式,人通过理解不断建构着自己的精神与现实世界。对于高等教育来说,其本身的形态和价值属性会因为人的理解方式不同而不同。人通过理解塑造着高等教育的历史、现在和未来。通常来说,人们倾向于从塑造可以感知的生命、智识活动的知识和实体机构的大学3个方式去理解高等教育。人的理解和高等教育的表达方式虽然并不是唯一的,但是通过这3种方式,人们可以更加直观深刻地体会到高等教育带给人们的感受。

  18. Effect of phase interaction on catalytic CO oxidation over the SnO2/Al2O3 model catalyst

    Science.gov (United States)

    Chai, Shujing; Bai, Xueqin; Li, Jing; Liu, Cheng; Ding, Tong; Tian, Ye; Liu, Chang; Xian, Hui; Mi, Wenbo; Li, Xingang

    2017-04-01

    We investigated the catalytic CO oxidation over the SnO2/Al2O3 model catalysts. Our results show that interaction between the Al2O3 and SnO2 phases results in the significantly improved catalytic activity because of the formation of the oxygen vacancies. The oxygen storage capacity of the SnO2/Al2O3 catalyst prepared by the physically mixed method is nearly two times higher than that of the SnO2, which probably results from the change of electron concentration on the interface of the SnO2 and Al2O3 phases. Introducing water vapor to the feeding gas would a little decrease the activity of the catalysts, but the reaction rate could completely recover after removal of water vapor. The kinetics results suggest that the surface Sn4+ cations are effective CO adsorptive sites, and the surface adsorbed oxygen plays an important role upon CO oxidation. The reaction pathways upon the SnO2-based catalysts for CO oxidation follow the Langmuir-Hinshelwood model.

  19. Modeling intraparticle transports during propylene polymerizations using supported metallocene and dual function metallocene as catalysts: Single particle model

    Directory of Open Access Journals (Sweden)

    Li Hua-Rong

    2014-01-01

    Full Text Available Two improved multigrain models (MGMs for preparing homopolypropylene and long chain branched polypropylene via propylene polymerization using silica-supported metallocene or dual function metallocene as catalysts are presented in this paper. The presented models are used to predict the intraparticle flow fields involved in the polymerizations. The simulation results show that the flow field distributions involve dare basically identical. The results also show that both the two polymerization processes have an initiation stage and the controlling step for them is reaction-diffusion-reaction with the polymerization proceeding. Furthermore, the simulation results show that the intra particle mass transfer resistance has significant effect on the polymerization but the heat transfer resistance can be ignored.

  20. Reaction mechanism of ethylene glycol decomposition on Pt model catalysts: A density functional theory study

    Science.gov (United States)

    Lv, Cun-Qin; Yang, Bo; Pang, Xian-Yong; Wang, Gui-Chang

    2016-12-01

    Understanding and controlling bond beak sequence is important in catalytic processes. The DFT-GGA method combined with slab model was performed to study the ethylene glycol decomposition on various Pt model catalysts such as close-packed Pt(111), stepped Pt(211) and a more open one, Pt(100). Calculation results show that the adsorption energies of ethylene glycol and other decomposition species depend on the coordination number of surface atom, that is, low coordination number correspond to high adsorption energy. Moreover, it was found that final products of ethylene glycol decomposition are CO and H2 on all model catalysts, but the reaction mechanism varies: On Pt(111), the first step is Osbnd H bond scission, followed by Csbnd H bond cleavage, namely C2H6O2 → HOCH2CH2O + H → HOCH2CHO + 2H→ HOCH2CO +3H → OCH2CO + 4H → OCHCO + 5H → CO + HCO + 5H → 2CO + 6H→ 2CO + 3H2; On Pt(211) and Pt(100), however, it is a second Osbnd H bond cleavage that follows the initial Osbnd H bond scission, that is, C2H6O2 → HOCH2CH2O + H → OCH2CH2O + 2H → OCHCH2O + 3H → OCHCHO + 4H → 2HCO + 4H → 2CO + 6H → 2CO + 3H2 on Pt(211), and C2H6O2 →HOCH2CH2O+ H → OCH2CH2O + 2H→OCHCH2O+3H→OCCH2O+4H→CO+H2CO+4H→CO+HCO+5H→2CO+6H→2CO+3H2 on Pt(100) For the catalytic order of ethylene glycol to form H2, it may be determined based on the rate-controlling step, and it is Pt(111) > Pt(211) > Pt(100).

  1. 3D-modelling of bifunctional core-shell catalysts for the production of fuels from biomass-based synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Wenjin; Lee, Seung Cheol; Li, Hui; Pfeifer, Peter; Dittmeyer, Roland [Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen (Germany). Inst. for Micro Process Engineering (IMVT)

    2013-09-01

    Until now, the main route for the production of DME from synthesis gas in industry is methanol synthesis on a metallic catalyst and subsequent dehydration of methanol on an acid catalyst (two-step process). A single-step process using bifunctional catalysts to perform the two steps simultaneously would be preferred e.g. due to thermodynamic considerations; but this is impeded by the higher volumetric heat release which may cause deactivation of the methanol synthesis catalyst function. Thus we propose to conduct the reaction in a microchannel reactor. However, in order to increase the productivity of the microchannel reactor and to lower the investment costs, we aim at a high selectivity and activity of the catalyst. The continuously removal of methanol by dehydration on an acidic ZSM-5 catalyst as shell improves the thermodynamic conditions of methanol synthesis in the CuO/ZnO/Al{sub 2}O{sub 3} core; thus, the synthesis gas conversion can be higher than that determined by the thermodynamics of pure methanol synthesis. The molecular sieving in the zeolite layer can further lead to higher selectivity of DME at milder reaction conditions. However, mass transport limitation of the synthesis gas to the catalyst core should not hinder the reaction, and therefore a more detailed investigation is required. In order to computer-aided optimize the catalyst structure and the operating conditions for core-shell catalysts, a simulation model should be developed to study the coupled reaction and transport processes in core-shell catalysts. In this simulation model the complicated interaction of diffusion and reaction in the zeolite layer (shell) must be detailed by a network model to describe its structure and the mechanisms effectively. In addition, suitable diffusion and kinetic models are required to describe the mass transport and reactions in the layer. Suitable networks, diffusion and kinetic models are discussed for 3D simulations in this contribution. (orig.)

  2. Adsorption and Wetting in Model Mesoporous Silicas and in Complex Metal Oxide Catalysts

    Science.gov (United States)

    Jayaraman, Karthik

    The surface of most metal oxides is covered by hydroxyl groups which influence many surface phenomena such as adsorption and wetting, catalysis and surface reactions. Surface chemistry of silica is a subject of exhaustive studies owing to a wide variety of practical applications of silica. In Chapter 1, a brief review of classification, synthesis and characterization of silica is provided. The hydroxylation of silica surface i.e the number of hydroxyl (-OH) groups on the surface is of utmost importance for its practical applications. In Chapter 2, a brief introduction to surface hydration of silica is provided followed by the gas adsorption measurements and characterization. Pore wetting is critical to many applications of mesoporous adsorbents, catalysts, and separation materials. In the work presented in Chapter 3, we employed the combined vapor adsorption study using nitrogen (77K) and water (293K) isotherms to evaluate the water contact angles for a series of ordered mesoporous silicas (ex:SBA-15). The proposed method of contact angle relies on the statistical film thickness (t-curve) of the adsorbed water. There were no t-curves for water for dehydroxylated or hydrophobic surfaces in literature and we addressed this issue by measuring t-curves for a series of model surfaces with known and varying silanol coverage. Using the radius of menisci ((H2O)), statistical film thickness t(H2O) from water isotherm, and the true radius of pores (rp(N 2)), from nitrogen isotherms, the water contact angle inside pores were calculated. As it was anticipated, the results obtained showed that the silica pore contact angles were strongly influenced by the number of the surface silanol groups and, therefore, by the thermal and hydration treatments of silicas. Phthalocyanines (Pcs) present an interesting class of catalytically active of molecules with unique spectroscopic, photoelectric, and sometimes magnetic properties. In the work presented in Chapter 4, we have undertaken a

  3. Nanocomposite catalyst with palladium nanoparticles encapsulated in a polymeric acid: A model for tandem environmental catalysis

    KAUST Repository

    Isimjan, Tayirjan T.

    2013-04-01

    The synthesis and characterization of a novel hybrid nanocomposite catalyst comprised of palladium nanoparticles embedded in polystyrene sulfonic acid (PSSH) and supported on metal oxides is reported. The catalysts are intended for application in green catalysis, and they are shown to be effective in the hydrolysisreduction sequence of tandem catalytic reactions required for conversion of 2-phenyl-1,3-dioxolane to toluene or of phenol to cyclohexane. The two distinct components in the catalyst, Pd nanoparticles and acidic PSSH, are capable of catalyzing sequential reactions in one pot under mild conditions. This work has demonstrated a powerful approach toward designing highperformance, multifunctional, scalable, and environmentally friendly nanostructured tandem catalysts. © 2013 American Chemical Society.

  4. A sequential vesicle pool model with a single release sensor and a ca(2+)-dependent priming catalyst effectively explains ca(2+)-dependent properties of neurosecretion

    DEFF Research Database (Denmark)

    Walter, Alexander M; da Silva Pinheiro, Paulo César; Verhage, Matthijs;

    2013-01-01

    identified. We here propose a Sequential Pool Model (SPM), assuming a novel Ca(2+)-dependent action: a Ca(2+)-dependent catalyst that accelerates both forward and reverse priming reactions. While both models account for fast fusion from the Readily-Releasable Pool (RRP) under control of synaptotagmin-1...... that the elusive 'alternative Ca(2+) sensor' for slow release might be the upstream priming catalyst, and that a sequential model effectively explains Ca(2+)-dependent properties of secretion without assuming parallel pools or sensors....

  5. Dealing with Organizational Double Binds: Three-way Interactive Effects of Role Stressors and Coping on Worker Exhaustion.

    Science.gov (United States)

    Hornung, Severin; Lampert, Bettina; Glaser, Jürgen

    2016-04-01

    Based on theory regarding the dynamics of organizational double binds, hypotheses were developed about interactive effects of role conflict, role ambiguity, and coping on psychological exhaustion. Hypotheses were tested in a sample of 948 civil servants employed by a government administration in Germany. The sample included 250 (26.4%) women (M age = 43.6 year, SD = 8.3) and average organizational tenure was 17.1 year (SD = 10.0). Moderated multiple regression supported the two hypothesized three-way interactions. Under conditions of high role conflict and high role ambiguity, exhaustion was lower in workers reporting high control coping than in workers reporting low control coping. Under conditions of high role conflict and high role ambiguity, worker exhaustion was more pronounced when support coping was high than when it was low. Problem-focused control coping seems crucial to maintain mental health in dealing with contradictory and unclear work role expectations. Emotion-focused support coping appears symptomatic of prolonged involvement in psychologically dysfunctional work situations that cannot otherwise be addressed. Implications are discussed in the context of growing awareness of the contradictory demands organizations impose on employees.

  6. A compact five-port waveguide structure and its application as a three-way power divider

    Science.gov (United States)

    Guo, Letian; Li, Jiawei; Ba, Tao; Huang, Wenhua; Shao, Hao

    2016-11-01

    A compact five-port waveguide structure consisting of three rectangular ports, one coaxial port, and one circular waveguide port is proposed. The three rectangular waveguides are uniformly distributed in space at angles of 120°, and the coaxial and circular waveguides are located at the top and bottom, respectively, of the rectangular waveguides. The ideal scattering matrix is derived from the symmetry properties of the structure. If the circular and coaxial ports are matched, then the entire five-port waveguide structure is automatically matched. Two connected inserted coaxial probes, a frustum, and a coaxial transition are used to match the five-port waveguide structure with a relatively wide bandwidth. The theoretical and experimental results are generally consistent with each other. With the circular port connected to the load, the five-port waveguide structure becomes a reciprocal TEM mode-to-three-way TE10 mode power divider. Measurements indicate that from 8 to 9.6 GHz, the return losses at the three rectangular ports and the coaxial port are greater than 20 dB and 17 dB, respectively. The isolation among the three rectangular ports is higher than 20 dB. The amplitude and phase imbalances in the division of power are less than 0.1 dB and 2°, respectively. The volume of the five-port waveguide structure is as small as 1.5 λ × 1.5λ × λ.

  7. Preparation and characterization of planar Ni–Au bimetallic model catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Fan, E-mail: fan.yang@chem.tamu.edu; Yao, Yunxi; Yan, Zhen; Min, Hlaing; Goodman, D. Wayne

    2013-10-15

    Ni–Au bimetallic model catalysts were prepared as thin films on Re(0 0 0 1) or Ru(0 0 0 1) single crystal substrates. Surface compositions and electronic structures of the Ni–Au thin films were characterized by low energy ion scattering spectroscopy and X-ray photoelectron spectroscopy, respectively. Surface alloys were prepared by annealing Ni–Au thin films from 500 to 800 K, resulting in substantial surface enrichment of Au. Annealing a Ni–Au thin film with a 1:1 bulk composition ratio at 700 K for 10 min resulted in a surface alloy with 84% (atomic concentration) of Au in the outermost surface layer. The surface atomic structure was investigated using CO as probe molecules, which exclusively adsorbs on the Ni atoms rather than on the Au atoms at room temperature. Polarization modulation infrared reflection absorption spectroscopy of CO adsorption on Ni–Au surface alloys showed that CO adsorption on two-fold bridge sites decreased and finally disappeared with an increase of Au surface concentration. The absence of Ni bridge site CO adsorption indicated that Ni atoms were isolated by Au atoms on Ni–Au alloyed surface.

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

    Science.gov (United States)

    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.

  9. Structure and properties of molybdenum oxide nitrides as model systems for selective oxidation catalysts

    Directory of Open Access Journals (Sweden)

    Lerch Martin

    2011-07-01

    Full Text Available Abstract Molybdenum oxide nitride (denoted as Mo(O,N3 was obtained by ammonolysis of α-MoO3 with gaseous ammonia. Electronic and geometric structure, reducibility, and conductivity of Mo(O,N3 were investigated by XRD, XAS, UV-Vis spectroscopy, and impedance measurements. Catalytic performance in selective propene oxidation was determined by online mass spectrometry und gas chromatography. Upon incorporation of nitrogen, Mo(O,N3 maintained the characteristic layer structure of α-MoO3. XRD analysis showed an increased structural disorder in the layers while nitrogen is removed from the lattice of Mo(O,N3 at temperatures above ~600 K. Compared to regular α-MoO3, Mo(O,N3 exhibited a higher electronic and ionic conductivity and an onset of reduction in propene at lower temperatures. Surprisingly, α-MoO3 and Mo(O,N3 exhibited no detectable differences in onset temperatures of propene oxidation and catalytic selectivity or activity. Apparently, the increased reducibility, oxygen mobility, and conductivity of Mo(O,N3 compared to α-MoO3 had no effect on the catalytic behavior of the two catalysts. The results presented confirm the suitability of molybdenum oxide nitrides as model systems for studying bulk contributions to selective oxidation.

  10. Molecular metal sulfide cluster model for substrate binding to oil-refinery hydrodesulfurization catalysts.

    Science.gov (United States)

    Herbst, Konrad; Monari, Magda; Brorson, Michael

    2002-03-25

    Reaction between [(eta5-Cp')3Mo3S4]+ and [Ni(1,5-cod)2] (Cp' = methylcyclopentadienyl; 1,5-cod = 1,5-cyclooctadiene) in THF at ambient temperature yielded a coordinatively unsaturated cubane-like cluster cation, [(eta5-Cp')3Mo3S4Ni]+. The ligand sphere at the Ni atom could be saturated by coordinating dimethyl sulfide, diethyl sulfide, di(tert-butyl) sulfide, tetrahydrothiophene, thiochroman-4-ol, 1,4-dithiane, pyridine, quinoline, or 4,4'-bipyridine. The products structurally model a mode of substrate coordination on proposed binding sites of heterogeneous MoNi sulfide hydrotreating catalysts. No stable coordination compounds could be isolated for thiophene derivatives. X-ray crystal structures are reported for the ligand-bridged dicluster compounds [[(eta5-Cp')3Mo3S4Ni]2(mu-C4H4S2)][pts]2 (C4H8S2 = 1,4-dithiane) and [[(eta5-Cp')3Mo3S4Ni]2(mu-bipy)][pts]2 (bipy = 4,4'-bipyridine).

  11. Evidence for the Active Phase of Heterogeneous Catalysts through In Situ Reaction Product Imaging and Multiscale Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Matera, S.; Blomberg, S.; Hoffmann, M. J.; Zetterberg, J.; Gustafson, J.; Lundgren, E.; Reuter, K.

    2015-06-17

    We use multiscale modeling to analyze laser-induced fluorescence (LIF) measurements of the CO oxidation reaction over Pd(100) at near-ambient reaction conditions. Integrating density functional theory-based kinetic Monte Carlo simulations of the active catalyst into fluid-dynamical simulations of the mass transport inside the reactor chamber, we calculate the reaction product concentration directly above the catalyst surface. Comparing corresponding data calculated for different surface models against the measured LIF signals, we can discriminate the one that predominantly actuates the experimentally measured catalytic activity. For the probed CO oxidation reaction conditions, the experimental activity is due to pristine Pd(100) possibly coexisting with other (oxidic) domains on the surface.

  12. Dynamic modeling of a H2O-permselective membrane reactor to enhance methanol synthesis from syngas considering catalyst deactivation

    Institute of Scientific and Technical Information of China (English)

    M.Farsi; A.Jahanmiri

    2012-01-01

    In this paper,the effect of water vapor removal on methanol synthesis capacity from syngas in a fixed-bed membrane reactor is studied considering long-term catalyst deactivation.A dynamic heterogeneous one-dimensional mathematical model that is composed of two sides is developed to predict the performance of this configuration.In this configuration,conventional methanol reactor is supported by an aluminasilica composite membrane layer for water vapor removal from reaction zone.To verify the accuracy of the considered model and assumptions,simulation results of the conventional methanol reactor is compared with the industrial plant data under the same process condition.The membrane reactor improves catalyst life time and enhances CO2 conversion to methanol by overcoming the limitation imposed by thermodynamic equilibrium.This configuration has enhanced the methanol production capacity about 4.06% compared with the industrial methanol reactor during the production time.

  13. Modelling of the partial oxidation of {alpha}, {beta}-unsaturated aldehydes on Mo-V-oxides based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Boehnke, H.; Petzoldt, J.C.; Stein, B.; Weimer, C.; Gaube, J.W. [Technische Univ. Darmstadt (Germany). Inst. fuer Chemische Technologie

    1998-12-31

    A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)

  14. Spectroscopic and catalytic investigations of VxOy/SBA-15 and magnesium vanadate model catalysts for selective propene oxidation

    OpenAIRE

    Walter, Anke

    2011-01-01

    The objective of the present work was elucidating structure-activity relationships concerning the individual role of vanadium sites in selective propene oxidation. Two suitable vanadium oxide model catalyst systems were employed: vanadium oxides supported on SBA-15, “VxOy/SBA-15”, and various magnesium vanadate phases. Detailed investigations on the preparation, thermal stability, structure, and structural evolution under reducing and propene oxidizing condition were conducted. Various in sit...

  15. Catalytic Efficiency Is a Function of How Rhodium(I) (5 + 2) Catalysts Accommodate a Conserved Substrate Transition State Geometry: Induced Fit Model for Explaining Transition Metal Catalysis.

    Science.gov (United States)

    Mustard, Thomas J L; Wender, Paul A; Cheong, Paul Ha-Yeon

    2015-03-06

    The origins of differential catalytic reactivities of four Rh(I) catalysts and their derivatives in the (5 + 2) cycloaddition reaction were elucidated using density functional theory. Computed free energy spans are in excellent agreement with known experimental rates. For every catalyst, the substrate geometries in the transition state remained constant (Catalytic efficiency is shown to be a function of how well the catalyst accommodates the substrate transition state geometry and electronics. This shows that the induced fit model for explaining biological catalysis may be relevant to transition metal catalysis. This could serve as a general model for understanding the origins of efficiencies of catalytic reactions.

  16. Stress and Fracture Strength Analysis for Three-Way Pipes%三通管道的应力与断裂强度分析

    Institute of Scientific and Technical Information of China (English)

    许京荆; 吴益民

    2001-01-01

    Three-way pipes, T and Y pipes, are very important connecting components in pipeline systems, their strength are related to the safety of pipelines. In the case that crack is not detected in the three-way pipe, ANSYS finite element program version 5.6 is applied to study the stress distribution of the three-way pipe and to obtain the optimum fillet radius in the crotch region of the two pipes. The reasonable intersection angle φ of the two pipes is also obtained. In the case that a surface crack is detected in the three-way pipe, the maximum stress intensity factor (SIF) near the front of the surface crack is studied.

  17. Three-way principal component analysis as a tool to evaluate the chemical stability of metal bearing residues from wastewater treatment by the ferrite process.

    Science.gov (United States)

    Pardo, Rafael; Vega, Marisol; Barrado, Enrique; Castrillejo, Yolanda; Sánchez, Isabel

    2013-11-15

    The chemical fractionation patterns of eight metals (Cd, Co, Cu, Cr, Mn, Ni, Pb and Zn) have been determined in 27 metal-bearing residues by using the BCR sequential extraction procedure. The residues were generated as by-products during the optimization of a semi-continuous reactor for metal removal from wastewater based on ferrite synthesis by co-precipitation. The three-dimensional X dataset (samples×metals×fractions) obtained by applying the BCR procedure has been analyzed by multivariate methods: matrix augmentation (MA-PCA) and three-way principal component analysis, 3-PCA (PARAFAC and Tucker3 models). MA-PCA and PARAFAC methods led to two-factor models giving a satisfactory but incomplete picture of the metal fractionation patterns, but the Tucker3 [2,1,2] model allowed to simultaneously describe both the 'pseudo-total' (acid-soluble) contents and the chemical fractionation by means of two non-null interactions g111 and g212 which explain 53.5% and 18.0% of the total variance, respectively. The A-mode loadings of the g212 interaction showed the close relationship between the magnetic character of the solid residues, i.e. the crystalline structure, and the chemical fractionation patterns of the metals resulting from the application of the BCR sequential extraction procedure.

  18. Three Ways of Tang Poetry into Music%论唐诗入乐的三种方式

    Institute of Scientific and Technical Information of China (English)

    向回; 张璐

    2016-01-01

    根据歌辞与音乐产生先后的不同,唐诗的入乐可分作由乐以定词、选词以配乐与因诗以作曲三种情况。不管何种入乐方式,都会在一定程度上反映出唐代文人与乐人互相成就的关系;而且同一曲调的不同歌辞,有时还可能以不同的方式入乐。唐代的宫中集体创作多以生产入乐歌词为目的,歌词与乐曲往往差不多同时创制,故而要求歌词与音乐双方能够很容易地匹配起来,使得讲求声律、极易入乐的近体诗在唐代成了一代乐章。%According to the order of words and music of poems, the poems into music in the Tang Dynasty can be divided into three ways: set words by music, choose words to match music, compose mu-sic for words. No matter what kind of way, to a certain extent, it reflects the mutual facilitating of the scholars and the musicians in the Tang Dynasty. Many words of the same tune sometimes could come into the music in the different ways. The chief purpose of the collective creation in the palace of the Tang Dynasty was to produce the poems with music, and the words and music could be created almost at the same time. The words and the music require match, so modern-style poetry that stresses rhythm and music became a particular literature in the Tang Dynasty.

  19. Meiotic behaviour in three interspecific three-way hybrids between Brachiaria ruziziensis and B. brizantha (Poaceae: Paniceae)

    Indian Academy of Sciences (India)

    Eleniza De Victor Adamowski; Maria Suely Pagliarini; Cacilda Borges Do Valle

    2008-04-01

    The meiotic behaviour of three three-way interspecific promising hybrids (H17, H27, and H34) was evaluated. These hybrids resulted from the crosses between B. ruziziensis × B. brizantha and crossed to another B. brizantha. Two half-sib hybrids (H27 and H34) presented an aneuploid chromosome number ($2n = 4x = 33$), whereas hybrid H17 was a tetraploid ($2n = 4x = 36$), as expected. Chromosome paired predominantly as multivalents suggesting that genetic recombination and introgression of specific target genes from B. brizantha into B. ruziziensis can be expected. Arrangement of parental genomes in distinct metaphase plates was observed in H27 and H34, which have different male genitors. Hybrids H17 and H34 have the same male genitor, but did not display this abnormality. In H17, abnormalities were more frequent from anaphase II, when many laggard chromosomes appeared, suggesting that each genome presented a different genetic control for meiotic phase timing. Despite the phylogenetic proximity among these two species, these three hybrids presented a high frequency of meiotic abnormalities, mainly those related to irregular chromosome segregation typical of polyploids, H34, 69.1%; H27, 56.1% and H17, 44.9%. From the accumulated results obtained through cytological studies in Brachiaria hybrids, it is evident that cytogenetical analysis is of prime importance in determining which genotypes can continue in the process of cultivar development and which can be successfully used in the breeding. Hybrids with high frequency of meiotic abnormalities can seriously compromise seed production, a key trait in assuring adoption of a new apomictic cultivar of Brachiaria for pasture formation.

  20. Meiotic behaviour in three interspecific three-way hybrids between Brachiaria ruziziensis and B. brizantha (Poaceae: Paniceae).

    Science.gov (United States)

    Adamowski, Eleniza de Victor; Pagliarini, Maria Suely; do Valle, Cacilda Borges

    2008-04-01

    The meiotic behaviour of three three-way interspecific promising hybrids (H17, H27, and H34) was evaluated. These hybrids resulted from the crosses between B. ruziziensis X B. brizantha and crossed to another B. brizantha. Two half-sib hybrids (H27 and H34) presented an aneuploid chromosome number (2n = 4x = 33), whereas hybrid H17 was a tetraploid (2n = 4x = 36), as expected. Chromosome paired predominantly as multivalents suggesting that genetic recombination and introgression of specific target genes from B. brizantha into B. ruziziensis can be expected. Arrangement of parental genomes in distinct metaphase plates was observed in H27 and H34, which have different male genitors. Hybrids H17 and H34 have the same male genitor, but did not display this abnormality. In H17, abnormalities were more frequent from anaphase II, when many laggard chromosomes appeared, suggesting that each genome presented a different genetic control for meiotic phase timing. Despite the phylogenetic proximity among these two species, these three hybrids presented a high frequency of meiotic abnormalities, mainly those related to irregular chromosome segregation typical of polyploids, H34, 69.1%; H27, 56.1% and H17, 44.9%. From the accumulated results obtained through cytological studies in Brachiaria hybrids, it is evident that cytogenetical analysis is of prime importance in determining which genotypes can continue in the process of cultivar development and which can be successfully used in the breeding. Hybrids with high frequency of meiotic abnormalities can seriously compromise seed production, a key trait in assuring adoption of a new apomictic cultivar of Brachiaria for pasture formation.

  1. Solving the non-isothermal reaction-diffusion model equations in a spherical catalyst by the variational iteration method

    Science.gov (United States)

    Wazwaz, Abdul-Majid

    2017-07-01

    In this work we address the Lane-Emden boundary value problems which appear in chemical applications, biochemical applications, and scientific disciplines. We apply the variational iteration method to solve two specific models. The first problem models reaction-diffusion equation in a spherical catalyst, while the second problem models the reaction-diffusion process in a spherical biocatalyst. We obtain reliable analytical expressions of the concentrations and the effectiveness factors. Proper graphs will be used to illustrate the obtained results. The proposed analysis demonstrates reliability and efficiency applicability of the employed method.

  2. Synthesis and evaluation of novel biochar-based and metal oxide-based catalysts for removal of model tar (toluene), ammonia, and hydrogen sulfide from simulated producer gas

    Science.gov (United States)

    Bhandari, Pushpak

    Gasification is a thermochemical conversion process in which carbonaceous feedstock is gasified in a controlled atmosphere to generate producer gas. The producer gas is used for production of heat, power, fuels and chemicals. Various contaminants such as tars, NH3, and H2S in producer gas possess many problems due to their corrosive nature and their ability to clog and deactivate catalysts. In this study, several catalysts were synthesized, characterized, and tested for removal of three contaminants (toluene (model tar), NH3, and H2S) from the biomass-generated producer gas. Biochar, a catalyst, was generated from gasification of switchgrass. Activated carbon and acidic surface activated carbon were synthesized using ultrasonication method from biochar. Acidic surface was synthesized by coating activated carbon with dilute acid. Mixed metal oxide catalysts were synthesized from hydrotalcite precursors using novel synthesis technique using microwave and ultrasonication. Surface area of activated carbon (˜900 m2/g) was significantly higher than that of its precursor biochar (˜60 m2/g). Surface area of metal oxide catalyst was approximately 180 m2/g after calcination. Biochar, activated carbon, and acidic surface activated carbon showed toluene removal efficiencies of approximately 78, 88, and 88 %, respectively, when the catalysts were tested individually with toluene in the presence of producer gas at 800 °C. The toluene removal efficiencies increased to 86, 91, and 97 % using biochar, activated carbon and acidic surface activated carbon, respectively in the presence of NH3 and H2S in the producer gas. Increase in toluene removal efficiencies in presence of NH3 and H2S indicates that NH3 and H 2S play a role in toluene reforming reactions during simultaneous removal of contaminants. Toluene removal efficiency for mixed metal oxide was approximately 83%. Ammonia adsorption capacities were 0.008 g NH3/g catalyst for biochar and 0.03g NH3/g catalyst for activated

  3. Pilot‐scale investigation and CFD modeling of particle deposition in low‐dust monolithic SCR DeNOx catalysts

    DEFF Research Database (Denmark)

    Heiredal, Michael Lykke; Jensen, Anker Degn; Thøgersen, Joakim Reimer

    2013-01-01

    Deposition of particles in selective catalytic reduction DeNOx monolithic catalysts was studied by low‐dust pilot‐scale experiments. The experiments showed a total deposition efficiency of about 30%, and the deposition pattern was similar to that observed in full‐scale low‐dust applications....... On extended exposure to the dust‐laden flue gas, complete blocking of channels was observed, showing that also in low‐dust applications soot blowing is necessary to keep the catalyst clean. A particle deposition model was developed in computational fluid dynamics, and simulations were carried out assuming...... either laminar or turbulent flow. Assuming laminar flow, the accumulated mass was underpredicted with a factor of about 17, whereas assuming turbulent flow overpredicted the experimental result with a factor of about 2. The simulations showed that turbulent diffusion in the monolith channels and inertial...

  4. Approximate solution for nonlinear model of the second and half order reactions in porous catalyst by decomposition method

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The problem of the process of coupled diffusion and reaction in catalyst pellets is considered for the case of second and half order reactions. The Adomian decomposition method is used to solve the non-linear model. For the second, half and first order reactions, analytical approximate solutions are obtained. The variation of reactant concentration in the catalyst pellet and the effectiveness factors at φ<10 are determined and compared with those by the BAND's finite difference numerical method developed by Newman. At lower values of φ, the decomposition solution with 3 terms gives satisfactory agreement with the numerical solution; at higher values of φ, as the term number in the decomposition method is increased, an acceptable agreement between the two methods is achieved. In general, the solution with 6 terms gives a satisfactory agreement.

  5. Homogeneous catalysts

    CERN Document Server

    Chadwick, John C; Freixa, Zoraida; van Leeuwen, Piet W N M

    2011-01-01

    This first book to illuminate this important aspect of chemical synthesis improves the lifetime of catalysts, thus reducing material and saving energy, costs and waste.The international panel of expert authors describes the studies that have been conducted concerning the way homogeneous catalysts decompose, and the differences between homogeneous and heterogeneous catalysts. The result is a ready reference for organic, catalytic, polymer and complex chemists, as well as those working in industry and with/on organometallics.

  6. Kinetics and mechanism of NH3 synthesis over Fe(100 and K/Fe(100 model catalysts

    Directory of Open Access Journals (Sweden)

    A. Z. Moshfegh

    2004-06-01

    Full Text Available   In this investigation kinetics and mechanism of NH3 synthesis over Fe(100 and K/Fe(100 model catalysts have been studied. In this context, adsorption kinetics of both N2/Fe (100 and H2/Fe (100systems is initially investigated. By using statistical mechanic approach, we have determined the adsorption coefficient for N2 and H2 molecules as well as transition probability of different states of adsorption and dissociation of the reactants molecules. The effect of surface catalyst temperature on the reaction rate (TOF is studied under different reactant partial pressures. The mechanism of NH3 synthesis is suggested based on LH surface reactions model. According to the obtained results, activation energy for the reaction over Fe (100 and K/Fe(100 (for θk=0.1ML was determined 19.6 and 11.1 kcal/mole, respectively. The order of reaction on both catalysts with respect to PN2 and PH2 was unity and negative, respectively. Based on our data analysis, the NH3 synthesis obeys Temkin isotherm.

  7. Oxidative-reforming of model biogas over NiO/Al2O3 catalysts: The influence of the variation of support synthesis conditions

    Science.gov (United States)

    Asencios, Yvan J. O.; Elias, Kariny F. M.; Assaf, Elisabete M.

    2014-10-01

    In this study, nickel catalysts (20 wt%) supported on γ-Al2O3 were prepared by the impregnation method. The γ-Al2O3, was synthesized by precipitation of bayerite gel obtained from aluminum scrap. The synthetic conditions of the bayerite gel varied as follows: precipitation pH ranging from 6 to 7; ageing temperature ranging from 25 to 80 °C, the calcination temperature for all samples was 500 °C. The catalysts and the supports were analyzed by temperature programmed reduction (H2-TPR), X-ray diffraction (XRD), physisorption of N2 (BET), X-ray absorption near-edge structure (XANES) and scanning electron microscopy (SEM). Isopropanol decomposition reactions over the catalysts were carried out to evaluate their acidity. SEM images of the spent catalysts showed that the morphology of the carbon formed during the reaction is of the filamentous type. The TPR analysis of the catalysts showed the presence of NiO species weakly interacted with the support as well as stoichiometric and non-stoichiometric nickel aluminate, the reduction of these species was also observed by XANES analysis. XRD analysis of the fresh catalyst showed peaks assigned to NiO, NiAl2O4 and γ-Al2O3. The best catalysts (samples NiAl7-25 and NiAl7-80) synthesized in this report showed high stability and high conversion values (CH4 (70%) and CO2 (78%)). These catalysts showed better performance than the catalyst supported on commercial γ-Al2O3, which showed a high coke formation which affected the course of the reaction. The γ-Al2O3 synthesized from bayerite obtained at neutral pH conditions was the best support for nickel catalysts in the oxidative-reforming of model biogas.

  8. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts: A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    Energy Technology Data Exchange (ETDEWEB)

    Manos Mavrikakis; James A. Dumesic; Amit A. Gokhale; Rahul P. Nabar; Calvin H. Bartholomew; Hu Zou; Brian Critchfield

    2006-03-03

    rate-determining steps. In the coming year, studies will focus on quantitative determination of the rates of kinetically-relevant elementary steps on Fe catalysts with/without K and Pt promoters and at various levels of Al{sub 2}O{sub 3} support, providing a database for understanding (1) effects of promoter and support on elementary kinetic parameters and (2) for validation of computational models that incorporate effects of surface structure and promoters. Kinetic parameters will be incorporated into a microkinetics model, enabling prediction of rate without invoking assumptions, e.g. of a rate-determining step or a most-abundant surface intermediate. Calculations using periodic, self-consistent Density Functional Theory (DFT) methods were performed on two model surfaces: (1) Fe(110) with 1/4 ML subsurface carbon, and (2) Fe(110) with 1/4 ML Pt adatoms. Reaction networks for FTS on these systems were characterized in full detail by evaluating the thermodynamics and kinetics of each elementary step. We discovered that subsurface C stabilizes all the reactive intermediates, in contrast to Pt, which destabilizes most of them. A comparative study of the reactivities of the modified-Fe surfaces against pure Fe is expected to yield a more comprehensive understanding of promotion mechanisms for FTS on Fe.

  9. Electrochemical properties of CO{sub x}/Pt(111) model catalyst surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Wadayama, T.; Todoroki, N.; Yoshida, H.; Yamada, Y. [Tohoku Univ., Sendai (Japan). Dept. of Materials Science

    2010-07-01

    Oxygen reduction reaction (ORR) activities for clean Pt(111) and Co-deposited Pt(111) (CO{sub x}/Pt(111)) model catalyst surfaces fabricated by molecular beam epitaxy (MBE) were evaluated. Low-energy electron diffration (LEED) and infrared reflection absorption spectroscopy (IRRAS) was used to investigate the CO{sub x}/Pt(111) surface structures. 1.0-L-carbon monoxide (CO) exposure to the clean Pt(111) at 323 K yielded linear-bonded and bridge-bonded CO-PT bands at 2092 and 1850 cm{sup -1}. 0.3nm-thick-Co deposition onto the clean Pt(111) at 343 K brought about small hexagons of satellites on a LEED pattern and a main IR band ascribable to Co-CO bonds is located at 2000 cm{sup -1}. In contrast, at 823-K-Co deposition, a LEED pattern is almost identical as that for the clean Pt(111): an absorbed CO band at 2080 cm{sup -1} dominated IR spectrum for the 1.0-L-CO exposed surface. The results suggest that the Co deposition at 823 K generates a Pt-enriched outermost surface (Pt-skin) formed through surface segregation of the substrate Pt atoms. A linear-sweep voltammetry (LSV) curve was recorded for the Co/Pt(111)-skin in O{sub 2}-saturated HCIO{sub 4}. Specific ORR activity for the Pt-skin is 10-times higher than that for the clean Pt(111). (orig.)

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

    Science.gov (United States)

    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.

  11. Specific detection of DNA and RNA targets using a novel isothermal nucleic acid amplification assay based on the formation of a three-way junction structure.

    Science.gov (United States)

    Wharam, S D; Marsh, P; Lloyd, J S; Ray, T D; Mock, G A; Assenberg, R; McPhee, J E; Brown, P; Weston, A; Cardy, D L

    2001-06-01

    The formation of DNA three-way junction (3WJ) structures has been utilised to develop a novel isothermal nucleic acid amplification assay (SMART) for the detection of specific DNA or RNA targets. The assay consists of two oligonucleotide probes that hybridise to a specific target sequence and, only then, to each other forming a 3WJ structure. One probe (template for the RNA signal) contains a non-functional single-stranded T7 RNA polymerase promoter sequence. This promoter sequence is made double-stranded (hence functional) by DNA polymerase, allowing T7 RNA polymerase to generate a target-dependent RNA signal which is measured by an enzyme-linked oligosorbent assay (ELOSA). The sequence of the RNA signal is always the same, regardless of the original target sequence. The SMART assay was successfully tested in model systems with several single-stranded synthetic targets, both DNA and RNA. The assay could also detect specific target sequences in both genomic DNA and total RNA from Escherichia coli. It was also possible to generate signal from E.coli samples without prior extraction of nucleic acid, showing that for some targets, sample purification may not be required. The assay is simple to perform and easily adaptable to different targets.

  12. Mining Outcome-relevant Brain Imaging Genetic Associations via Three-way Sparse Canonical Correlation Analysis in Alzheimer’s Disease

    Science.gov (United States)

    Hao, Xiaoke; Li, Chanxiu; Du, Lei; Yao, Xiaohui; Yan, Jingwen; Risacher, Shannon L.; Saykin, Andrew J.; Shen, Li; Zhang, Daoqiang; Weiner, Michael W.; Aisen, Paul; Petersen, Ronald; Jack, Clifford R.; Mason, Sara S.; Albers, Colleen S.; Knopman, David; Johnson, Kris; Jagust, William; Trojanowki, John Q.; Toga, Arthur W.; Beckett, Laurel; Green, Robert C.; Farlow, Martin R.; Marie Hake, Ann; Matthews, Brandy R.; Brosch, Jared R.; Herring, Scott; Hunt, Cynthia; Shaw, Leslie M.; Ances, Beau; Morris, John C.; Carroll, Maria; Creech, Mary L.; Franklin, Erin; Mintun, Mark A.; Schneider, Stacy; Oliver, Angela; Kaye, Jeffrey; Quinn, Joseph; Silbert, Lisa; Lind, Betty; Carter, Raina; Dolen, Sara; Schneider, Lon S.; Pawluczyk, Sonia; Beccera, Mauricio; Teodoro, Liberty; Spann, Bryan M.; Brewer, James; Vanderswag, Helen; Fleisher, Adam; Tariot, Pierre; Burke, Anna; Trncic, Nadira; Reeder, Stephanie; Heidebrink, Judith L.; Lord, Joanne L.; Doody, Rachelle S.; Villanueva-Meyer, Javier; Chowdhury, Munir; Rountree, Susan; Dang, Mimi; Stern, Yaakov; Honig, Lawrence S.; Bell, Karen L.; Marson, Daniel; Griffith, Randall; Clark, David; Geldmacher, David; Brockington, John; Roberson, Erik; Love, Marissa Natelson; Grossman, Hillel; Mitsis, Effie; Shah, Raj C.; deToledo-Morrell, Leyla; Duara, Ranjan; Varon, Daniel; Greig, Maria T.; Roberts, Peggy; Albert, Marilyn; Onyike, Chiadi; D’Agostino, Daniel; Kielb, Stephanie; Galvin, James E.; Cerbone, Brittany; Michel, Christina A.; Pogorelec, Dana M.; Rusinek, Henry; de Leon, Mony J.; Glodzik, Lidia; De Santi, Susan; Doraiswamy, P. Murali; Petrella, Jeffrey R.; Borges-Neto, Salvador; Wong, Terence Z.; Coleman, Edward; Smith, Charles D.; Jicha, Greg; Hardy, Peter; Sinha, Partha; Oates, Elizabeth; Conrad, Gary; Porsteinsson, Anton P.; Goldstein, Bonnie S.; Martin, Kim; Makino, Kelly M.; Ismail, M. Saleem; Brand, Connie; Mulnard, Ruth A.; Thai, Gaby; Mc-Adams-Ortiz, Catherine; Womack, Kyle; Mathews, Dana; Quiceno, Mary; Levey, Allan I.; Lah, James J.; Cellar, Janet S.; Burns, Jeffrey M.; Swerdlow, Russell H.; Brooks, William M.; Apostolova, Liana; Tingus, Kathleen; Woo, Ellen; Silverman, Daniel H. S.; Lu, Po H.; Bartzokis, George; Graff-Radford, Neill R.; Parfitt, Francine; Kendall, Tracy; Johnson, Heather; van Dyck, Christopher H.; Carson, Richard E.; MacAvoy, Martha G.; Varma, Pradeep; Chertkow, Howard; Bergman, Howard; Hosein, Chris; Black, Sandra; Stefanovic, Bojana; Caldwell, Curtis; Hsiung, Ging-Yuek Robin; Feldman, Howard; Mudge, Benita; Assaly, Michele; Finger, Elizabeth; Pasternack, Stephen; Rachisky, Irina; Trost, Dick; Kertesz, Andrew; Bernick, Charles; Munic, Donna; Mesulam, Marek-Marsel; Lipowski, Kristine; Weintraub, Sandra; Bonakdarpour, Borna; Kerwin, Diana; Wu, Chuang-Kuo; Johnson, Nancy; Sadowsky, Carl; Villena, Teresa; Turner, Raymond Scott; Johnson, Kathleen; Reynolds, Brigid; Sperling, Reisa A.; Johnson, Keith A.; Marshall, Gad; Yesavage, Jerome; Taylor, Joy L.; Lane, Barton; Rosen, Allyson; Tinklenberg, Jared; Sabbagh, Marwan N.; Belden, Christine M.; Jacobson, Sandra A.; Sirrel, Sherye A.; Kowall, Neil; Killiany, Ronald; Budson, Andrew E.; Norbash, Alexander; Johnson, Patricia Lynn; Obisesan, Thomas O.; Wolday, Saba; Allard, Joanne; Lerner, Alan; Ogrocki, Paula; Tatsuoka, Curtis; Fatica, Parianne; Fletcher, Evan; Maillard, Pauline; Olichney, John; DeCarli, Charles; Carmichael, Owen; Kittur, Smita; Borrie, Michael; Lee, T.-Y.; Bartha, Rob; Johnson, Sterling; Asthana, Sanjay; Carlsson, Cynthia M.; Potkin, Steven G.; Preda, Adrian; Nguyen, Dana; Bates, Vernice; Capote, Horacio; Rainka, Michelle; Scharre, Douglas W.; Kataki, Maria; Adeli, Anahita; Zimmerman, Earl A.; Celmins, Dzintra; Brown, Alice D.; Pearlson, Godfrey D.; Blank, Karen; Anderson, Karen; Flashman, Laura A.; Seltzer, Marc; Hynes, Mary L.; Santulli, Robert B.; Sink, Kaycee M.; Gordineer, Leslie; Williamson, Jeff D.; Garg, Pradeep; Watkins, Franklin; Ott, Brian R.; Querfurth, Henry; Tremont, Geoffrey; Salloway, Stephen; Malloy, Paul; Correia, Stephen; Rosen, Howard J.; Miller, Bruce L.; Perry, David; Mintzer, Jacobo; Spicer, Kenneth; Bachman, David; Pomara, Nunzio; Hernando, Raymundo; Sarrael, Antero; Relkin, Norman; Chaing, Gloria; Lin, Michael; Ravdin, Lisa; Smith, Amanda; Raj, Balebail Ashok; Fargher, Kristin

    2017-01-01

    Neuroimaging genetics is an emerging field that aims to identify the associations between genetic variants (e.g., single nucleotide polymorphisms (SNPs)) and quantitative traits (QTs) such as brain imaging phenotypes. In recent studies, in order to detect complex multi-SNP-multi-QT associations, bi-multivariate techniques such as various structured sparse canonical correlation analysis (SCCA) algorithms have been proposed and used in imaging genetics studies. However, associations between genetic markers and imaging QTs identified by existing bi-multivariate methods may not be all disease specific. To bridge this gap, we propose an analytical framework, based on three-way sparse canonical correlation analysis (T-SCCA), to explore the intrinsic associations among genetic markers, imaging QTs, and clinical scores of interest. We perform an empirical study using the Alzheimer’s Disease Neuroimaging Initiative (ADNI) cohort to discover the relationships among SNPs from AD risk gene APOE, imaging QTs extracted from structural magnetic resonance imaging scans, and cognitive and diagnostic outcomes. The proposed T-SCCA model not only outperforms the traditional SCCA method in terms of identifying strong associations, but also discovers robust outcome-relevant imaging genetic patterns, demonstrating its promise for improving disease-related mechanistic understanding. PMID:28291242

  13. Catalyst Design for the Electrocatalytic Hydrogenation of Model Compounds in the Presence of Sulfur

    Science.gov (United States)

    Murphy, Sean

    In this research, the electrocatalytic hydrogenation of 2-cyclohexen-1-one by Ni-Wand W-S catalysts is investigated. The objective was to demonstrate catalytic activity of sulfide-based electrodes for the hydrogenation reaction in the presence of sulfur containing molecules representative of those found in bitumen distillate fractions. Ni and Pd catalysts were investigated as control standards for the hydrogenation reaction. Both catalysts were found to be ineffective in the presence of sulfur. Ni-W composite films supported on aluminum have been shown to be catalytically active for the electrocatalytic hydrogenation of 2-cyclohexen-1-one, but are poisoned in the presence of sulfur. WS2 catalysts particles supported on vitreous carbon have been shown to be active for the electrocatalytic hydrogenation in the presence of sulfur. The ionic liquid 1-butyl-3-methyl-imidazlium tetrafluoroborate was investigated as a solvent for e1ectrocatalytic hydrogenation reactions. It was found to be incompatible with a vitreous carbon anode and reacted immediately producing an insulating film.

  14. Aqueous-Phase Preparation of Model HDS Catalysts on Planar Alumina Substrates: Support Effect on Mo Adsorption and Sulfidation.

    Science.gov (United States)

    Bara, Cédric; Plais, Lucie; Larmier, Kim; Devers, Elodie; Digne, Mathieu; Lamic-Humblot, Anne-Félicie; Pirngruber, Gerhard D; Carrier, Xavier

    2015-12-23

    The role of the oxide support on the structure of the MoS2 active phase (size, morphology, orientation, sulfidation ratio, etc.) remains an open question in hydrotreating catalysis and biomass processing with important industrial implications for the design of improved catalytic formulations. The present work builds on an aqueous-phase surface-science approach using four well-defined α-alumina single crystal surfaces (C (0001), A (112̅0), M (101̅0), and R (11̅02) planes) as surrogates for γ-alumina (the industrial support) in order to discriminate the specific role of individual support facets. The reactivity of the various surface orientations toward molybdenum adsorption is controlled by the speciation of surface hydroxyls that determines the surface charge at the oxide/water interface. The C (0001) plane is inert, and the R (11̅02) plane has a limited Mo adsorption capacity while the A (112̅0) and M (101̅0) surfaces are highly reactive. Sulfidation of model catalysts reveals the highest sulfidation degree for the A (112̅0) and M (101̅0) planes suggesting weak metal/support interactions. Conversely, a low sulfidation rate and shorter MoS2 slabs are found for the R (11̅02) plane implying stronger Mo-O-Al bonds. These limiting cases are reminiscent of type I/type II MoS2 nanostructures. Structural analogies between α- and γ- alumina surfaces allow us to bridge the material gap with real Al2O3-supported catalysts. Hence, it can be proposed that Mo distribution and sulfidation rate are heterogeneous and surface-dependent on industrial γ-Al2O3-supported high-surface-area catalysts. These results demonstrate that a proper control of the γ-alumina morphology is a strategic lever for a molecular-scale design of hydrotreating catalysts.

  15. Displacement of Hexanol by the Hexanoic Acid Overoxidation Product in Alcohol Oxidation on a Model Supported Palladium Nanoparticle Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Buchbinder, Avram M.; Ray, Natalie A.; Lu, Junling; Van Duyne, Richard P.; Stair, Peter C; Weitz, Eric; Geiger, Franz M.

    2011-11-09

    This work characterizes the adsorption, structure, and binding mechanism of oxygenated organic species from cyclohexane solution at the liquid/solid interface of optically flat alumina-supported palladium nanoparticle surfaces prepared by atomic layer deposition (ALD). The surface-specific nonlinear optical vibrational spectroscopy, sum-frequency generation (SFG), was used as a probe for adsorption and interfacial molecular structure. 1-Hexanoic acid is an overoxidation product and possible catalyst poison for the aerobic heterogeneous oxidation of 1-hexanol at the liquid/solid interface of Pd/Al₂O₃ catalysts. Single component and competitive adsorption experiments show that 1-hexanoic acid adsorbs to both ALD-prepared alumina surfaces and alumina surfaces with palladium nanoparticles, that were also prepared by ALD, more strongly than does 1-hexanol. Furthermore, 1-hexanoic acid adsorbs with conformational order on ALD-prepared alumina surfaces, but on surfaces with palladium particles the adsorbates exhibit relative disorder at low surface coverage and become more ordered, on average, at higher surface coverage. Although significant differences in binding constant were not observed between surfaces with and without palladium nanoparticles, the palladium particles play an apparent role in controlling adsorbate structures. The disordered adsorption of 1-hexanoic acid most likely occurs on the alumina support, and probably results from modification of binding sites on the alumina, adjacent to the particles. In addition to providing insight on the possibility of catalyst poisoning by the overoxidation product and characterizing changes in its structure that result in only small adsorption energy changes, this work represents a step toward using surface science techniques that bridge the complexity gap between fundamental studies and realistic catalyst models.

  16. Oxidative-reforming of model biogas over NiO/Al{sub 2}O{sub 3} catalysts: The influence of the variation of support synthesis conditions

    Energy Technology Data Exchange (ETDEWEB)

    Asencios, Yvan J.O., E-mail: yvan.jesus@unifesp.br [Departamento de Ciências do Mar, Universidade Federal de São Paulo, Av. Alm. Saldanha da Gama, 89, Ponta da Praia, CEP: 11030-400, Santos-SP (Brazil); Elias, Kariny F.M. [Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador Sãocarlense, 400, 13560-970, São Carlos-SP (Brazil); Assaf, Elisabete M., E-mail: eassaf@iqsc.usp.br [Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador Sãocarlense, 400, 13560-970, São Carlos-SP (Brazil)

    2014-10-30

    high coke formation which affected the course of the reaction. The γ-Al{sub 2}O{sub 3} synthesized from bayerite obtained at neutral pH conditions was the best support for nickel catalysts in the oxidative-reforming of model biogas.

  17. Effects of a potent peroxynitrite decomposition catalyst in murine models of endotoxemia and sepsis.

    Science.gov (United States)

    Soriano, Francisco Garcia; Lorigados, Clara Batista; Pacher, Pal; Szabó, Csaba

    2011-06-01

    Excessive free-radical production due to various bacterial components released during bacterial infection has been linked to cell death and tissue injury. Peroxynitrite is a highly reactive oxidant produced by the combination of nitric oxide (NO) and superoxide anion, which has been implicated in cell death and tissue injury in various forms of critical illness. Pharmacological decomposition of peroxynitrite may represent a potential therapeutic approach in diseases associated with the overproduction of NO and superoxide. In the present study, we tested the effect of a potent peroxynitrite decomposition catalyst in murine models of endotoxemia and sepsis. Mice were injected i.p. with LPS 40 mg/kg with or without FP15 [Fe(III) tetrakis-2-(N-triethylene glycol monomethyl ether)pyridyl porphyrin] (0.1, 0.3, 1, 3, or 10 mg/kg per hour). Mice were killed 12 h later, followed by the harvesting of samples from the lung, liver, and gut for malondialdehyde and myeloperoxidase measurements. In other subsets of animals, blood samples were obtained by cardiac puncture at 1.5, 4, and 8 h after LPS administration for cytokine (TNF-α, IL-1β, and IL-10), nitrite/nitrate, alanine aminotransferase, and blood urea nitrogen measurements. Endotoxemic animals showed an increase in survival from 25% to 80% at the FP15 doses of 0.3 and 1 mg/kg per hour. The same dose of FP15 had no effect on plasma levels of nitrite/nitrate. There was a reduction in liver and lung malondialdehyde in the endotoxemic animals pretreated with FP15, as well as in hepatic myeloperoxidase and biochemical markers of liver and kidney damage (alanine aminotransferase and blood urea nitrogen). In a bacterial model of sepsis induced by cecal ligation and puncture, FP15 treatment (0.3 mg/kg per day) significantly protected against mortality. The current data support the view that peroxynitrite is a critical factor mediating liver, gut, and lung injury in endotoxemia and septic shock: its pharmacological

  18. Catalysts as Sensors—A Promising Novel Approach in Automotive Exhaust Gas Aftertreatment

    Directory of Open Access Journals (Sweden)

    Ralf Moos

    2010-07-01

    Full Text Available Sensors that detect directly and in situ the status of automotive exhaust gas catalysts by monitoring the electrical properties of the catalyst coating itself are overviewed. Examples included in this review are the in-situ determination of the electrical impedance of three-way catalysts based on ceria-zirconia solutions and of lean NOx traps of earth-alkaline based coatings, as well as approaches to determine the ammonia loading in Fe-SCR-zeolites with electrical ac measurements. Even more sophisticated approaches based on interactions with electromagnetic waves are also reviewed. For that purpose, metallic stick-like antennas are inserted into the exhaust pipe. The catalyst properties are measured in a contactless manner, directly indicating the catalyst status. The radio frequency probes gauge the oxygen loading degree of three-way catalysts, the NOx-loading of lean NOx traps, and the soot loading of Diesel particulate filters

  19. Catalysts as sensors--a promising novel approach in automotive exhaust gas aftertreatment.

    Science.gov (United States)

    Moos, Ralf

    2010-01-01

    Sensors that detect directly and in situ the status of automotive exhaust gas catalysts by monitoring the electrical properties of the catalyst coating itself are overviewed. Examples included in this review are the in-situ determination of the electrical impedance of three-way catalysts based on ceria-zirconia solutions and of lean NO(x) traps of earth-alkaline based coatings, as well as approaches to determine the ammonia loading in Fe-SCR-zeolites with electrical ac measurements. Even more sophisticated approaches based on interactions with electromagnetic waves are also reviewed. For that purpose, metallic stick-like antennas are inserted into the exhaust pipe. The catalyst properties are measured in a contactless manner, directly indicating the catalyst status. The radio frequency probes gauge the oxygen loading degree of three-way catalysts, the NO(x)-loading of lean NO(x) traps, and the soot loading of Diesel particulate filters.

  20. Oxidative coupling of methane in a fixed bed reactor over perovskite catalyst: A simulation study using experimental kinetic model

    Institute of Scientific and Technical Information of China (English)

    Nakisa Yaghobi; Mir Hamid Reza Ghoreishy

    2008-01-01

    The oxidative coupling of methane (OCM) to ethylene over a perovskite titanate catalyst in a fixed bed reactor was studied experimentally and numerically. The two-dimensional steady state model accounted for separate energy equations for the gas and solid phases coupled with an experimental kinetic model. A lumped kinetic model containing four main species CH4, O2, COx (CO2, CO), and C2 (C2H4 and C2H6) was used with a plug flow reactor model as well. The results from the model agreed with the experimental data. The model was used to analyze the influence of temperature and feed gas composition on the conversion and selectivity of the reactor performance. The analytical results indicate that the conversion decreases, whereas, C2 selectivity increases by increasing gas hourly space velocity (GHSV) and the methane conversion also decreases by increasing the methane to oxygen ratio.

  1. Fuel penalty comparison for (Electrically) heated catalyst technology

    NARCIS (Netherlands)

    Kessels, J.T.B.A.; Foster, D.L.; Bleuanus, W.A.J.

    2010-01-01

    The conversion efficiency of three way catalytic converters is mainly defined by the temperature range wherein they are operating. Traditionally, ignition retard has been used to reduce the light-off time of the catalyst. This is however associated with a fuel penalty. With increasing vehicle

  2. Fuel penalty comparison for (Electrically) heated catalyst technology

    NARCIS (Netherlands)

    Kessels, J.T.B.A.; Foster, D.L.; Bleuanus, W.A.J.

    2010-01-01

    The conversion efficiency of three way catalytic converters is mainly defined by the temperature range wherein they are operating. Traditionally, ignition retard has been used to reduce the light-off time of the catalyst. This is however associated with a fuel penalty. With increasing vehicle electr

  3. Investigation of process variables and intensification effects of ultrasound applied in oxidative desulfurization of model diesel over MoO3/Al2O3 catalyst.

    Science.gov (United States)

    Akbari, Azam; Omidkhah, Mohammadreza; Darian, Jafar Towfighi

    2014-03-01

    A new heterogeneous sonocatalytic system consisting of a MoO3/Al2O3 catalyst and H2O2 combined with ultrasonication was studied to improve and accelerate the oxidation of model sulfur compounds of diesel, resulting in a significant enhancement in the process efficiency. The influence of ultrasound on properties, activity and stability of the catalyst was studied in detail by means of GC-FID, PSD, SEM and BET techniques. Above 98% conversion of DBT in model diesel containing 1000 μg/g sulfur was obtained by new ultrasound-assisted desulfurization at H2O2/sulfur molar ratio of 3, temperature of 318 K and catalyst dosage of 30 g/L after 30 min reaction, contrary to the 55% conversion obtained during the silent process. This improvement was considerably affected by operation parameters and catalyst properties. The effects of main process variables were investigated using response surface methodology in silent process compared to ultrasonication. Ultrasound provided a good dispersion of catalyst and oxidant by breakage of hydrogen bonding and deagglomeration of them in the oil phase. Deposition of impurities on the catalyst surface caused a quick deactivation in silent experiments resulting only 5% of DBT oxidation after 6 cycles of silent reaction by recycled catalyst. Above 95% of DBT was oxidized after 6 ultrasound-assisted cycles showing a great improvement in stability by cleaning the surface during ultrasonication. A considerable particle size reduction was also observed after 3 h sonication that could provide more dispersion of catalyst in model fuel.

  4. Modeling of carbon monoxide oxidation kinetics over NASA carbon dioxide laser catalysts

    Science.gov (United States)

    Herz, Richard K.

    1989-01-01

    The recombination of CO and O2 formed by the dissociation of CO2 in a sealed CO2 laser discharge zone is examined. Conventional base-metal-oxide catalysts and conventional noble-metal catalysts are not effective in recombining the low O2/CO ratio at the low temperatures used by the lasers. The use of Pt/SnO2 as the noble-metal reducible-oxide (NMRO), or other related materials from Group VIIIA and IB and SnO2 interact synergistically to produce a catalytic activity that is substantially higher than either componet separately. The Pt/SnO2 and Pd/SnO2 were reported to have significant reaction rates at temperatures as low as -27 C, conditions under which conventional catalysts are inactive. The gas temperature range of lasers is 0 + or - 40 C. There are three general ways in which the NMRO composite materials can interact synergistically: one component altering the properties of another component; the two components each providing independent catalytic functions in a complex reaction mechanism; and the formation of catalytic sites through the combination of two components at the atomic level. All three of these interactions may be important in low temperature CO oxidation over NMRO catalysts. The effect of the noble metal on the oxide is discussed first, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

  5. Catalyst mixtures

    Energy Technology Data Exchange (ETDEWEB)

    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.

  6. Photo-oxidation catalysts

    Science.gov (United States)

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

    2009-07-14

    Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

  7. Conversion of syngas to liquid hydrocarbons over a two-component (Cr{sub 2}O{sub 3}-ZnO and ZSM-5 zeolite) catalyst: kinetic modelling and catalyst deactivation

    Energy Technology Data Exchange (ETDEWEB)

    Erena, J.; Arandes, J.M.; Bilbao, J.; Gayubo, A.G. [Universidad del Pais Vasco, Bilbao (Spain). Dept. de Ingeneria Quimica; De Lasa, H.I. [University of Western Ontario, London, ONT (Canada). Chemical Reactor Engineering Centre

    2000-05-01

    The present study describes the kinetics of syngas transformation into liquid hydrocarbons (boiling point in the gasoline range) using as catalyst a mixture of a metallic component, Cr{sub 2}O{sub 3}-ZnO, and of an acidic component, ZSM-5 zeolite. Experimental results were obtained in an isothermal fixed-bed integral reactor. The validity of several kinetic models, available for methanol synthesis, is analysed and modifications are proposed. These changes involve a rate equation with a CO{sub 2} concentration-dependent term. Catalyst deactivation is also evaluated and the effect of the operating conditions on coke deposition is established. Moreover, the rate of CO conversion and the change of catalytic activity with time-on-stream were described using a kinetic model showing a weak influence of temperature. (Author)

  8. Catalytic Steam Reforming of Toluene as a Model Compound of Biomass Gasification Tar Using Ni-CeO2/SBA-15 Catalysts

    Directory of Open Access Journals (Sweden)

    Erik Dahlquist

    2013-07-01

    Full Text Available Nickel supported on SBA-15 doped with CeO2 catalysts (Ni-CeO2/SBA-15 was prepared, and used for steam reforming of toluene which was selected as a model compound of biomass gasification tar. A fixed-bed lab-scale set was designed and employed to evaluate the catalytic performances of the Ni-CeO2/SBA-15 catalysts. Experiments were performed to reveal the effects of several factors on the toluene conversion and product gas composition, including the reaction temperature, steam/carbon (S/C ratio, and CeO2 loading content. Moreover, the catalysts were subjected to analysis of their carbon contents after the steam reforming experiments, as well as to test the catalytic stability over a long experimental period. The results indicated that the Ni-CeO2/SBA-15 catalysts exhibited promising capabilities on the toluene conversion, anti-coke deposition and catalytic stability. The toluene conversion reached as high as 98.9% at steam reforming temperature of 850 °C and S/C ratio of 3 using the Ni-CeO2(3wt%/SBA-15 catalyst. Negligible coke formation was detected on the used catalyst. The gaseous products mainly consisted of H2 and CO, together with a little CO2 and CH4.

  9. Cluster-support interactions and morphology of MoS2 nanoclusters in a graphite-supported hydrotreating model catalyst.

    Science.gov (United States)

    Kibsgaard, Jakob; Lauritsen, Jeppe V; Laegsgaard, Erik; Clausen, Bjerne S; Topsøe, Henrik; Besenbacher, Flemming

    2006-10-25

    Supported MoS(2) nanoparticles constitute the active component of the important hydrotreating catalysts used for industrial upgrading and purification of the oil feedstock for the production of fossil fuels with a low environmental load. We have synthesized and studied a model system of the hydrotreating catalyst consisting of MoS(2) nanoclusters supported on a graphite surface in order to resolve a number of very fundamental questions related to the atomic-scale structure and morphology of the active clusters and in particular the effect of a substrate used in some types of hydrotreating catalysts. Scanning tunneling microscopy (STM) is used to image the atomic-scale structure of graphite-supported MoS(2) nanoclusters in real space. It is found that the pristine graphite (0001) surface does not support a high dispersion of MoS(2), but by introducing a small density of defects in the surface, highly dispersed MoS(2) nanoclusters could be synthesized on the graphite. From high-resolution STM images it is found that MoS(2) nanoclusters synthesized at low temperature in a sulfiding atmosphere preferentially grow as single-layer clusters, whereas clusters synthesized at 1200 K grow as multilayer slabs oriented with the MoS(2)(0001) basal plane parallel to the graphite surface. The morphology of both single-layer and multilayer MoS(2) nanoclusters is found to be preferentially hexagonal, and atom-resolved images of the top facet of the clusters provide new atomic-scale information on the MoS(2)-HOPG bonding. The structure of the two types of catalytically interesting edges terminating the hexagonal MoS(2) nanoclusters is also resolved in atomic detail in STM images, and from these images it is possible to reveal the atomic structure of both edges and the location and coverage of sulfur and hydrogen adsorbates.

  10. Combined high-pressure cell-ultrahigh vacuum system for fast testing of model metal alloy catalysts using scanning mass spectrometry

    DEFF Research Database (Denmark)

    Johansson, Martin; Jørgensen, Jan Hoffmann; Chorkendorff, Ib

    2004-01-01

    An apparatus for fabrication, surface analysis in ultrahigh vacuum, and testing of the catalytic activity of model metal alloy catalysts is described. Arrays of model catalysts are produced by electron-beam deposition of up to four metals simultaneously onto a substrate. The surface analysis...... techniques available are scanning electron microscopy, x-ray photoemission spectroscopy, ion scattering spectroscopy, Auger electron spectroscopy, sputter profiling, and temperature programmed desorption. The catalytic activity of the model catalysts is tested individually by scanning a combined gas delivery...... be studied on a substrate 10 mm in diameter. A high pressure cell with an all-metal sealed ultrahigh vacuum lock is also described as part of the work. ©2004 American Institute of Physics....

  11. One-dimensional isothermal multicomponent diffusion-reaction model and its application to methanol synthesis over commercial Cu-based catalyst

    Directory of Open Access Journals (Sweden)

    Lei Kun

    2015-03-01

    Full Text Available The present work was a study on global reaction rate of methanol synthesis. We measured experimentally the global reaction rate in the internal recycle gradientless reactor over catalyst SC309. The diffusion-reaction model of methanol synthesis was suggested. For model we chose the hydrogenation of CO and CO2 as key reaction. CO and CO2 were key components in our model. The internal diffusion effectiveness factors of CO and CO2 in the catalyst were calculated by the numerical integration. A comparison with the experiment showed that all the absolute values of the relative error were less than 10%. The simulation results showed that decreasing reaction temperature and catalyst diameter were conducive to reduce the influence of the internal diffusion on the methanol synthesis.

  12. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts: A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    Energy Technology Data Exchange (ETDEWEB)

    Manos Mavrikakis; James A. Dumesic; Rahul P. Nabar

    2006-09-29

    Work continued on the development of a microkinetic model of Fischer-Tropsch synthesis (FTS) on supported and unsupported Fe catalysts. The following aspects of the FT mechanism on unsupported iron catalysts were investigated on during this third year: (1) the collection of rate data in a Berty CSTR reactor based on sequential design of experiments; (2) CO adsorption and CO-TPD for obtaining the heat of adsorption of CO on polycrystalline iron; and (3) isothermal hydrogenation (IH) after Fischer Tropsch reaction to identify and quantify surface carbonaceous species. Rates of C{sub 2+} formation on unsupported iron catalysts at 220 C and 20 atm correlated well to a Langmuir-Hinshelwood type expression, derived assuming carbon hydrogenation to CH and OH recombination to water to be rate-determining steps. From desorption of molecularly adsorbed CO at different temperatures the heat of adsorption of CO on polycrystalline iron was determined to be 100 kJ/mol. Amounts and types of carbonaceous species formed after FT reaction for 5-10 minutes at 150, 175, 200 and 285 C vary significantly with temperature. Mr. Brian Critchfield completed his M.S. thesis work on a statistically designed study of the kinetics of FTS on 20% Fe/alumina. Preparation of a paper describing this work is in progress. Results of these studies were reported at the Annual Meeting of the Western States Catalysis and at the San Francisco AIChE meeting. In the coming period, studies will focus on quantitative determination of the rates of kinetically-relevant elementary steps on unsupported Fe catalysts with/without K and Pt promoters by SSITKA method. This study will help us to (1) understand effects of promoter and support on elementary kinetic parameters and (2) build a microkinetics model for FTS on iron. Calculations using periodic, self-consistent Density Functional Theory (DFT) methods were performed on models of defected Fe surfaces, most significantly the stepped Fe(211) surface. Binding

  13. Pd-Au bimetallic catalysts: understanding alloy effects from planar models and (supported) nanoparticles.

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Feng; Goodman, Wayne D.

    2012-12-21

    Pd-Au bimetallic catalysts often display enhanced catalytic activities and selectivities compared with Pd-alone catalysts. This enhancement is often caused by two alloy effects, i.e., ensemble and ligand effects. The ensemble effect is dilution of surface Pd by Au. With increasing surface Au coverages, contiguous Pd ensembles disappear and isolated Pd ensembles form. For certain reactions, for example vinyl acetate synthesis, this effect is responsible for reaction rate enhancement via the formation of highly active surface sites, e.g., isolated Pd pairs. The disappearance of contiguous Pd ensembles also switches off side reactions catalyzed by these sites. This explains selectivity increase of certain reactions, for example direct H2O2 synthesis. The ligand effect is electronic perturbation of Au to Pd. By direct charge transfer or affecting bond length, the ligand effect causes the Pd d band to be more filled and the d-band center away from the Fermi level. Both changes make Pd more "atomic like" therefore binding reactants and products weaker. For certain reactions, this eliminates the so-called "self poisoning" and enhances activity/selectivity.

  14. Disorder effects on EXAFS modeling for catalysts working at elevated temperatures

    Science.gov (United States)

    Sun, Xueping; Sun, Fanfei; Sun, Zhihu; Chen, Jing; Du, Xianlong; Wang, Jianqiang; Jiang, Zheng; Huang, Yuying

    2017-08-01

    In-situ X-ray absorption fine structure spectroscopy (XAFS) has been widely used to study the structure around active site of catalysts at elevated pressures and temperatures for decades. However, methods of XAFS data analysis can vary significantly, depending on the disorder degree of the material system investigated. In this work, in-situ XAFS was explored to investigate the structural evolutions of the industry CuO/ZnO/Al2O3 catalyst for methanol synthesis at elevated temperatures in nitrogen (N2) atmosphere. Due to the large Debye-Waller factor, data analysis using the conventional Gaussian mode resulted in erroneously contracted Cu-Cu bond distances which made the conventional Gaussian mode invalid in this system. To account for the deviation from harmonic behavior, the cumulant expansion technique was used to correct the error in the bond contraction, and the frequency pattern could be fully reproduced by considering cumulants up to C3. In order to elucidate the contributions of the structure and thermal components to the Debye-Waller factors, the Einstein method was also used to analyze the data that provides a straightforward proof regarding the effect of the temperature on the in-situ XAFS experiment.

  15. PLASTIC WASTE CONVERSION TO LIQUID FUELS OVER MODIFIED-RESIDUAL CATALYTIC CRACKING CATALYSTS: MODELING AND OPTIMIZATION USING HYBRID ARTIFICIAL NEURAL NETWORK – GENETIC ALGORITHM

    Directory of Open Access Journals (Sweden)

    Istadi Istadi

    2012-04-01

    Full Text Available The plastic waste utilization can be addressed toward different valuable products. A promising technology for the utilization is by converting it to fuels. Simultaneous modeling and optimization representing effect of reactor temperature, catalyst calcinations temperature, and plastic/catalyst weight ratio toward performance of liquid fuel production was studied over modified catalyst waste. The optimization was performed to find optimal operating conditions (reactor temperature, catalyst calcination temperature, and plastic/catalyst weight ratio that maximize the liquid fuel product. A Hybrid Artificial Neural Network-Genetic Algorithm (ANN-GA method was used for the modeling and optimization, respectively. The variable interaction between the reactor temperature, catalyst calcination temperature, as well as plastic/catalyst ratio is presented in surface plots. From the GC-MS characterization, the liquid fuels product was mainly composed of C4 to C13 hydrocarbons.KONVERSI LIMBAH PLASTIK MENJADI BAHAN BAKAR CAIR DENGAN METODE PERENGKAHAN KATALITIK MENGGUNAKAN KATALIS BEKAS YANG TERMODIFIKASI: PEMODELAN DAN OPTIMASI MENGGUNAKAN GABUNGAN METODE ARTIFICIAL NEURAL NETWORK DAN GENETIC ALGORITHM. Pemanfaatan limbah plastik dapat dilakukan untuk menghasilkan produk yang lebih bernilai tinggi. Salah satu teknologi yang menjanjikan adalah dengan mengkonversikannya menjadi bahan bakar. Permodelan, simulasi dan optimisasi simultan yang menggambarkan efek dari suhu reaktor, suhu kalsinasi katalis, dan rasio berat plastik/katalis terhadap kinerja produksi bahan bakar cair telah dipelajari menggunakan katalis bekas termodifikasi Optimisasi ini ditujukan untuk mencari kondisi operasi optimum (suhu reaktor, suhu kalsinasi katalis, dan rasio berat plastik/katalis yang memaksimalkan produk bahan bakar cair. Metode Hybrid Artificial Neural Network-Genetic Algorithm (ANN-GA telah digunakan untuk permodelan dan optimisasi simultan tersebut. Inetraksi antar variabel

  16. Highly dispersed metal catalyst

    Energy Technology Data Exchange (ETDEWEB)

    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.

  17. A DLVO model for catalyst motion in metal-assisted chemical etching based upon controlled out-of-plane rotational etching and force-displacement measurements.

    Science.gov (United States)

    Hildreth, Owen J; Rykaczewski, Konrad; Fedorov, Andrei G; Wong, Ching P

    2013-02-07

    Metal-assisted Chemical Etching of silicon has recently emerged as a powerful technique to fabricate 1D, 2D, and 3D nanostructures in silicon with high feature fidelity. This work demonstrates that out-of-plane rotational catalysts utilizing polymer pinning structures can be designed with excellent control over rotation angle. A plastic deformation model was developed establishing that the catalyst is driven into the silicon substrate with a minimum pressure differential across the catalyst thickness of 0.4-0.6 MPa. Force-displacement curves were gathered between an Au tip and Si or SiO(2) substrates under acidic conditions to show that Derjaguin and Landau, Verwey and Overbeek (DLVO) based forces are capable of providing restorative forces on the order of 0.2-0.3 nN with a calculated 11-18 MPa pressure differential across the catalyst. This work illustrates that out-of-plane rotational structures can be designed with controllable rotation and also suggests a new model for the driving force for catalyst motion based on DLVO theory. This process enables the facile fabrication of vertically aligned thin-film metallic structures and scalloped nanostructures in silicon for applications in 3D micro/nano-electromechanical systems, photonic devices, nanofluidics, etc.

  18. Kinetic Studies of Oxidative Coupling of Methane Reaction on Model Catalysts

    KAUST Repository

    Khan, Abdulaziz M.

    2016-04-26

    With the increasing production of natural gas as a result of the advancement in the technology, methane conversion to more valuable products has become a must. One of the most attractive processes which allow the utilization of the world’s most abundant hydrocarbon is the oxidative coupling. The main advantage of this process is the ability of converting methane into higher paraffins and olefins (primarily C2) in a direct way using a single reactor. Nevertheless, low C2+ yields have prevented the process to be commercialized despite the fact that great number of attempts to prepare catalysts were conducted so that it can be economically viable. Due to these limitations, understanding the mechanism and kinetics of the reaction can be utilized in improving the catalysts’ performance. The reaction involves the formation of methyl radicals that undergo gas-phase radical reactions. CH4 activation is believed to be done the surface oxygen species. However, recent studies showed that, in addition to the surface oxygen mediated pathway, an OH radical mediated pathway have a large contribution on the CH4 activation. The experiments of Li/MgO, Sr/La2O3 and NaWO4/SiO2 catalysts revealed variation of behavior in activity and selectivity. In addition, water effect analysis showed that Li/MgO deactivate at the presence of water due to sintering phenomena and the loss of active sites. On the other hand, negative effect on the C2 yield and CH4 conversion rate was observed with Sr/La2O3 with increasing the water partial pressure. Na2WO4/SiO2 showed a positive behavior with water in terms of CH4 conversion and C2 yield. In addition, the increment in CH4 conversion rate was found to be proportional with PO2 ¼ PH2O ½ which is consistent with the formation of OH radicals and the OH-mediated pathway. Experiments of using ring-dye laser, which is used to detect OH in combustion experiments, were tried in order to detect OH radicals in the gas-phase of the catalyst. Nevertheless

  19. Catalyst Architecture

    DEFF Research Database (Denmark)

    Kiib, Hans; Marling, Gitte; Hansen, Peter Mandal

    2014-01-01

    How can architecture promote the enriching experiences of the tolerant, the democratic, and the learning city - a city worth living in, worth supporting and worth investing in? Catalyst Architecture comprises architectural projects, which, by virtue of their location, context and their combination...... of programs, have a role in mediating positive social and/or cultural development. In this sense, we talk about architecture as a catalyst for: sustainable adaptation of the city’s infrastructure appropriate renovation of dilapidated urban districts strengthening of social cohesiveness in the city development...

  20. Characterization of hydro-treating catalysts through model reactions and infrared spectroscopy: contribution to the understanding of the working catalyst on real feed; Caracterisation de catalyseurs d'hydrotraitement par reactions modeles et spectroscopie infrarouge: apport a la comprehension du fonctionnement sur charge reelle

    Energy Technology Data Exchange (ETDEWEB)

    Dujardin, Ch.

    2002-07-01

    The activity of commercial CoMo/(P)Al{sub 2}O{sub 3} hydro-treating catalysts for a gas-oil feed has been compared to that obtained for model molecules, thiophene and 2,6-dimethyl-aniline. Thiophene reaction at atmospheric pressure does not distinguish the catalysts with or without phosphorus. The reaction scheme for 2.6-dimethyl-aniline under hydrogen pressure has been established on a series of catalysts promoted with various cobalt contents. It presents three parallel routes: de-aromatization followed by either hydrogenation-elimination to dimethyl-cyclohexane or elimination to xylene, and disproportionation. We evidenced also a direct denitrogenation reaction contributing to the formation of xylene. This process is enhanced by phosphorus. We showed that the hydrogenation route is nicely correlated with the activity for hydro-desulfurization of the gas-oil feed on the catalysts containing or not phosphorus. Moreover: the fraction of xylene produced by direct denitrogenation can be related to the hydrogenation of the poly-aromatic compounds of the gas-oil. The catalytic sites have been identified by carbon monoxide adsorption at 100 K followed by infrared spectroscopy on the catalysts sulfided in situ under flow. The adsorption distinguishes the coordinative unsaturated sulfur sites of the un-promoted and cobalt promoted molybdenum atoms. Theses sites are responsible for the de-aromatization step of 2.6-dimethyl-aniline. The sulfided catalyst exhibits about half of the potential sites expected from the geometrical mode] of the molybdenum disulfide slabs. Post-treating the sulfide catalyst by hydrogen creates highly unsaturated sites, specifically attached to the un-promoted molybdenum atoms, and associated to the activity of the catalyst for direct denitrogenation. The phosphorus doped catalysts require high hydrogen pressure to generate theses sites. (author)

  1. Dry (CO{sub 2}) reforming of methane over Pt catalysts studied by DFT and kinetic modeling

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Juntian [Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Ministry of Education of PRC, Chongqing University, Chongqing, 400044 (China); College of Power Engineering, Chongqing University, Chongqing, 400044 (China); Du, Xuesen, E-mail: xuesendu@cqu.edu.cn [Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Ministry of Education of PRC, Chongqing University, Chongqing, 400044 (China); College of Power Engineering, Chongqing University, Chongqing, 400044 (China); Ran, Jingyu, E-mail: jyran@189.cn [Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Ministry of Education of PRC, Chongqing University, Chongqing, 400044 (China); College of Power Engineering, Chongqing University, Chongqing, 400044 (China); Wang, Ruirui [Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Ministry of Education of PRC, Chongqing University, Chongqing, 400044 (China); College of Power Engineering, Chongqing University, Chongqing, 400044 (China)

    2016-07-15

    Graphical abstract: - Highlights: • CH appears to be the most abundant species on Pt(1 1 1) surface in CH{sub 4} dissociation. • CO{sub 2}* + H* → COOH* + * → CO* + OH* is the dominant reaction pathway in CO{sub 2} activation. • Major reaction pathway in CH oxidation: CH* + OH* → CHOH* + * → CHO* + H* → CO* + 2H*. • C* + OH* → COH* + * → CO* + H* is the dominant reaction pathway in C oxidation. - Abstract: Dry reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial importance. In order to design catalysts that minimize the deactivation and improve the selectivity and activity for a high H{sub 2}/CO yield, it is necessary to understand the elementary reaction steps involved in activation and conversion of CO{sub 2} and CH{sub 4}. In our present work, a microkinetic model based on density functional theory (DFT) calculations is applied to explore the reaction mechanism for methane dry reforming on Pt catalysts. The adsorption energies of the reactants, intermediates and products, and the activation barriers for the elementary reactions involved in the DRM process are calculated over the Pt(1 1 1) surface. In the process of CH{sub 4} direct dissociation, the kinetic results show that CH dissociative adsorption on Pt(1 1 1) surface is the rate-determining step. CH appears to be the most abundant species on the Pt(1 1 1) surface, suggesting that carbon deposition is not easy to form in CH{sub 4} dehydrogenation on Pt(1 1 1) surface. In the process of CO{sub 2} activation, three possible reaction pathways are considered to contribute to the CO{sub 2} decomposition: (I) CO{sub 2}* + * → CO* + O*; (II) CO{sub 2}* + H* → COOH* + * → CO* + OH*; (III) CO{sub 2}* + H* → mono-HCOO* + * → bi-HCOO* + * [CO{sub 2}* + H* → bi-HCOO* + *] → CHO* + O*. Path I requires process to overcome the activation barrier of 1.809 eV and the forward reaction is calculated to be strongly endothermic by 1.430 eV. In

  2. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    Energy Technology Data Exchange (ETDEWEB)

    Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-01-01

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

  3. Heterogeneous Catalysts

    NARCIS (Netherlands)

    Dakka, J.; Sheldon, R.A.; Sanderson, W.A.

    1997-01-01

    Abstract of GB 2309655 (A) Heterogeneous catalysts comprising one or more metal compounds selected from the group consisting of tin, molybdenum, tungsten, zirconium and selenium compounds deposited on the surface of a silicalite are provided. Preferably Sn(IV) and/or Mo(VI) are employed. The cat

  4. Polymer versus phosphine stabilized Rh nanoparticles as components of supported catalysts: implication in the hydrogenation of cyclohexene model molecule.

    Science.gov (United States)

    Ibrahim, M; Garcia, M A S; Vono, L L R; Guerrero, M; Lecante, P; Rossi, L M; Philippot, K

    2016-11-28

    The solution synthesis of rhodium nanoparticles (Rh NPs) was achieved from the organometallic complex [Rh(η(3)-C3H5)3] under mild reaction conditions in the presence of a polymer (PVP), a monophosphine (PPh3) and a diphosphine (dppb) as a stabilizer, leading to very small Rh NPs of 2.2, 1.3 and 1.7 nm mean size, with PVP, PPh3 and dppb, respectively. The surface properties of these nanoparticles were compared using a model catalysis reaction namely, hydrogenation of cyclohexene, first under colloidal conditions and then under supported conditions after their immobilization onto an amino functionalized silica-coated magnetite support. PVP-stabilized Rh NPs were the most active catalyst whatever the catalytic conditions as a result of a strong coordination of the phosphine ligands at the metal surface that blocks some surface atoms even after several recycles of the supported nanocatalysts and limit the reactivity of the metallic surface.

  5. Effect of substrate preparation on the structure and chemisorption properties of Pd/MgO model catalyst

    Science.gov (United States)

    Henry, C. R.; Poppa, H.

    1988-01-01

    Pd/MgO model catalysts are prepared by vapor deposition of Pd particles on MgO thin films which are deposited, at different temperatures, on UHV cleaved mica. MgO films and Pd particles are characterized in situ by Auger electron spectroscopy and energy-loss spectroscopy and ex situ by transmission electron microscopy. Succesive temperature programmed desorption (TPD) of CO shows a different evolution of the morphology of the Pd particles deposited on MgO films prepared at low and high temperature. In addition, on MgO prepared at low temperature, the smallest particles show a continuous decay of CO adsorption during TPD due to contamination by support species.

  6. 2D and 3D imaging of the gas phase close to an operating model catalyst by planar laser induced fluorescence.

    Science.gov (United States)

    Blomberg, Sara; Zhou, Jianfeng; Gustafson, Johan; Zetterberg, Johan; Lundgren, Edvin

    2016-11-16

    In recent years, efforts have been made in catalysis related surface science studies to explore the possibilities to perform experiments at conditions closer to those of a technical catalyst, in particular at increased pressures. Techniques such as high pressure scanning tunneling/atomic force microscopy (HPSTM/AFM), near ambient pressure x-ray photoemission spectroscopy (NAPXPS), surface x-ray diffraction (SXRD) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) at semi-realistic conditions have been used to study the surface structure of model catalysts under reaction conditions, combined with simultaneous mass spectrometry (MS). These studies have provided an increased understanding of the surface dynamics and the structure of the active phase of surfaces and nano particles as a reaction occurs, providing novel information on the structure/activity relationship. However, the surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface. Therefore, the catalytic activity of the sample itself will act as a gas-source or gas-sink, and will affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, we have applied planar laser induced fluorescence (PLIF) to the gas phase in the vicinity of an active model catalysts. Our measurements demonstrate that the gas composition differs significantly close to the catalyst and at the position of the MS, which indeed should have a profound effect on the surface structure. However, PLIF applied to catalytic reactions presents several beneficial properties in addition to investigate the effect of the catalyst on the effective gas composition close to the model catalyst. The high spatial and temporal resolution of PLIF provides a unique tool to visualize the on-set of catalytic reactions and to compare different model catalysts in the same reactive environment. The technique can be

  7. 2D and 3D imaging of the gas phase close to an operating model catalyst by planar laser induced fluorescence

    Science.gov (United States)

    Blomberg, Sara; Zhou, Jianfeng; Gustafson, Johan; Zetterberg, Johan; Lundgren, Edvin

    2016-11-01

    In recent years, efforts have been made in catalysis related surface science studies to explore the possibilities to perform experiments at conditions closer to those of a technical catalyst, in particular at increased pressures. Techniques such as high pressure scanning tunneling/atomic force microscopy (HPSTM/AFM), near ambient pressure x-ray photoemission spectroscopy (NAPXPS), surface x-ray diffraction (SXRD) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) at semi-realistic conditions have been used to study the surface structure of model catalysts under reaction conditions, combined with simultaneous mass spectrometry (MS). These studies have provided an increased understanding of the surface dynamics and the structure of the active phase of surfaces and nano particles as a reaction occurs, providing novel information on the structure/activity relationship. However, the surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface. Therefore, the catalytic activity of the sample itself will act as a gas-source or gas-sink, and will affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, we have applied planar laser induced fluorescence (PLIF) to the gas phase in the vicinity of an active model catalysts. Our measurements demonstrate that the gas composition differs significantly close to the catalyst and at the position of the MS, which indeed should have a profound effect on the surface structure. However, PLIF applied to catalytic reactions presents several beneficial properties in addition to investigate the effect of the catalyst on the effective gas composition close to the model catalyst. The high spatial and temporal resolution of PLIF provides a unique tool to visualize the on-set of catalytic reactions and to compare different model catalysts in the same reactive environment. The technique can be

  8. An improved single crystal adsorption calorimeter for determining gas adsorption and reaction energies on complex model catalysts

    Science.gov (United States)

    Fischer-Wolfarth, Jan-Henrik; Hartmann, Jens; Farmer, Jason A.; Flores-Camacho, J. Manuel; Campbell, Charles T.; Schauermann, Swetlana; Freund, Hans-Joachim

    2011-02-01

    A new ultrahigh vacuum microcalorimeter for measuring heats of adsorption and adsorption-induced surface reactions on complex single crystal-based model surfaces is described. It has been specifically designed to study the interaction of gaseous molecules with well-defined model catalysts consisting of metal nanoparticles supported on single crystal surfaces or epitaxial thin oxide films grown on single crystals. The detection principle is based on the previously described measurement of the temperature rise upon adsorption of gaseous molecules by use of a pyroelectric polymer ribbon, which is brought into mechanical/thermal contact with the back side of the thin single crystal. The instrument includes (i) a preparation chamber providing the required equipment to prepare supported model catalysts involving well-defined nanoparticles on clean single crystal surfaces and to characterize them using surface analysis techniques and in situ reflectivity measurements and (ii) the adsorption/reaction chamber containing a molecular beam, a pyroelectric heat detector, and calibration tools for determining the absolute reactant fluxes and adsorption heats. The molecular beam is produced by a differentially pumped source based on a multichannel array capable of providing variable fluxes of both high and low vapor pressure gaseous molecules in the range of 0.005-1.5 × 1015 molecules cm-2 s-1 and is modulated by means of the computer-controlled chopper with the shortest pulse length of 150 ms. The calorimetric measurements of adsorption and reaction heats can be performed in a broad temperature range from 100 to 300 K. A novel vibrational isolation method for the pyroelectric detector is introduced for the reduction of acoustic noise. The detector shows a pulse-to-pulse standard deviation ≤15 nJ when heat pulses in the range of 190-3600 nJ are applied to the sample surface with a chopped laser. Particularly for CO adsorption on Pt(111), the energy input of 15 nJ (or 120 nJ cm

  9. Production performance, egg quality and biochemical parameters of three way crossbred chickens with reciprocal F1 crossbred chickens in sub-tropical environment

    Directory of Open Access Journals (Sweden)

    Tabinda Khawaja

    2013-03-01

    Full Text Available A total of 225 hens (18 weeks of age of each Rhode Island Red male x Fayoumi female (RIFI, Fayoumi male x Rhode Island Red female (FIRI and White Leghorn male x FIRI female (RLH were maintained on deep litter system for a period of 72 weeks of age. In floor pens, each crossbred chicken was randomly distributed between pens, with 21 to 24 birds of the same breed per pen (2.00 to 2.50 ft2/bird. The results revealed that the age of sexual maturity was lowest in RIFI followed by FIRI and RLH chickens. The highest egg production was obtained by three-way crossbred chickens (RLH as compared with two-way crossbred chickens (RIFI and FIRI. The highest egg weight was observed in RLH than those of FIRI and RIFI crossbred chickens. The internal egg quality parameters included yolk weight, albumen weight, yolk + albumen weight and albumen height were same in all crossbred chickens. There was non-significant (p>0.05 difference in blood glucose, triglyceride, cholesterol, calcium, protein, uric acid and ALP values among all crossbred chickens. It may be concluded that three-way crossbred chickens (RLH showed better egg traits than two-way crossbred chickens (RIFI and FIRI with lower mortality. The RIFI crossbred chickens achieved sexual maturity earlier than both FIRI and RLH crossbred chickens with lower egg traits.

  10. Effects of mycoplasmal pneumonia of swine (MPS) lung lesion-selected Landrace pigs on MPS resistance and immune competence in three-way crossbred pigs.

    Science.gov (United States)

    Borjigin, Liushiqi; Shimazu, Tomoyuki; Katayama, Yuki; Watanabe, Kouichi; Kitazawa, Haruki; Roh, Sang-Gun; Aso, Hisashi; Katoh, Kazuo; Satoh, Masahiro; Suda, Yoshihito; Sakuma, Akiko; Nakajo, Mituru; Suzuki, Keiichi

    2016-09-09

    To clarify the genetic influence of mycoplasmal pneumonia of swine (MPS) lesion-selected Landrace (La) on MPS resistance and immune characteristics in three-way crossbred pigs (LaWaDa), the LaWaDa pigs were compared with the non-selected crossbred (LbWbDb) and purebred (La) pigs. The MPS lesion score in the three lines was as follows: La line < LaWaDa line < LbWbDb line, with significant differences among the lines. The proportions of myeloid cells and T cells were lower and higher, respectively, in the LaWaDa pigs compared with those in the other two lines. Messenger RNA (mRNA) expression of interleukin (IL)-6, IL-10, transforming growth factor-β, and interferon-γ in peripheral blood was significantly increased after vaccination in the La and LaWaDa lines. IL-4 mRNA expression in the LaWaDa line was intermediate to the La and LbWbDb lines. Furthermore, principal component analysis for immune traits and MPS lesions was executed to clarify the characteristics of each pig line. These findings suggest that the immune responses in the three pig lines are genetically distinct and that MPS resistance and some immunity characteristics from the La line were transmitted to the three-way crossbred pigs.

  11. Using in-situ synchrotron x-ray diffraction to investigate phase transformation and lattice relaxation of a three-way piezo-phototronic soft material

    Science.gov (United States)

    Ko, Wen-Ching; Hsu, Yu-Hsiang; Weng, Shih-Chang; Chang, Chung-Kai; Lee, Ming-Tao; Chuang, Wei-Tsung; Thong, Hao-Cheng; Ali, Muhammad; Huang, E.-Wen

    2017-07-01

    A poly(vinylidene fluoride-co-trifluoro-ethylene) piezoelectric polymer is blended with nano particles of titanium oxide phthalocyanine to bridge photoconductive and piezoelectric effects. In this study, a system is examined by in situ synchrotron x-ray to test a three-way piezo-phototronic soft-material design. The sample is heated for in situ phase transformation characterization. The semi-crystalline poly (vinylidene fluoride-co-trifluoro-ethylene) polymer gradually transforms to an amorphous structure. A complementary piezoelectric experiment before and after the heating experiment shows that the piezoelectric performance is proportional to the phase ratio. Secondly, the system is examined to test its phototronic effect. Piezoelectric responses are measured by controlling the light illumination. The positive and negative controls of light illumination which validate this newly-designed system can be modulated by a three-way piezo-phototronic effect. In-situ synchrotron x-ray diffraction experiments are employed to measure the microstructure evolution as a function of applied voltage up to 800 V. We then turned off both the light and the applied voltage to examine the kinetic behavior of the system. There is orientation-dependent anisotropic relaxation. We compared the lattice-strain evolutions. Piezo-phototronic creep is found in the (110), but not the (310) planes.

  12. Isothermal Kinetics Modelling of the Fischer-Tropsch Synthesis over the Spray-Dried Fe-Cu-K Catalyst

    Institute of Scientific and Technical Information of China (English)

    Xiaohui Guo; Ying Liu; Jie Chang; Liang Bai; Yuanyuan Xu; Hongwei Xiang; Yongwang Li

    2006-01-01

    The isothermal kinetics of the Fischer-Tropsch synthesis (FTS) over Fe-Cu-K spray-dried catalyst was studied in a spinning basket reactor. The experiments were carried out at a constant temperature of 523 K, n(H2)/n(CO) feed ratios of 0.8-2.0, reactor pressures of 1.1-2.5 MPa, and space velocity of 0.556× 10-3 Nm3/kgcat.s. Kinetic model for hydrocarbon formation was derived on the basis of simplified carbide mechanism to reduce the number of parameters. Two individual rate constants for methane and ethene were considered. Furthermore, the model was modified empirically by non-intrinsic effect, such as physisorption and fictitious olefin pressures that were taken into account, and the influences of secondary reaction of α-olefins on product distribution. The simulation results showed that the experimental phenomena of FTS and the deviations from ASF distribution, such as the relatively high yield of methane and low yield of ethene observed experimentally could be depicted basically.

  13. A genetically optimized kinetic model for ethanol electro-oxidation on Pt-based binary catalysts used in direct ethanol fuel cells

    Science.gov (United States)

    Sánchez-Monreal, Juan; García-Salaberri, Pablo A.; Vera, Marcos

    2017-09-01

    A one-dimensional model is proposed for the anode of a liquid-feed direct ethanol fuel cell. The complex kinetics of the ethanol electro-oxidation reaction is described using a multi-step reaction mechanism that considers free and adsorbed intermediate species on Pt-based binary catalysts. The adsorbed species are modeled using coverage factors to account for the blockage of the active reaction sites on the catalyst surface. The reaction rates are described by Butler-Volmer equations that are coupled to a one-dimensional mass transport model, which incorporates the effect of ethanol and acetaldehyde crossover. The proposed kinetic model circumvents the acetaldehyde bottleneck effect observed in previous studies by incorporating CH3CHOHads among the adsorbed intermediates. A multi-objetive genetic algorithm is used to determine the reaction constants using anode polarization and product selectivity data obtained from the literature. By adjusting the reaction constants using the methodology developed here, different catalyst layers could be modeled and their selectivities could be successfully reproduced.

  14. Catalyst Architecture

    DEFF Research Database (Denmark)

    Kiib, Hans; Marling, Gitte; Hansen, Peter Mandal

    2014-01-01

    of programs, have a role in mediating positive social and/or cultural development. In this sense, we talk about architecture as a catalyst for: sustainable adaptation of the city’s infrastructure appropriate renovation of dilapidated urban districts strengthening of social cohesiveness in the city development...... meaningful for everyone. The exhibited works are designed by SANAA, Diller Scofidio + Renfro, James Corner Field Operation, JBMC Arquitetura e Urbanismo, Atelier Bow-Wow, Ateliers Jean Nouvel, COBE, Transform, BIG, Topotek1, Superflex, and by visual artist Jane Maria Petersen....

  15. Ni/γ-Al2O3 Catalyst for CO2 Reforming of Benzene as a Model Compound of Biomass Gasification Tar: Promotional Effect of Ultrasonic Treatment on Catalytic Performance

    Science.gov (United States)

    Li, B.; Chen, H. P.; Yang, H. P.; Yang, G. L.; Wang, X. H.; Zhang, S. H.

    This paper aims to understand the promotional effect of ultrasonic treatment on catalytic performance of Ni/γ-Al2O3 catalyst for CO2 reforming of benzene as a model compound of tar derived from biomass gasification, and the catalytic cracking mechanism was also discussed. Firstly, three Ni/γ-Al2O3catalysts were prepared by ultrasonic impregnation as the ultrasonic power variantat0, 120 and 500W, andthephysicochemical property of catalysts were characterized using N2-adsorption, SEM and XRD, etc. Then the catalytic performance of three catalysts for CO2 reforming of benzene wastestedin amicro-reactor.Theoutlet gaswas measured using a Micro-GC. Finally, the coking amount on the catalyst surface was measured by thermogravimetry (TG). The results showed that ultrasonic treatment significanüy modified the pore size distribution of the catalysts especiallyin theporesize range of 10-50nm andalso improved the capability of the coke resistance. It's beneficial to increase the lifetime of the catalyst. Meanwhile, lower ultrasonic power(120W) was more favorableto improve the coke resistance of the catalyst in the power range tested (120 and 500W). The main surface reactions over Ni/γ-Al2O3 catalysts included two steps: Firstly, benzeneadsorbed on the catalyst surface, the metal active sites dehydrogenation took place, and the residual molecule fragments (coke precursor) wouldcondense further which led to coke formation.Then, CO2 reacted with coke precursor and coke for coke elimination. The first step carriedout very quickly, and the second step was the rate-determining step.To reduce the cokedeposition on the catalyst surface, the performance of CO2 adsorption and activation and surface oxygen transmission capacity should be improved further.

  16. Mathematical Modelling of Catalytic Fixed-Bed Reactor for Carbon Dioxide Reforming of Methane over Rh/Al2O3 Catalyst

    Directory of Open Access Journals (Sweden)

    Nor Aishah Saidina Amin

    2010-10-01

    Full Text Available A one-dimensional mathematical model was developed to simulate the performance of catalytic fixed bed reactor for carbon dioxide reforming of methane over Rh/Al2O3 catalyst at atmospheric pressure. The reactions involved in the system are carbon dioxide reforming of methane (CORM and reverse water gas shift reaction (RWGS. The profiles of CH4 and CO2 conversions, CO and H2 yields, molar flow rate and mole raction of all species as well as reactor temperature along the axial bed of catalyst were simulated. In addition, the effects of different reactor temperature on the reactor performance were also studied. The models can also be applied to analyze the performances of lab-scale micro reactor as well as pilot-plant scale reactor with certain modifications and model verification with experimental data. © 2008 BCREC UNDIP. All rights reserved.[Received: 20 August 2008; Accepted: 25 September 2008][How to Cite: N.A.S. Amin, I. Istadi, N.P. Yee. (2008. Mathematical Modelling of Catalytic Fixed-Bed Reactor for Carbon Dioxide Reforming of Methane over Rh/Al2O3 Catalyst. Bulletin of Chemical Reaction Engineering and Catalysis, 3 (1-3: 21-29.  doi:10.9767/bcrec.3.1-3.7120.21-29][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.3.1-3.7120.21-29 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/7120

  17. Conjugation of a 3-(1H-phenanthro[9,10-d]imidazol-2-yl)-1H-indole intercalator to a triplex oligonucleotide and to a three-way junction.

    Science.gov (United States)

    Fatthalla, Maha I; Elkholy, Yehya M; Abbas, Nermeen S; Mandour, Adel H; Jørgensen, Per T; Bomholt, Niels; Pedersen, Erik B

    2012-01-01

    A new intercalating nucleic acid monomer M comprising a 4-(1-indole)-butane-1,2-diol moiety was synthesized via a classical alkylation reaction of indole-3-carboxaldehyde followed by a condensation reaction with phenanthrene-9,10-dione in the presence of ammonium acetate to form a phenanthroimidazole moiety linked to the indole ring. Insertion of the new intercalator as a bulge into a Triplex Forming Oligonucleotide resulted in good thermal stability of the corresponding Hoogsteen-type triplexes. Molecular modeling supports the possible intercalating ability of M. Hybridisation properties of DNA/DNA and RNA/DNA three-way junctions (TWJ) with M in the branching point were also evaluated by their thermal stability at pH 7. DNA/DNA TWJ showed increase in thermal stability compared to wild type oligonucleotides whereas this was not the case for RNA/DNA TWJ. Copyright © 2011 Elsevier Ltd. All rights reserved.

  18. Thermal and adsorbate effects on the activity and morphology of size-selected Pdn/TiO2 model catalysts

    Science.gov (United States)

    Kaden, William E.; Kunkel, William A.; Roberts, F. Sloan; Kane, Matthew; Anderson, Scott L.

    2014-03-01

    Model catalysts containing size-selected Pdn (n = 1,2,4,7,10,16,20,25) deposited on rutile TiO2(110) deactivate during repeated CO oxidation temperature-programmed reaction (TPR) cycles, and the deactivation process has been probed using a combination of X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), low-energy ion scattering (ISS), temperature-dependent ion scattering (TD-ISS), annealing experiments, and temperature-programmed desorption following exposure to CO and O2 reactants. Results from such experiments suggest the cluster deactivation proceeds via an alloy-like, strong metal-support interaction (SMSI) effect that chemically modifies the clusters via electronic interactions between the supported metal atoms and Ti from the support. Threshold measurements show that this effect detrimentally affects CO-oxidation activity prior to the formation of an encapsulating overlayer by severely weakening the COPd bond strengths for binding configurations on top of the clusters. Oxidation appears to provide means of partially restoring the clusters to their initial state, but after sufficient exposure to reducing environments and elevated temperatures, all Pdn become covered by an overlayer and begin to electronically and chemically resemble freshly deposited atoms, which are completely inactive towards the probe reaction. In addition, we find evidence of oxygen spillover induced by co-adsorbed CO during TPRs for all active Pdn clusters.

  19. Catalytic reforming of toluene as tar model compound: effect of Ce and Ce-Mg promoter using Ni/olivine catalyst.

    Science.gov (United States)

    Zhang, Ruiqin; Wang, Huajian; Hou, Xiaoxue

    2014-02-01

    Tar produced by biomass gasification as a route of renewable energy must be removed before the gas can be used. This study was undertaken using toluene as a model tar compound for evaluating its steam reforming conversion with three Ni-based catalysts, Ni/olivine, Ni-Ce/olivine and Ni-Ce-Mg/olivine. Effects of Ce and Mg promoters on the reaction activity and coke deposition were studied. Overall the performance of Ce and Mg promoted Ni/olivine catalysts is better than that of only Ce promoter and Ni/olivine alone. The experimental results indicate that Ni-Ce-Mg/olivine catalysts could improve the resistance to carbon deposition, enhance energy gases yield and resist 10ppm H2S poison at 100mLmin(-1) for up to 400min. Furthermore, the activity of catalysts was related to the steam/carbon (S/C) ratios; at S/C ratio=5, T=790°C, space velocity=782h(-1) and t=2h, the Ni-Ce-Mg/olivine system yielded 89% toluene conversion, 5.6Lh(-1) product gas rate, 62.6mol% H2 content and 10% (mol useful gas mol(-1) toluene) energy yield. Moreover, at low S/C ratio, it had higher reaction activity and better ability to prevent coking. There is a small amount of carbon deposition in the form of amorphous carbon after 7h. Various characterization techniques such as XRD, FTIR and thermogravimetric were performed to investigate the coke deposition of Ni/olivine, Ni-Ce/olivine and Ni-Ce-Mg/olivine. It is suggested that 3% Ni-1% Ce-1% Mg/olivine was the most promising catalyst due to its minimum coke amount and the lower activation energy of coke burning.

  20. Development of GREET Catalyst Module

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhichao [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division; Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division; Cronauer, Donald C. [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division

    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.

  1. The Women's Health Care Empowerment Model as a Catalyst for Change in Developing Countries.

    Science.gov (United States)

    Mitroi, Lavinia R; Sahak, Medina; Sherzai, Ayesha Z; Sherzai, Dean

    2016-01-01

    Women's empowerment has been attempted through a number of different fields including the realms of politics, finance, and education, yet none of these domains are as promising as health care. Here we review preliminary work in this domain and introduce a model for women's empowerment through involvement in health care, titled the "women's health care empowerment model." Principles upon which our model is built include: acknowledging the appropriate definition of empowerment within the cultural context, creating a women's network for communication, integrating local culture and tradition into training women, and increasing the capability of women to care for their children and other women.

  2. Quantity and quality of secoiridoids and lignans in extra virgin olive oils: the effect of two- and three-way decanters on Leccino and Raggiola olive cultivars.

    Science.gov (United States)

    Antonini, Elena; Farina, Alfonso; Scarpa, Emanuele Salvatore; Frati, Alessandra; Ninfali, Paolino

    2016-01-01

    In this investigation, 14 extra virgin olive oils (EVOOs), produced with Leccino and Raggiola olive cultivars, by a new two-way (2W) decanter were compared with 14 EVOOs produced by means of a conventional three-way (3W) decanter. The 2W EVOOs had higher phenol concentrations, as shown by high-performance liquid chromatography/diode array detection (HPLC-DAD) analysis and yielded a higher extraction of the 3,4-DHPEA-EDA (oleacein), 3,4-DHPEA-EA (oleuropein aglycone) and p-HPEA-EDA (oleocanthal). The concentrations of lignans, (+)-pinoresinol and (+)-1-acetoxypinoresinol, detected by HPLC-FLD equipment, were higher in the 2W EVOOs than they were in EVOOs produced using the 3W system. Total phenols, detected by the Folin-Ciocalteu assay, were lower than those obtained by HPLC, but they significantly correlated (p olive secoiridoid concentration.

  3. A new three-way variant t(15;22;17)(q22;q11.2;q21) in acute promyelocytic leukemia.

    Science.gov (United States)

    Kato, Takayasu; Hangaishi, Akira; Ichikawa, Motoshi; Motokura, Toru; Takahashi, Tsuyoshi; Kurokawa, Mineo

    2009-03-01

    Acute promyelocytic leukemia (APL) is characterized by the t(15;17)(q22;q21), which results in the fusion of the promyelocytic leukemia (PML) gene at 15q22 with the retinoic acid alpha-receptor (RARA) at 17q21. We report the case of a 44-year-old man with APL carrying a new complex variant translocation (15;22;17). Karyotypic analysis with G-banding of bone marrow cells revealed t(15;22;17) (q22;q11.2;q21). Fluorescence in situ hybridization with a PML/RARA dual-color DNA probe showed the fusion signals. RT-PCR analysis showed long-form PML/RARA fusion transcripts. A complete remission was attained with a course of conventional chemotherapy with all-trans retinoic acid (ATRA). This is the first report of a new three-way translocation of 22q11 involvement with APL.

  4. Quality assessment of the saffron samples using second-order spectrophotometric data assisted by three-way chemometric methods via quantitative analysis of synthetic colorants in adulterated saffron

    Science.gov (United States)

    Masoum, Saeed; Gholami, Ali; Hemmesi, Marjan; Abbasi, Saleheh

    2015-09-01

    Saffron is a valuable culinary spice that can be used not only for dyes and cooking, but also for many medical purposes. Due to its high price and restriction of its production, various fraud manners in its production have been growing. Addition of synthetic colorants to saffron is the most common way for adulteration. In this work, chemometric methods are proposed to resolve the three-dimensional absorbance spectra-pH data for simultaneous determination of the two colorants Tartrazin and Sunset yellow, in adulterated saffron. The rank deficiency in the concentration mode impaired the system. Therefore, to extirpate the ambiguity, which results from rank deficiency, three-way variation array V was generated by subtracting the first pH spectrum from each spectrum at each pH. This allows the extraction of extent reaction profile and mixture reaction spectral profiles, as well as the relative concentrations of the analytes.

  5. 优质肉用羊三元杂交技术%Three-way Cross Technology of Excellent Meat Sheep Breeds

    Institute of Scientific and Technical Information of China (English)

    彭龙; 赛很图娅; 汤化军; 赵芳; 张文敬; 王君

    2012-01-01

    利用阴道海绵栓法和孕马血清同期化处理试验母羊,通过人工授精的方式,采用杜泊种公羊和巴美肉羊种公羊与巴寒杂交F1代母羊和杜寒杂交F1代母羊进行三元杂交,作为试验组;选择同龄当地小尾寒羊种公羊和小尾寒羊母羊自然交配,作为对照组,进行比较,观察杂交改良后的效果。结果表明,杂交F1代母羊的受胎率、产羔率低于小尾寒羊,但在生产性能方面,三元杂交F2代羔羊平均初生重和1月龄体重比当地小尾寒羊分别提高1.68kg和2.02kg;在相同的饲养管理条件下,三元杂交F2代羔羊体高、体长、胸围等均高于当地同龄小尾寒羊,其生长发育速度显著快于当地小尾寒羊。由此可以得出,以杜泊种公羊和巴美肉羊种公羊与巴寒杂交F1代母羊和杜寒杂交F1代母羊进行三元杂交改良,改良效果明显。%After tested female sheep were treated by using vaginal sponge method and pregnant mare serum, male Dorper sheep and male Bamei sheep were improved by three-way cross with female Bahan F1 hybrid sheep and female Duhan F1 hybrid sheep by using artificial insemination, meanwhile male small-tail Hart sheep of the same age was mated with female small-tail Han sheep, which was taken as control. The improvement effect was observed. Results showed that the conception rate and lambing rate of female FI hybrid sheep were lower than that of small-tail Han sheep; but in the aspect of production performance, the average birth weight and the weight at 1 month of age of F2 three-way hybrid sheep were increased by 1.68 kg and 2.02 kg compared with local small-tail Han sheep; under the same feeding and management conditions, the height at withers, body length and heart girth F2 three-way hybrid sheep were higher than that of local small-tail Han sheep. Therefore, the improvement effect was obvious when male Dorper sheep and male Bamei sheep were improved by three-way cross with female Bahan Fi hybrid

  6. Pore network model of the cathode catalyst layer of proton exchange membrane fuel cells: Analysis of water management and electrical performance

    OpenAIRE

    El Hannach, Mohamed; Prat, Marc; Pauchet, Joël

    2012-01-01

    International audience; A pore network modeling approach is developed to study multiphase transport phenomena inside a porous structure representative of the Cathode Catalyst Layer (CCL) of Proton Exchange Membrane Fuel Cell. A full coupling between two-phase transport, charge transport and heat transport is considered. The liquid water evaporation is also taken into account. The current density profile and the liquid water distribution and production are investigated to understand the liquid...

  7. KINETIC MODELING OF A FISCHER-TROPSCH REACTION OVER A COBALT CATALYST IN A SLURRY BUBBLE COLUMN REACTOR FOR INCORPORATION INTO A COMPUTATIONAL MULTIPHASE FLUID DYNAMICS MODEL

    Energy Technology Data Exchange (ETDEWEB)

    Anastasia Gribik; Doona Guillen, PhD; Daniel Ginosar, PhD

    2008-09-01

    Currently multi-tubular fixed bed reactors, fluidized bed reactors, and slurry bubble column reactors (SBCRs) are used in commercial Fischer Tropsch (FT) synthesis. There are a number of advantages of the SBCR compared to fixed and fluidized bed reactors. The main advantage of the SBCR is that temperature control and heat recovery are more easily achieved. The SBCR is a multiphase chemical reactor where a synthesis gas, comprised mainly of H2 and CO, is bubbled through a liquid hydrocarbon wax containing solid catalyst particles to produce specialty chemicals, lubricants, or fuels. The FT synthesis reaction is the polymerization of methylene groups [-(CH2)-] forming mainly linear alkanes and alkenes, ranging from methane to high molecular weight waxes. The Idaho National Laboratory is developing a computational multiphase fluid dynamics (CMFD) model of the FT process in a SBCR. This paper discusses the incorporation of absorption and reaction kinetics into the current hydrodynamic model. A phased approach for incorporation of the reaction kinetics into a CMFD model is presented here. Initially, a simple kinetic model is coupled to the hydrodynamic model, with increasing levels of complexity added in stages. The first phase of the model includes incorporation of the absorption of gas species from both large and small bubbles into the bulk liquid phase. The driving force for the gas across the gas liquid interface into the bulk liquid is dependent upon the interfacial gas concentration in both small and large bubbles. However, because it is difficult to measure the concentration at the gas-liquid interface, coefficients for convective mass transfer have been developed for the overall driving force between the bulk concentrations in the gas and liquid phases. It is assumed that there are no temperature effects from mass transfer of the gas phases to the bulk liquid phase, since there are only small amounts of dissolved gas in the liquid phase. The product from the

  8. Mathematical Modelling of Catalytic Fixed-Bed Reactor for Carbon Dioxide Reforming of Methane over Rh/Al2O3 Catalyst

    Directory of Open Access Journals (Sweden)

    New Pei Yee

    2008-04-01

    Full Text Available A one-dimensional mathematical model was developed to simulate the performance of catalytic fixed bedreactor for carbon dioxide reforming of methane over Rh/Al2O3 catalyst at atmospheric pressure. The reactionsinvolved in the system are carbon dioxide reforming of methane (CORM and reverse water gas shiftreaction (RWGS. The profiles of CH4 and CO2 conversions, CO and H2 yields, molar flow rate and molefraction of all species as well as reactor temperature along the axial bed of catalyst were simulated. In addition,the effects of different reactor temperature on the reactor performance were also studied. The modelscan also be applied to analyze the performances of lab-scale micro reactor as well as pilot-plant scale reactorwith certain modifications and model verification with experimental data. © 2008 BCREC UNDIP. All rights reserved.[Received: 20 August 2008; Accepted: 25 September 2008][How to Cite: N.A.S. Amin, I. Istadi, N.P. Yee. (2008. Mathematical Modelling of Catalytic Fixed-Bed Reactor for Carbon Dioxide Reforming of Methane over Rh/Al2O3 Catalyst. Bulletin of Chemical Reaction Engineering and Catalysis, 3 (1-3: 21-29. doi:10.9767/bcrec.3.1-3.19.21-29

  9. Decomposition of lignin model compounds by Lewis acid catalysts in water and ethanol

    NARCIS (Netherlands)

    Guvenatam, Burcu; Heeres, Erik H.J.; Pidko, Evgeny A.; Hensen, Emiel J. M.

    2015-01-01

    The conversion of benzyl phenyl ether, diphenyl ether, diphenyl methane and biphenyl as representative model compounds for alpha-O-4, 5-O-4, alpha(1) (methylene bridges) and 5-5' lignin linkages was investigated. We compared the use of metal chlorides and acetates. The reactions were studied in sub-

  10. Decomposition of lignin model compounds by Lewis acid catalysts in water and ethanol

    NARCIS (Netherlands)

    Guvenatam, Burcu; Heeres, Erik H.J.; Pidko, Evgeny A.; Hensen, Emiel J. M.

    2015-01-01

    The conversion of benzyl phenyl ether, diphenyl ether, diphenyl methane and biphenyl as representative model compounds for alpha-O-4, 5-O-4, alpha(1) (methylene bridges) and 5-5' lignin linkages was investigated. We compared the use of metal chlorides and acetates. The reactions were studied in sub-

  11. Catalyst Architecture

    DEFF Research Database (Denmark)

    the projects as case studies, which contribute with strategic knowledge rather than generalizing from average considerations. These are ‘strategic projects’ where we have looked for the specific and the particular (Flyvbjerg 1991). According to the case studies, we use the case study method developed by Bent......’ interpretations and architectural strategies are included in the analyses. This implies that there is a large variation of empirical knowledge about the selected problems. That is the reason why we give a short introduction to the exact use of approaches and methods in the beginning of each case study. Based...... in experience? Which design qualities do the best examples of architecture as urban catalysts have, and how can we as citizens, politicians and professionals use knowledge about this in the development of our cities as good places to live? We wish to throw light on these key questions through case studies...

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

    Energy Technology Data Exchange (ETDEWEB)

    Kwolek, Emma J. [Iowa State Univ., Ames, IA (United States)

    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.

  13. Reaction mechanism of coal liquefaction: hydrogenolysis of model compound using synthetic pyrite as catalysts. 7. Property change of synthetic pyrite catalyst with the time after production; Sekitan ekika hanno kiko (model kagobutsu no hanno). 7. Gosei ryukatetsu shokubai no keiji henka ni tsuite

    Energy Technology Data Exchange (ETDEWEB)

    Ito, H.; Meno, H.; Uemaki, O.; Shibata, T.; Tsuji, T. [Hokkaido University, Sapporo (Japan)

    1996-10-28

    Reactions of various model compounds were investigated using synthetic pyrites for coal liquefaction. In this study, successive changes of the catalysts were investigated from the reactions of model compounds by using three different synthetic pyrites with the lapse of time after production. Benzyl phenyl ether, dibenzyl, and n-octylbenzene were used as model compounds. Reactions were conducted in an autoclave, into which sample, catalyst, decalin as solvent, and initial hydrogen pressure 10 MPa were charged. The autoclave was held at 450 or 475{degree}C of reaction temperature for 1 hour. The catalyst with a shorter lapse of time after production acted to hydrogen transfer, and inhibited the formation of condensation products due to the stabilization of decomposed fragment. It also acted to isomerization of materials by cutting alkyl side chains. When adding sulfur to the catalyst with longer lapse of time after production under these reaction conditions, it inhibited the formation of condensation products for the reaction of benzyl phenyl ether. However, it did not provide the effect for the reaction of n-octylbenzene. 5 refs., 3 figs.

  14. Dehydrogenation Kinetics and Modeling Studies of MgH2 Enhanced by Transition Metal Oxide Catalysts Using Constant Pressure Thermodynamic Driving Forces

    Directory of Open Access Journals (Sweden)

    Saidi Temitope Sabitu

    2012-06-01

    Full Text Available The influence of transition metal oxide catalysts (ZrO2, CeO2, Fe3O4 and Nb2O5 on the hydrogen desorption kinetics of MgH2 was investigated using constant pressure thermodynamic driving forces in which the ratio of the equilibrium plateau pressure (pm to the opposing plateau (pop was the same in all the reactions studied. The results showed Nb2O5 to be vastly superior to other catalysts for improving the thermodynamics and kinetics of MgH2. The modeling studies showed reaction at the phase boundary to be likely process controlling the reaction rates of all the systems studied.

  15. Development of a complete kinetic model for the Fischer-Tropsch synthesis over Co/Al{sub 2}O{sub 3} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Visconti, C.G.; Tronconi, E.; Lietti, L.; Forzatti, P. [Politecnico di Milano (Italy). Dipt. di Chimica, Materiali e Ingegneria Chimica ' ' G.Natta' ' ; Zennaro, R. [EniTecnologie, San Donato Milanese (Italy). Catalysis and Process Technology Research Centre

    2006-07-01

    A global kinetic model of the FTS over a Co/Al{sub 2}O{sub 3} state-of-the-art catalyst is developed in a fixed bed micro-reactor under conditions relevant to industrial operation (temperature, 210- 235 C; pressure, 8-25 bar; H{sub 2}/CO feed molar ratio, 1.8-2.7; gas hourly space velocity, 2000- 7000 cm{sup 3}(STP)/h/g{sub catalyst}). On the basis of proposed reaction mechanisms, developed according to the carbide theory and the alkyl mechanism, the kinetic expressions for n-paraffins and {alpha}-olefins formation are derived. Both the calculated CO conversion and the hydrocarbons distribution (up to N=49) in FTS reaction are satisfactorily predicted. (orig.)

  16. Electrochemical catalyst recovery method

    Science.gov (United States)

    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.

  17. Application of a Coated Film Catalyst Layer Model to a High Temperature Polymer Electrolyte Membrane Fuel Cell with Low Catalyst Loading Produced by Reactive Spray Deposition Technology

    OpenAIRE

    Myles, Timothy D.; Siwon Kim; Radenka Maric; Mustain, William E.

    2015-01-01

    In this study, a semi-empirical model is presented that correlates to previously obtained experimental overpotential data for a high temperature polymer electrolyte membrane fuel cell (HT-PEMFC). The goal is to reinforce the understanding of the performance of the cell from a modeling perspective. The HT-PEMFC membrane electrode assemblies (MEAs) were constructed utilizing an 85 wt. % phosphoric acid doped Advent TPS® membranes for the electrolyte and gas diffusion electrodes (GDEs) manufactu...

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

    Science.gov (United States)

    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.

  19. Monolithic Catalysts with Low Noble-Metal Content for Exhaust Purification of Small Gasoline Engines

    Institute of Scientific and Technical Information of China (English)

    Zhang Lijuan; Mao Xiaobo; Chen Yaoqiang; Zhong Junbo; Wang Jianli; Zhao Ming; Gong Maochu

    2007-01-01

    A series of low noble-metal content monolithic catalysts for exhaust purification of small gasoline engines was investigated, and it was found that the Pt/Rh-OSM/Al2O3 (where OSM was oxygen storage material) catalyst with Ce0.5Zr0.5-MnOx(3%MnOx) OSM held low light-off temperature for CO, HC, and NO;quite wide three-way window, and outstanding thermal stability. The catalyst could efficiently control exhaust emission of small gasoline engines.

  20. Synthesis and characterization of mesoporous hydrocracking catalysts

    Science.gov (United States)

    Munir, D.; Usman, M. R.

    2016-08-01

    Mesoporous catalysts have shown great prospective for catalytic reactions due to their high surface area that aids better distribution of impregnated metal. They have been found to contain more adsorption sites and controlled pore diameter. Hydrocracking, in the presence of mesoporous catalyst is considered more efficient and higher conversion of larger molecules is observed as compared to the cracking reactions in smaller microporous cavities of traditional zeolites. In the present study, a number of silica-alumina based mesoporous catalysts are synthesized in the laboratory. The concentration and type of surfactants and quantities of silica and alumina sources are the variables studied in the preparation of catalyst supports. The supports prepared are well characterized using SEM, EDX, and N2-BET techniques. Finally, the catalysts are tested in a high pressure autoclave reactor to study the activity and selectivity of the catalysts for the hydrocracking of a model mixture of plastics comprising of LDPE, HDPE, PP, and PS.

  1. EFFECTS OF CATALYST MORPHOLOGY ON HYDROTREATING REACTIONS

    Directory of Open Access Journals (Sweden)

    TYE CHING THIAN

    2008-08-01

    Full Text Available Due to the new environmental regulations for fuel quality, refineries need to process cleaner fuel. This requires an improvement in performance of hydrotreating catalysts. Improvements in catalyst activity require knowledge of the relationships between catalyst morphology and activity. Molybdenum sulfide, the generally agreed catalysts that give the best performance in hydrocracking and hydrotreating was investigated for its morphology effects on hydrotreating reactions. Three types of MoS2 catalysts with different morphology were studied. They are crystalline MoS2, exfoliated MoS2 and MoS2 derived from a precursor, molybdenum naphthenate. Exfoliated MoS2 with minimal long range order, with much higher rim edges has shown relative higher hydrogenation activity. Generally, results of MoS2 catalyst activities in hydrogenation, hydrodesulfurization, hydrodenitrogenation and hydrideoxy¬gena¬tion are in agreement with the rim-edge model.

  2. RNA Nanoparticles Derived from Three-Way Junction of Phi29 Motor pRNA Are Resistant to I-125 and Cs-131 Radiation

    Science.gov (United States)

    Li, Hui; Rychahou, Piotr G.; Cui, Zheng; Pi, Fengmei; Evers, B. Mark; Shu, Dan

    2015-01-01

    Radiation reagents that specifically target tumors are in high demand for the treatment of cancer. The emerging field of RNA nanotechnology might provide new opportunities for targeted radiation therapy. This study investigates whether chemically modified RNA nanoparticles derived from the packaging RNA (pRNA) three-way junction (3WJ) of phi29 DNA-packaging motor are resistant to potent I-125 and Cs-131 radiation, which is a prerequisite for utilizing these RNA nanoparticles as carriers for targeted radiation therapy. pRNA 3WJ nanoparticles were constructed and characterized, and the stability of these nanoparticles under I-125 and Cs-131 irradiation with clinically relevant doses was examined. RNA nanoparticles derived from the pRNA 3WJ targeted tumors specifically and they were stable under irradiation of I-125 and Cs-131 with clinically relevant doses ranging from 1 to 90 Gy over a significantly long time up to 20 days, while control plasmid DNA was damaged at 20 Gy or higher. PMID:26017686

  3. Three-way complex variant translocation involving short arm chromosome (1;9;22)(p36;q34;q11) in a chronic myeloid leukemia patient

    Science.gov (United States)

    ASIF, MUHAMMAD; HUSSAIN, ABRAR; MALIK, ARIF; RASOOL, MAHMOOD

    2015-01-01

    Chronic myeloid leukemia (CML) is a disease of the clonal hematopoietic stem cells caused by a balanced translocation between the long arms of chromosomes 9 and 22. Overall, 90–95% of CML patients present with a Philadelphia (Ph) chromosome t(9;22)(q34;q11) translocation and in addition, variant complex translocations, involving a third chromosome, are observed in 5–8% of CML patients. Cytogenic testing using bone marrow sample was performed and the FISH test was used for the detection of BCR-ABL fusion gene and complete blood analysis of CML patient was also performed. Results of hematological analysis showed the induced values of white blood cells (168,5000/mm3) and platelets (300,000/mm3) and FISH analysis test showed that 98% cells were positive for BCR/ABL gene translocation. The present study describes a three-way (1;9;22)(p36;q34;q11) Ph chromosome translocation in a 24-year-old female with CML. The patient, who was in the chronic phase of the disease, was treated with daily dose of 400 mg/dl with imatinib mesylateand was monitored constantly at various intervals over a 6-month period. Many studies reported that certain CML patents with variant translocation responded poorly to imatinib. In the current case report, the CML patient exhibited a suboptimal response to imatinib, denoting a poor prognosis. PMID:26622740

  4. A signal-on electrochemical aptasensor for ultrasensitive detection of endotoxin using three-way DNA junction-aided enzymatic recycling and graphene nanohybrid for amplification

    Science.gov (United States)

    Bai, Lijuan; Chai, Yaqin; Pu, Xiaoyun; Yuan, Ruo

    2014-02-01

    Endotoxin, also known as lipopolysaccharide (LPS), is able to induce a strong immune response on its internalization into mammalian cells. To date, aptamer-based biosensors for LPS detection have been rarely reported. This work describes a new signal-on electrochemical aptasensor for the ultrasensitive detection of LPS by combining the three-way DNA hybridization process and nanotechnology-based amplification. With the help of DNA1 (associated with the concentration of target LPS), the capture probe hybridizes with DNA1 and the assistant probe to open its hairpin structure and form a ternary ``Y'' junction structure. The DNA1 can be released from the structure in the presence of nicking endonuclease to initiate the next hybridization process. Then a great deal of cleaved capture probe produced in the cyclic process can bind with DNA2-nanocomposite, which contains the electroactive toluidine blue (Tb) with the amplification materials graphene (Gra) and gold nanoparticles (AuNPs). Thus, an enhanced electrochemical signal can be easily read out. With the cascade signal amplification, this newly designed protocol provides an ultrasensitive electrochemical detection of LPS down to the femtogram level (8.7 fg mL-1) with a linear range of 6 orders of magnitude (from 10 fg mL-1 to 50 ng mL-1). Moreover, the high sensitivity and specificity make this method versatile for the detection of other biomolecules by changing the corresponding sequences of the capture probe and the assistant probe.

  5. Genetic analysis of fertility restoration under CGMS system in rice (Oryza sativa L.) using three-way test-cross method

    Indian Academy of Sciences (India)

    Philip Shalini; Swaminathan Manonmani; Sabariappan Robin

    2015-03-01

    We studied the genetics of fertility restoration by producing three-way test cross (TWTC) hybrids involved different combinations of restorers, maintainers and partial restorers of rice. Pollen and spikelet fertility of 16 TWTC hybrids were studied. Six TWTC involving restorer/restorer combinations as male parents produced progenies with fertility levels ranging from complete to zero. No specific ratio of segregation was observed. The crosses involving maintainer/maintainer combinations as male parents showed fully fertile and partial fertile/sterile plants in their progenies. These could be due to nonallelic gene interactions for fertility restoration between the two restorer or maintainer parents, or due to the influence of some modifying genes in the nuclear genome. TWTC involving partial restorer / restorer and partial restorer/partial restorer as the male parents also produced fully fertile and partial fertile/sterile plants suggesting the complex genetics of fertility restoration in rice. There were no previous results depicting the complementation effects of maintainers for fertility restoration.

  6. Theoretical investigations of olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cundari, T.R.; Gordon, M.S. [North Dakota State Univ., Fargo, ND (United States)

    1992-01-01

    An ab initio analysis of the electronic structure of high-valent, transition-metal alkylidenes as models for olefin metathesis catalysts is presented. The catalyst models studied fall into three categories: {open_quotes}new{close_quotes} metathesis catalyst models-tetrahedral M(OH){sup 2}(XH)(CH{sub 2}) complexes; {open_quotes}old{close_quotes} metathesis catalyst models-tetrahedral MCl{sub 2}(Y)(CH{sub 2}) complexes and alkylidene-substituted Mo metathesis catalysts, Mo(OH){sub 2}(NH)(=C(H)Z). The effect on the bonding caused by modification of either the metal, ligands, or alkylidene substitutents is considered. 21 refs., 2 figs., 5 tabs.

  7. Bonding and vibrations of CH xO and CH x species ( x = 1-3) on a palladium nanoparticle representing model catalysts

    Science.gov (United States)

    Kozlov, Sergey M.; Cabeza, Gabriela F.; Neyman, Konstantin M.

    2011-04-01

    This computational study deals with the adsorption of CH3, CH2, CH, CH2OH, CH3O, CH2O and CHO species on a nanoparticle Pd79 that mimics experimentally investigated model Pd catalysts. We quantify structural, energetic and vibrational parameters of these adsorption complexes and analyse their dependence on the adsorption site. Most of the considered low coordinated adsorption sites are found to be favoured by 20-50 kJ/mol over the sites on (1 1 1) facets. Some of the studied species have distinguishable vibrational parameters at different adsorption sites of the model nanoparticle, making possible spectroscopic characterization of respective adsorption complexes.

  8. Hydrogenation of fast pyrolyis oil and model compounds in a two-phase aqueous organic system using homogeneous ruthenium catalysts

    NARCIS (Netherlands)

    Mahfud, F. H.; Ghijsen, F.; Heeres, H. J.

    2007-01-01

    The use of homogeneous ruthenium catalysts to hydrogenate the water-soluble fraction of pyrolysis oil is reported. Pyrolysis oil, which is obtained by fast pyrolysis of lignocellulosic biomass at 450-600 degrees C, contains significant amounts of aldehydes and ketones (e.g. 1-hydroxy-2-propanone (1)

  9. Mass-selected nanoparticles of PtxY as model catalysts for oxygen electroreduction

    DEFF Research Database (Denmark)

    Hernandez-Fernandez, Patricia; Masini, Federico; McCarthy, David Norman

    2014-01-01

    Low-temperature fuel cells are limited by the oxygen reduction reaction, and their widespread implementation in automotive vehicles is hindered by the cost of platinum, currently the best-known catalyst for reducing oxygen in terms of both activity and stability. One solution is to decrease the a...

  10. Modeling Geometric Arrangements of TiO2-Based Catalyst Substrates and Isotropic Light Sources to Enhance the Efficiency of a Photocatalystic Oxidation (PCO) Reactor

    Science.gov (United States)

    Richards, Jeffrey T.; Levine, Lanfang H.; Husk, Geoffrey K.

    2011-01-01

    The closed confined environments of the ISS, as well as in future spacecraft for exploration beyond LEO, provide many challenges to crew health. One such challenge is the availability of a robust, energy efficient, and re-generable air revitalization system that controls trace volatile organic contaminants (VOCs) to levels below a specified spacecraft maximum allowable concentration (SMAC). Photocatalytic oxidation (PCO), which is capable of mineralizing VOCs at room temperature and of accommodating a high volumetric flow, is being evaluated as an alternative trace contaminant control technology. In an architecture of a combined air and water management system, placing a PCO unit before a condensing heat exchanger for humidity control will greatly reduce the organic load into the humidity condensate loop ofthe water processing assembly (WPA) thereby enhancing the life cycle economics ofthe WPA. This targeted application dictates a single pass efficiency of greater than 90% for polar VOCs. Although this target was met in laboratory bench-scaled reactors, no commercial or SBIR-developed prototype PCO units examined to date have achieved this goal. Furthermore, the formation of partial oxidation products (e.g., acetaldehyde) was not eliminated. It is known that single pass efficiency and partial oxidation are strongly dependent upon the contact time and catalyst illumination, hence the requirement for an efficient reactor design. The objective of this study is to maximize the apparent contact time and illuminated catalyst surface area at a given reactor volume and volumetric flow. In this study, a Ti02-based photocatalyst is assumed to be immobilized on porous substrate panels and illumination derived from linear isotropic light sources. Mathematical modeling using computational fluid dynamics (CFD) analyses were performed to investigate the effect of: 1) the geometry and configuration of catalyst-coated substrate panels, 2) porosity of the supporting substrate, and 3

  11. Reduce NOx Emissions by Adsorber-Reduction Catalyst on Lean Burn Gasoline Engine

    Directory of Open Access Journals (Sweden)

    Dongpeng Yue

    2013-09-01

    Full Text Available The effect of a new catalyst system composed of traditional three way catalyst converter and adsorber-reduction catalysis converter on the emission characteristics and BSFC (Breake Specific Fuel Consumption- BSFCof a lean burn gasoline engine operated were investigated in this paper under different schemes of catalyst converter arrangement and different speeds and loads. The results show that the position of Three Way Catalyst is before the NOx adsorber Catalyst was the best scheme of catalyst converter arrangement. Which has the highest converter efficiency of reduction NOx emission in lean burn gasoline engine. The effects of speed on the exhaust emission and BSFC were also related to the ratio of lean burn time to rich burn time and the absolute value of both time of the adsorber-reduction catalyst converter. The load of the engine was the main influential factor to the exhaust emission characteristics and BSFC of lean burn gasoline engine, and the more load of the engine was, the more NOx emission , the less NOx conversion rate (CNOx and the better BSFC were.

  12. Foundation Flash Catalyst

    CERN Document Server

    Goralski, Greg

    2010-01-01

    This book offers an introduction to Flash Catalyst for designers with intermediate to advanced skills. It discusses where Catalyst sits within the production process and how it communicates with other programs. It covers all of the features of the Flash Catalyst workspace, teaching you how to create designs from scratch, how to build application designs and add functionality, and how to master the Catalyst/Flex workflow. * Introduces Flash Catalyst * Focuses on production process * Covers the interrelation between Flash Catalyst and Photoshop/Illustrator/Flex/Flash What you'll learn Starting f

  13. Effect of using a Planecta™ port with a three-way stopcock on the natural frequency of blood pressure transducer kits.

    Science.gov (United States)

    Fujiwara, Shigeki; Tachihara, Keiichi; Mori, Satoshi; Ouchi, Kentaro; Yokoe, Chizuko; Imaizumi, Uno; Morimoto, Yoshinari; Miki, Yoichiro; Toyoguchi, Izumi; Yoshida, Kazu-Ichi; Yokoyama, Takeshi

    2016-12-01

    Blood pressure transducer kits are equipped with two types of Planecta™ ports-the flat-type Planecta™ port (FTP) and the Planecta™ port with a three-way stopcock (PTS). We reported that FTP application decreased the natural frequency of the kits. However, Planecta™ is an invaluable tool as it prevents infection, ensures technical simplicity, and excludes air. Hence, an ideal Planecta™ port that does not decrease the frequency characteristics is required. As a first step in this direction, we aimed to assess the influence of PTSs on the natural frequency of blood transducer kits. A DTXplus transducer kit (DT4812J; Argon Medical Devices, TX, USA) was used along with ≥1 PTSs (JMS, Hiroshima, Japan), and the frequency characteristics were assessed. The natural frequency and damping coefficient of each kit were obtained by using frequency characteristics analysis software, and these parameters were evaluated by plotting them on Gardner's chart. Regardless of whether one or two PTSs were inserted, the natural frequency of the kits only slightly decreased (from 42.5 to 41.1 Hz, when 2 PTSs were used). Thus, the frequency characteristics of the kits with PTSs were adequate for pressure monitoring. The insertion of ≥2 FTPs in pressure transducer kits should be avoided, as they markedly decrease the natural frequency and lead to underdamping. However, the effect of PTS insertion in pressure transducer kits on the frequency characteristics is minimal. Thus, we found that the use of PTS markedly improved the frequency characteristics as compared to the use of FTP.

  14. Design of heterogeneous catalysts

    DEFF Research Database (Denmark)

    Frey, Anne Mette

    was inspired by a computational screening, suggesting that alloys such as Ni-Fe, Co-Ni, and Co-Fe should show superior activity to the industrially used nickel catalyst. Especially the Ni-Fe system was considered to be interesting, since such alloy catalysts should be both more active and cheaper than the Ni...... well, and the best catalyst prepared had a C5+ yield almost a factor of two higher than a standard air calcined Co catalyst. In the NH3-SCR reaction it is desirable to develop an active and stable catalyst for NOx removal in automotive applications, since the traditionally used vanadium-based catalyst...... pose an environmental risk. The focus was put on iron-containing zeolite catalysts, since these recently have shown great potential as catalysts for the process. A number of different zeolites were compared. BEA was found to be the most active, thus focus was put on this material. Different preparation...

  15. Sulphur condensation influence in Claus catalyst performance.

    Science.gov (United States)

    Mora, R L

    2000-12-01

    The Claus process is an efficient way of removing H(2)S from acid gas streams and this is widely practised in industries such as natural gas processing, oil refining and metal smelting. Increasingly strict pollution control regulations require maximum sulphur recovery from the Claus unit in order to minimise sulphur-containing effluent. The most widely used Claus catalyst in sulphur recovery units is non-promoted spherical activated alumina. Properties associated with optimum non-promoted Claus catalyst performance include high surface area, appropriate pore size distribution and enhanced physical properties. The objective of this paper is to outline a procedure in order to estimate Claus catalyst effectiveness after pore plugging due to sulphur condensation. Catalyst deactivation due to pore plugging by sulphur is modelled employing a Bethe lattice and its corresponding performance is described by means of a modified effectiveness factor. Model results show an improvement in the modified effectiveness factor due to modifications in catalyst porous structure.

  16. Pd Close Coupled Catalyst

    Institute of Scientific and Technical Information of China (English)

    Zhong Hua SHI; Mao Chu GONG; Yao Qiang CHEN

    2006-01-01

    A catalyst comprised novel high surface area alumina support was prepared to control emission of automobiles. The results showed that prepared catalyst could satisfy the requirements of a high performance close coupled catalyst for its good catalytic activity at low temperature and good stability at high temperature.

  17. Monte Carlo simulation of the PEMFC catalyst layer

    Institute of Scientific and Technical Information of China (English)

    WANG Hongxing; CAO Pengzhen; WANG Yuxin

    2007-01-01

    The performance of the polymer electrolyte membrane fuel cell (PEMFC) is greatly controlled by the structure of the catalyst layer.Low catalyst utilization is still a significant obstacle to the commercialization of the PEMFC.In order to get a fundamental understanding of the electrode structure and to find the limiting factor in the low catalyst utilization,it is necessary to develop the mechanical model on the effect of catalyst layer structure on the catalyst utilization and the performance of the PEMFC.In this work,the structure of the catalyst layer is studied based on the lattice model with the Monte Carlo simulation.The model can predict the effects of some catalyst layer components,such as Pt/C catalyst,electrolyte and gas pores,on the utilization of the catalyst and the cell performance.The simulation result shows that the aggregation of conduction grains can greatly affect the degree of catalyst utilization.The better the dispersion of the conduction grains,the larger the total effective area of the catalyst is.To achieve higher utilization,catalyst layer components must be distributed by means of engineered design,which can prevent aggregation.

  18. Effect of Low-fat Milk Consumption Compared to Apple Juice and Water on the Energy Intake Among 10-12-Year-Old Obese Boys: A Three-way Cross-over Clinical Trial

    Science.gov (United States)

    Mehrabani, Sanaz; Salehi-Abargouei, Amin; Asemi, Mehdi; Mehrabani, Sepideh; Feizi, Awat; Safavi, Seyyed Morteza

    2014-01-01

    Background: Appetite lowering characteristics of dairy have attracted scientists to look for its effect on energy intake particularly among children. In the present study, we tried to assess the effect of low-fat milk on total and short-term energy intake among obese boys in a randomized three-way cross-over clinical trial. Methods: A total of 34 obese 10-12-year-old boys were randomized to consume three beverages (low-fat milk, apple juice, or water) with a fixed energy breakfast for two consecutive days, 1 week apart. Ad libitum lunch was provided for subjects 5 h later. The energy intake from breakfast till lunch and total energy intake on intervention days, and 2 days after intervention were compared. Generalized linear model repeated measures procedure in which test beverages were considered as repeated factors. Results: Energy intake from breakfast till lunch was lower when low-fat milk consumption was included in the breakfast compared with water and apple juice (adjusted mean ± standard error: Low-fat milk = 1484.33 ± 15.30 Kcal, apple juice = 1543.39 ± 20.70 Kcal, water = 1606.6 ± 19.94 Kcal; P 0.05). Conclusions: One serving of low-fat milk might affect the energy intake in a short-term period. The possible effect of frequent consumption of dairy products on long-term energy intake among children is needed to be examined. PMID:25538836

  19. General Motors Phase II Catalyst System

    Energy Technology Data Exchange (ETDEWEB)

    Canale, R.P.; Winegarden, S.R.; Carlson, C.R.; Miles, D.L.

    1978-01-01

    Three-way catalysts provide a means of catalytically achieving lower NOx emission levels while maintaining good control of HC and CO emissions. However, very accurate control of air-fuel ratio is necessary. The precise air-fuel ratio control required is accomplished by employing a closed loop fuel metering system in conjunction with an exhaust gas sensor and an electronic control unit. To gain production experience with this type of system, General Motors is introducing it on two 1978 engine families sold in California. One is a 2.5 liter L-4 engine and the other is a 3.8 liter V-6 engine. Closed loop controlled carburetors are used on both systems. The components used on both systems are described and emission and fuel economy results are reviewed.

  20. Presenting a new kinetic model for methanol to light olefins reactions over a hierarchical SAPO-34 catalyst using the Langmuir–Hinshelwood–Hougen–Watson mechanism

    Science.gov (United States)

    Javad Azarhoosh, Mohammad; Halladj, Rouein; Askari, Sima

    2017-10-01

    In this study, a new kinetic model for methanol to light olefins (MTO) reactions over a hierarchical SAPO-34 catalyst using the Langmuir–Hinshelwood–Hougen–Watson (LHHW) mechanism was presented and the kinetic parameters was obtained using a genetic algorithm (GA) and genetic programming (GP). Several kinetic models for the MTO reactions have been presented. However, due to the complexity of the reactions, most reactions are considered lumped and elementary, which cannot be deemed a completely accurate kinetic model of the process. Therefore, in this study, the LHHW mechanism is presented as kinetic models of MTO reactions. Because of the non-linearity of the kinetic models and existence of many local optimal points, evolutionary algorithms (GA and GP) are used in this study to estimate the kinetic parameters in the rate equations. Via the simultaneous connection of the code related to modelling the reactor and the GA and GP codes in the MATLAB R2013a software, optimization of the kinetic models parameters was performed such that the least difference between the results from the kinetic models and experiential results was obtained and the best kinetic parameters of MTO process reactions were achieved. A comparison of the results from the model with experiential results showed that the present model possesses good accuracy.

  1. Presenting a new kinetic model for methanol to light olefins reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson mechanism.

    Science.gov (United States)

    Azarhoosh, Mohammad Javad; Halladj, Rouein; Askari, Sima

    2017-10-25

    In this study, a new kinetic model for methanol to light olefins (MTO) reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism was presented and the kinetic parameters was obtained using a genetic algorithm (GA) and genetic programming (GP). Several kinetic models for the MTO reactions have been presented. However, due to the complexity of the reactions, most reactions are considered lumped and elementary, which cannot be deemed a completely accurate kinetic model of the process. Therefore, in this study, the LHHW mechanism is presented as kinetic models of MTO reactions. Because of the non-linearity of the kinetic models and existence of many local optimal points, evolutionary algorithms (GA and GP) are used in this study to estimate the kinetic parameters in the rate equations. Via the simultaneous connection of the code related to modelling the reactor and the GA and GP codes in the MATLAB R2013a software, optimization of the kinetic models parameters was performed such that the least difference between the results from the kinetic models and experiential results was obtained and the best kinetic parameters of MTO process reactions were achieved. A comparison of the results from the model with experiential results showed that the present model possesses good accuracy.

  2. Modeling the cathode in a proton exchange membrane fuel cell using density functional theory How the carbon support can affect durability and activity of a platinum catalyst

    Science.gov (United States)

    Groves, Michael Nelson

    The current global energy and environmental challenges need to be addressed by developing a new portfolio of clean power producing devices. The proton exchange membrane fuel cell has the potential to be included and can fit into a variety of niches ranging from portable electronics to stationary residential applications. One of the many barriers to commercial viability is the cost of the cathode layer which requires too much platinum metal to achieve a comparable power output as well as would need to be replaced more frequently when compared to conventional sources for most applications. Using density functional theory, an ab initio modeling technique, these durability and activity issues are examined for platinum catalysts on graphene and carbon nanotube supports. The carbon supports were also doped by replacing individual carbon atoms with other second row elements (beryllium, boron, nitrogen, and oxygen) and the effect on the platinum-surface interaction along with the interaction between the platinum and the oxygen reduction reaction intermediates are discussed. Keywords: proton exchange membrane fuel cell, density functional theory, platinum catalyst, oxygen reduction reaction, doped carbon surfaces

  3. Novel Oxidative Desulfurization of a Model Fuel with H2O2 Catalyzed by AlPMo12O40 under Phase Transfer Catalyst-Free Conditions

    Directory of Open Access Journals (Sweden)

    Márcio José da Silva

    2013-01-01

    Full Text Available A novel process was developed for oxidative desulfurization (ODS in the absence of a phase transfer catalyst (PTC using only Keggin heteropolyacids and their aluminum salts as catalysts. Reactions were performed in biphasic mixtures of isooctane/acetonitrile, with dibenzothiophene (DBT as a model sulfur compound and hydrogen peroxide as the oxidant. Remarkably, only the AlPMo12O40-catalyzed reactions resulted in complete oxidation of DBT into DBT sulfone, which was totally extracted by acetonitrile, reducing the sulfur content of isooctane from the 1000 ppm to  H3PMo12O40 > AlPW12O40 > H3PW12O40. The absence of a PTC, acidic organic peroxides, and the use of hydrogen peroxide, an environmentally benign oxidant, make up the positive aspects of AlPMo12O40-catalyzed ODS reactions. In these reactions, high rates of DBT removal (ca. 100% were achieved within a short time (ca. 2 hours and under mild reaction conditions.

  4. Influence of supports on catalytic behavior of nickel catalysts in carbon dioxide reforming of toluene as a model compound of tar from biomass gasification.

    Science.gov (United States)

    Kong, Meng; Fei, Jinhua; Wang, Shuai; Lu, Wen; Zheng, Xiaoming

    2011-01-01

    A series of supported Ni catalysts including Ni/MgO, Ni/γ-Al2O3, Ni/α-Al2O3, Ni/SiO2 and Ni/ZrO2 was tested in CO2 reforming of toluene as a model compound of tar from biomass gasification in a fluidized bed reactor, and characterized by the means of temperature programmed reduction with hydrogen (H2-TPR), XRD, TEM and temperature programmed oxidation (TPO). Combining the characterization results with the performance tests, the activity of catalyst greatly depended on Ni particles size, and the stability was affected by the coke composition. Both of them (Ni particle size and coke composition) were closely related to the interaction between nickel and support which would determine the chemical environment where Ni inhabited. The best catalytic performance was observed on Ni/MgO due to the strong interaction between NiO and MgO via the formation of Ni-Mg-O solid solution, and the highest dispersion of Ni particle in the basic environment.

  5. DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov

    2009-02-20

    The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst shows the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable

  6. DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov

    2009-03-03

    The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst shows the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  8. Catalyst Alloys Processing

    Science.gov (United States)

    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.

  9. Resin Catalyst Hybrids

    Institute of Scientific and Technical Information of China (English)

    S. Asaoka

    2005-01-01

    @@ 1Introduction: What are resin catalyst hybrids? There are typically two types of resin catalyst. One is acidic resin which representative is polystyrene sulfonic acid. The other is basic resin which is availed as metal complex support. The objective items of this study on resin catalyst are consisting of pellet hybrid, equilibrium hybrid and function hybrid of acid and base,as shown in Fig. 1[1-5].

  10. Classification of jet fuels by fuzzy rule-building expert systems applied to three-way data by fast gas chromatography--fast scanning quadrupole ion trap mass spectrometry.

    Science.gov (United States)

    Sun, Xiaobo; Zimmermann, Carolyn M; Jackson, Glen P; Bunker, Christopher E; Harrington, Peter B

    2011-01-30

    A fast method that can be used to classify unknown jet fuel types or detect possible property changes in jet fuel physical properties is of paramount interest to national defense and the airline industries. While fast gas chromatography (GC) has been used with conventional mass spectrometry (MS) to study jet fuels, fast GC was combined with fast scanning MS and used to classify jet fuels into lot numbers or origin for the first time by using fuzzy rule-building expert system (FuRES) classifiers. In the process of building classifiers, the data were pretreated with and without wavelet transformation and evaluated with respect to performance. Principal component transformation was used to compress the two-way data images prior to classification. Jet fuel samples were successfully classified with 99.8 ± 0.5% accuracy for both with and without wavelet compression. Ten bootstrapped Latin partitions were used to validate the generalized prediction accuracy. Optimized partial least squares (o-PLS) regression results were used as positively biased references for comparing the FuRES prediction results. The prediction results for the jet fuel samples obtained with these two methods were compared statistically. The projected difference resolution (PDR) method was also used to evaluate the fast GC and fast MS data. Two batches of aliquots of ten new samples were prepared and run independently 4 days apart to evaluate the robustness of the method. The only change in classification parameters was the use of polynomial retention time alignment to correct for drift that occurred during the 4-day span of the two collections. FuRES achieved perfect classifications for four models of uncompressed three-way data. This fast GC/fast MS method furnishes characteristics of high speed, accuracy, and robustness. This mode of measurement may be useful as a monitoring tool to track changes in the chemical composition of fuels that may also lead to property changes.

  11. A randomized three-way cross-over study in healthy pituitary-suppressed women to compare the bioavailability of human chorionic gonadotrophin (Pregnyl®) after intramuscular and subcutaneous administration

    NARCIS (Netherlands)

    Mannaerts, B.M.J.L.; Geurts, T.B.P.; Odink, J.

    1998-01-01

    The objective of this study was to compare the bioavailability of s.c. and i.m. administration of human chorionic gonadotrophin (HCG; Pregnyl®). In a randomized, single centre, three-way cross-over study, 18 healthy pituitary-suppressed volunteers were assigned to single HCG injections of 5000 and 1

  12. Novel micro-reactor flow cell for investigation of model catalysts using in situ grazing-incidence X-ray scattering

    DEFF Research Database (Denmark)

    Kehres, Jan; Pedersen, Thomas; Masini, Federico

    2016-01-01

    -incidence small-angle X-ray scattering (GISAXS) in transmission through 10 µm-thick entrance and exit windows by using micro-focused beams. An additional thinning of the Pyrex glass reactor lid allows simultaneous acquisition of the grazing-incidence wide-angle X-ray scattering (GIWAXS). In situ experiments......The design, fabrication and performance of a novel and highly sensitive micro-reactor device for performing in situ grazing-incidence X-ray scattering experiments of model catalyst systems is presented. The design of the reaction chamber, etched in silicon on insulator (SIO), permits grazing...... at synchrotron facilities are performed utilizing the micro-reactor and a designed transportable gas feed and analysis system. The feasibility of simultaneous in situ GISAXS/GIWAXS experiments in the novel micro-reactor flow cell was confirmed with CO oxidation over mass-selected Ru nanoparticles....

  13. Modelling Methods of Magnetohydrodynamic Phenomena Occurring in a Channel of the Device Used to Wash Out the Spent Automotive Catalyst by a Liquid Metal

    Directory of Open Access Journals (Sweden)

    Fornalczyk A.

    2016-06-01

    Full Text Available The recovery of precious metals is necessary for environmental and economic reasons. Spent catalysts from automotive industry containing precious metals are very attractive recyclable material as the devices have to be periodically renovated and eventually replaced. This paper presents the method of removing platinum from the spent catalytic converters applying lead as a collector metal in a device used to wash out by using mangetohydrodynamic stirrer. The article includes the description of the methods used for modeling of magnetohydrodynamic phenomena (coupled analysis of the electromagnetic, temperature and flow fields occurring in this particular device. The paper describes the general phenomena and ways of coupling the various physical fields for this type of calculation. The basic computational techniques with a discussion of their advantages and disadvantages are presented.

  14. Recent Developments in Doping and Structural Modification of Ceria-Based Catalysts

    Institute of Scientific and Technical Information of China (English)

    Feng Changgen; Fan Guodong

    2005-01-01

    Recent development in the modification of ceria-based catalysts for exhaust gas treatment was reviewed with the dependence of redox properties on structural characters of materials. The doping of ceria with different cations such as rare earth or transition metal oxides results in improvement of structural stability, catalytic function and resistance to sintering at high temperatures. Aging and reduction treatment at high temperatures promote ceria reduction and is beneficial for oxygen storage capacity of the three-way catalysts. Chemical filing technique is very effective in modifying the redox property in the low temperature regions.

  15. Near Critical Catalyst Reactant Branching Processes with Controlled Immigration

    CERN Document Server

    Budhiraja, Amarjit

    2012-01-01

    Near critical catalyst-reactant branching processes with controlled immigration are studied. The reactant population evolves according to a branching process whose branching rate is proportional to the total mass of the catalyst. The bulk catalyst evolution is that of a classical continuous time branching process; in addition there is a specific form of immigration. Immigration takes place exactly when the catalyst population falls below a certain threshold, in which case the population is instantaneously replenished to the threshold. Such models are motivated by problems in chemical kinetics where one wants to keep the level of a catalyst above a certain threshold in order to maintain a desired level of reaction activity. A diffusion limit theorem for the scaled processes is presented, in which the catalyst limit is described through a reflected diffusion, while the reactant limit is a diffusion with coefficients that are functions of both the reactant and the catalyst. Stochastic averaging principles under ...

  16. FY 1997 report on the development of excellent catalysts for creation of new industries. New frontier catalyst 21; 1997 nendo chosa hokokusho (shinsangyo sosei no tame no excellence catalyst no kaihatsu). New frontier catalyst 21

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-03-01

    Survey was made for establishment of an effective fast search technique of practical catalysts. Catalyst technology is an important basic technology for industrial fields such as energy and environment fields. In many cases, catalysts have been developed by trial and error consuming a long time and huge research cost. Study was made on efficient analysis and measurement techniques, and systematic production technique of advanced catalysts based on these techniques. This survey was effective in finding a guidance for improving catalysts used in the previous processes, and facilitating searches for fields previously slow in development of catalysts. Advanced catalysts possible to actively selectively produce target products under high pressure/temperature conditions are much in demand. Recently in-situ analysis technology for observing molecules and material surfaces under ultrahigh-pressure/temperature conditions has been studied. Observational study was made on catalytic behavior under catalytic reaction condition using partial oxidation, selective hydrogenation and isomerization as model reactions. 111 refs., 103 figs., 9 tabs.

  17. Mechanism of NO decomposition on perovskite (-like) catalysts

    Institute of Scientific and Technical Information of China (English)

    ZHU Junjiang; XIAO Dehai; LI Jing; YANG Xiangguang; WU Yue

    2005-01-01

    @@ NOx emitting from industrial and mobile exhaust are serious pollutant in air atmosphere, and the removal of them is an urgent task of today in environment-protection field[1,2]. Although the present three-way-catalyst (TWC)can remove NOx from the mobile exhaust effectively, it will be out of work as lean-burn strategies are used to increase energy efficiency (for example, the diesel engine operated in the lean-burn condition), hence, the technology that can remove NOx in the presence of excess oxygen is desired[3]. In addition, because the capability of noblemetal catalyst for NOx removal is weak at high temperatures (>873 K)[4], it is thus necessary to comprehend the process of NOx decomposition, which would help to solve the problem of NOx removal.

  18. Phenomenological-based kinetics modelling of dehydrogenation of ethylbenzene to styrene over a Mg 3 Fe 0.25 Mn 0.25 Al 0.5 hydrotalcite catalyst

    KAUST Repository

    Hossain, Mohammad M.

    2012-05-18

    This communication reports a mechanism-based kinetics modelling for the dehydrogenation of ethylbenzene to styrene (ST) using Mg3Fe0.25Mn0.25Al0.5 catalyst. Physicochemical characterisation of the catalyst indicates that the presence of basic sites Mg2+O2- on the catalysts along with Fe3+ is responsible for the catalytic activity. The kinetics experiments are developed using a CREC Fluidised Riser Simulator. Based on the experimental observations and the possible mechanism of the various elementary steps, Langmuir-Hinshelwood type kinetics model are developed. To take into account of the possible catalyst deactivation a reactant conversion-based deactivation function is also introduced into the model. Parameters are estimated by fitting of the experimental data implemented in MATLAB. Results show that one site type Langmuir-Hinshelwood model appropriately describes the experimental data, with adequate statistical fitting indicators and also satisfied the thermodynamic restraints. The estimated heat of adsorptions of EB (64kJ/mole) is comparable to the values available in the literature. The activation energy for the formation of ST (85.5kJ/mole) found to be significantly lower than that of the cracking product benzene (136.6kJ/mole). These results are highly desirable in order to achieve high selectivity of the desired product ST. © 2012 Canadian Society for Chemical Engineering.

  19. A new kinetic model based on the remote control mechanism to fit experimental data in the selective oxidation of propene into acrolein on biphasic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Abdeldayem, H.M.; Ruiz, P.; Delmon, B. [Unite de Catalyse et Chimie des Materiaux Divises, Universite Catholique de Louvain, Louvain-La-Neuve (Belgium); Thyrion, F.C. [Unite des Procedes Faculte des Sciences Appliquees, Universite Catholique de Louvain, Louvain-La-Neuve (Belgium)

    1998-12-31

    A new kinetic model for a more accurate and detailed fitting of the experimental data is proposed. The model is based on the remote control mechanism (RCM). The RCM assumes that some oxides (called `donors`) are able to activate molecular oxygen transforming it to very active mobile species (spillover oxygen (O{sub OS})). O{sub OS} migrates onto the surface of the other oxide (called `acceptor`) where it creates and/or regenerates the active sites during the reaction. The model contains tow terms, one considering the creation of selective sites and the other the catalytic reaction at each site. The model has been tested in the selective oxidation of propene into acrolein (T=380, 400, 420 C; oxygen and propene partial pressures between 38 and 152 Torr). Catalysts were prepared as pure MoO{sub 3} (acceptor) and their mechanical mixtures with {alpha}-Sb{sub 2}O{sub 4} (donor) in different proportions. The presence of {alpha}-Sb{sub 2}O{sub 4} changes the reaction order, the activation energy of the reaction and the number of active sites of MoO{sub 3} produced by oxygen spillover. These changes are consistent with a modification in the degree of irrigation of the surface by oxygen spillover. The fitting of the model to experimental results shows that the number of sites created by O{sub SO} increases with the amount of {alpha}-Sb{sub 2}O{sub 4}. (orig.)

  20. A fluid dynamic model for catalyst flow in riser of a FCC cold pilot unity is validated by gamma ray transmission measurements

    Energy Technology Data Exchange (ETDEWEB)

    Souza Netto, Wilson F. de; Brito, Marcio F. P.; Dantas, Carlos C.; Silva, Jose Marcos F. da; Freitas, Romero B., E-mail: wilson.netto@ufpe.br, E-mail: jmfs5@yahoo.com.br, E-mail: romero.borgesf@gmail.com, E-mail: ccd@ufpe.br, E-mail: marciopaixaobrito@hotmail.com [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil); Santos, Valdemir A. dos, E-mail: vas@unicap.br [Universidade Catolica de Pernambuco (UNICAP), Recife, PE (Brazil). Dept. de Quimica; Barbosa, Enivaldo S., E-mail: enivaldo@dem.ufcg.edu.br [Universidade Federal de Campina Grande (UFCG), Campina Grande, PB (Brazil). Unidade Academica de Engenharia Mecanica

    2013-07-01

    An one-dimensional model was previously used to describe solid flow and operational conditions tests. By radial gamma ray profile a two-dimensional model was evaluated taken volumetric solid fraction as experimental parameters. Literature data provide a first test for solution of the two-dimensional model equations. Then, Axial and radial catalyst profiles were measured by gamma ray transmission in the riser of the Cold Flow Pilot Unit. For fluid flow, the mathematical model is established based on the equations of conservation of momentum and mass. However, in multicomponent flows, one should have a correction factor in these equations taking into account the influence of each component in the flow. This factor is the volumetric fraction of each component. The volumetric fraction of solids was obtained by measuring the pressure profile and calculating the solids specific mass relative to riser volume. With the technique of gamma transmission radiation could be measured in one single point of the riser, direct measurement, then several points to get a more precise axial profile and better definition. The data obtained were used as parameters for the differential equations of fluid dynamic model and MATLAB solved. (author)

  1. Ceramic catalyst materials

    Energy Technology Data Exchange (ETDEWEB)

    Sault, A.G.; Gardner, T.J. [Sandia National Laboratories, Albuquerque, NM (United States); Hanprasopwattanna, A.; Reardon, J.; Datye, A.K. [Univ. of New Mexico, Albuquerque, NM (United States)

    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.

  2. Magnetic catalyst bodies

    NARCIS (Netherlands)

    Teunissen, Wendy; Bol, A.A.; Geus, John W.

    2001-01-01

    After a discussion about the importance of the size of the catalyst bodies with reactions in the liquid-phase with a suspended catalyst, the possibilities of magnetic separation are dealt with. Deficiencies of the usual ferromagnetic particles are the reactivity and the clustering of the particles.

  3. External Catalyst Breakup Phenomena

    Science.gov (United States)

    1976-06-01

    14-18 Mesh Catalyst 127 4-12 Hot Gas Thermal Fatigue Test Results for 25-30 Mesh Catalyst 128 4-13 Hot Gas Thermal Aging Test Results 131 - 19 - LISI ...magnitude of the thermal and internal pressure solution3, These solucions siu- Li.L fti’r oir =ztcrii ad the pressure and temperature profiles of

  4. Catalyst for Ammonia Oxidation

    DEFF Research Database (Denmark)

    2015-01-01

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

  5. Reducible oxide based catalysts

    Science.gov (United States)

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

    2010-04-06

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

  6. Alloy catalyst material

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention relates to a novel alloy catalyst material for use in the synthesis of hydrogen peroxide from oxygen and hydrogen, or from oxygen and water. The present invention also relates to a cathode and an electrochemical cell comprising the novel catalyst material, and the process use...

  7. Optimal catalyst curves: Connecting density functional theory calculations with industrial reactor design and catalyst selection

    DEFF Research Database (Denmark)

    Jacobsen, C.J.H.; Dahl, Søren; Boisen, A.

    2002-01-01

    For ammonia synthesis catalysts a volcano-type relationship has been found experimentally. We demonstrate that by combining density functional theory calculations with a microkinetic model the position of the maximum of the volcano curve is sensitive to the reaction conditions. The catalytic...... ammonia synthesis activity, to a first approximation, is a function only of the binding energy of nitrogen to the catalyst. Therefore, it is possible to evaluate which nitrogen binding energy is optimal under given reaction conditions. This leads to the concept of optimal catalyst curves, which illustrate...... the nitrogen binding energies of the optimal catalysts at different temperatures, pressures, and synthesis gas compositions. Using this concept together with the ability to prepare catalysts with desired binding energies it is possible to optimize the ammonia process. In this way a link between first...

  8. Performance of Co/MgO catalyst for CO2 reforming of toluene as a model compound of tar derived from biomass gasification

    Institute of Scientific and Technical Information of China (English)

    Xiuxiu Bao; Meng Kong; Wen Lu; Jinhua Fei∗; Xiaoming Zheng

    2014-01-01

    Catalytic performances of the CO2 reforming of toluene on Co/MgO catalysts with different cobalt loadings were evaluated in a fluidized-bed reactor. The results showed that the conversion of toluene and the stability of Co/MgO increased, but the apparent reaction rate decreased at the initial stage with increasing the amount of metallic Co formed from the reduction of Co/MgO catalysts at 700◦C. The deactivation of Co/MgO catalysts was mainly resulted from that a part of the metallic Co was oxidized by CO2 and could not be re-reduced by H2 at reaction temperature. Therefore, the excess metallic Co on the higher Co loading catalysts was beneficial to the catalyst stability.

  9. Highly sensitive silicon microreactor for catalyst testing

    DEFF Research Database (Denmark)

    Henriksen, Toke Riishøj; Olsen, Jakob Lind; Vesborg, Peter Christian Kjærgaard;

    2009-01-01

    by directing the entire gas flow through the catalyst bed to a mass spectrometer, thus ensuring that nearly all reaction products are present in the analyzed gas flow. Although the device can be employed for testing a wide range of catalysts, the primary aim of the design is to allow characterization of model...... catalysts which can only be obtained in small quantities. Such measurements are of significant fundamental interest but are challenging because of the low surface areas involved. The relationship between the reaction zone gas flow and the pressure in the reaction zone is investigated experimentally......, it is found that platinum catalysts with areas as small as 15 mu m(2) are conveniently characterized with the device. (C) 2009 American Institute of Physics. [doi:10.1063/1.3270191]...

  10. Catalysts, methods of making catalysts, and methods of use

    KAUST Repository

    Renard, Laetitia

    2014-03-06

    Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

  11. Three-way FMRI-DTI-methylation data fusion based on mCCA+jICA and its application to schizophrenia.

    Science.gov (United States)

    Sui, Jing; He, Hao; Liu, Jingyu; Yu, Qingbao; Adali, Tulay; Pearlson, Godfrey D; Calhoun, Vince D

    2012-01-01

    Multi-modal fusion is an effective approach in biomedical imaging which combines multiple data types in a joint analysis and overcomes the problem that each modality provides a limited view of the brain. In this paper, we propose an exploratory fusion model, we term "mCCA+jICA", by combining two multivariate approaches: multi-set canonical correlation analysis (mCCA) and joint independent component analysis (jICA). This model can freely combine multiple, disparate data sets and explore their joint information in an accurate and effective manner, so that high decomposition accuracy and valid modal links can be achieved simultaneously. We compared mCCA+jICA with its alternatives in simulation and applied it to real fMRI-DTI-methylation data fusion, to identify brain abnormalities in schizophrenia. The results replicate previous reports and add to our understanding of the neural correlates of schizophrenia, and suggest more generally a promising approach to identify potential brain illness biomarkers.

  12. Determination of tartrazine in beverage samples by stopped-flow analysis and three-way multivariate calibration of non-linear kinetic-spectrophotometric data.

    Science.gov (United States)

    Schenone, Agustina V; Culzoni, María J; Marsili, Nilda R; Goicoechea, Héctor C

    2013-06-01

    The performance of MCR-ALS was studied in the modeling of non-linear kinetic-spectrophotometric data acquired by a stopped-flow system for the quantitation of tartrazine in the presence of brilliant blue and sunset yellow FCF as possible interferents. In the present work, MCR-ALS and U-PCA/RBL were firstly applied to remove the contribution of unexpected components not included in the calibration set. Secondly, a polynomial function was used to model the non-linear data obtained by the implementation of the algorithms. MCR-ALS was the only strategy that allowed the determination of tartrazine in test samples accurately. Therefore, it was applied for the analysis of tartrazine in beverage samples with minimum sample preparation and short analysis time. The proposed method was validated by comparison with a chromatographic procedure published in the literature. Mean recovery values between 98% and 100% and relative errors of prediction values between 4% and 9% were indicative of the good performance of the method.

  13. Study on molecular modelling of the selectivity of catalysts for heavy petroleum fractions hydrocracking; Etude sur molecule modele des parametres regissant la selectivite des catalyseurs d'hydrocraquage des charges lourdes

    Energy Technology Data Exchange (ETDEWEB)

    Leite, L.

    2000-10-19

    Hydrocracking is a catalytic petroleum refining process that is commonly applied to upgrade the heavier fractions obtained from the distillation of crude oils. Nowadays the European demand for good quality middle distillates (kerosene and gas-oil) is high and one important goal for the refining is to transform selectively feedstocks into middle distillates. To understand how this transformation occurs, studies on model compounds have been investigated. Numerous studies have been devoted to paraffin hydrocracking. However theses molecules do not fully represent heavy petroleum fraction. Taking into account that the trend in the future will be to treat heavier feedstocks containing a large quantity of PNA (Polynuclear Aromatic hydrocarbons), the understanding of their transformation under hydrocracking conditions is a key point. In this study, we studied hydrocracking of phenanthrene over platinum on acid solids catalysts. Our main aim was to compare hydrocracking catalysts in term of catalytic activity and selectivity toward primary products thanks to our model reaction and to correlate these catalytic performances with acid solid properties and especially to rationalize the effects due to the acidity and the porosity of the acid solids. Catalytic experiments emphasised an effect of the porous structure on the selectivities. The acidity of the catalysts seemed to impose the catalytic activity but did not permit to explain the selectivities. This 'effect of the structure' has been clarified with the simulation of intermediate products adsorption and diffusion in the studied structures thanks to a molecular modelling study. Indeed, the selectivities obtained during phenanthrene hydrocracking have been linked up with the intermediate products adsorption energies in the structures. The results of this study permit to propose that the key-step for selectivities determination is the physical desorption of the primary products. (author)

  14. Impact of liquid water on oxygen reaction in cathode catalyst layer of proton exchange membrane fuel cell: A simple and physically sound model

    Science.gov (United States)

    Zhang, Xiaoxian; Gao, Yuan

    2016-06-01

    When cells work at high current density, liquid water accumulates in their catalyst layer (CL) and the gaseous oxygen could dissolve into the water and the ionomer film simultaneously; their associated dissolved concentrations in equilibrium with the gaseous oxygen are also different. Based on a CL acquired using tomography, we present new methods in this paper to derive agglomerate models for partly saturated CL by viewing the movement and reaction of the dissolved oxygen in the two liquids (water and ionomer) and the agglomerate as two independent random processes. Oxygen dissolved in the water moves differently from oxygen dissolved in the ionomer, and to make the analysis tractable, we use an average distribution function to describe the average movement of all dissolved oxygen. A formula is proposed to describe this average distribution function, which, in combination with the exponential distribution assumed in the literature for oxygen reaction, leads to a simple yet physically sound agglomerate model. The model has three parameters which can be directly calculated from CL structure rather than by calibration. We explain how to calculate these parameters under different water contents for a given CL structure, and analyse the impact of liquid water on cell performance.

  15. Modeling the effect of doping on the catalyst-assisted growth and field emission properties of plasma-grown graphene sheet

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Neha; Sharma, Suresh C.; Sharma, Rinku [Department of Applied Physics, Delhi Technological University (DTU), Shahbad Daulatpur, Bawana Road, Delhi-110042 (India)

    2016-08-15

    A theoretical model describing the effect of doping on the plasma-assisted catalytic growth of graphene sheet has been developed. The model accounts the charging rate of the graphene sheet, kinetics of all the plasma species, including the doping species, and the growth rate of graphene nuclei and graphene sheet due to surface diffusion, and accretion of ions on the catalyst nanoparticle. Using the model, it is observed that nitrogen and boron doping can strongly influence the growth and field emission properties of the graphene sheet. The results of the present investigation indicate that nitrogen doping results in reduced thickness and shortened height of the graphene sheet; however, boron doping increases the thickness and height of the graphene sheet. The time evolutions of the charge on the graphene sheet and hydrocarbon number density for nitrogen and boron doped graphene sheet have also been examined. The field emission properties of the graphene sheet have been proposed on the basis of the results obtained. It is concluded that nitrogen doped graphene sheet exhibits better field emission characteristics as compared to undoped and boron doped graphene sheet. The results of the present investigation are consistent with the existing experimental observations.

  16. Catalyst in Basic Oleochemicals

    Directory of Open Access Journals (Sweden)

    Eva Suyenty

    2007-10-01

    Full Text Available Currently Indonesia is the world largest palm oil producer with production volume reaching 16 million tones per annum. The high crude oil and ethylene prices in the last 3 – 4 years contribute to the healthy demand growth for basic oleochemicals: fatty acids and fatty alcohols. Oleochemicals are starting to replace crude oil derived products in various applications. As widely practiced in petrochemical industry, catalyst plays a very important role in the production of basic oleochemicals. Catalytic reactions are abound in the production of oleochemicals: Nickel based catalysts are used in the hydrogenation of unsaturated fatty acids; sodium methylate catalyst in the transesterification of triglycerides; sulfonic based polystyrene resin catalyst in esterification of fatty acids; and copper chromite/copper zinc catalyst in the high pressure hydrogenation of methyl esters or fatty acids to produce fatty alcohols. To maintain long catalyst life, it is crucial to ensure the absence of catalyst poisons and inhibitors in the feed. The preparation methods of nickel and copper chromite catalysts are as follows: precipitation, filtration, drying, and calcinations. Sodium methylate is derived from direct reaction of sodium metal and methanol under inert gas. The sulfonic based polystyrene resin is derived from sulfonation of polystyrene crosslinked with di-vinyl-benzene. © 2007 BCREC UNDIP. All rights reserved.[Presented at Symposium and Congress of MKICS 2007, 18-19 April 2007, Semarang, Indonesia][How to Cite: E. Suyenty, H. Sentosa, M. Agustine, S. Anwar, A. Lie, E. Sutanto. (2007. Catalyst in Basic Oleochemicals. Bulletin of Chemical Reaction Engineering and Catalysis, 2 (2-3: 22-31.  doi:10.9767/bcrec.2.2-3.6.22-31][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.2.2-3.6.22-31 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/6

  17. ALKALI RESISTANT CATALYST

    DEFF Research Database (Denmark)

    2008-01-01

    The present invention concerns the selective removal of nitrogen oxides (NOx) from gasses. In particular, the invention concerns a process, a catalyst and the use of a catalyst for the selective removal of nitrogen oxides in the presence of ammonia from gases containing a significant amount...... of alkali metal and/or alkali-earth compounds which process comprises using a catalyst combined of (i) a formed porous superacidic support, said superacidic support having an Hammett acidity stronger than Ho=-12, and (ii) a metal oxide catalytic component deposited on said superacidic support selected from...

  18. Ab Initio-Based Kinetic Modeling for the Design of Molecular Catalysts: The Case of H 2 Production Electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ho, Ming-Hsun; Rousseau, Roger; Roberts, John A. S.; Wiedner, Eric S.; Dupuis, Michel; DuBois, Daniel L.; Bullock, R. Morris; Raugei, Simone

    2015-09-04

    Design of fast, efficient electrocatalysts for energy production and energy utilization requires a systematic approach to predict and tune the energetics of reaction intermediates and the kinetic barriers between them as well as to tune reaction conditions (e.g., concentration of reactants, acidity of the reaction medium, and applied electric potential). Thermodynamics schemes based on the knowledge of pKa values, hydride donor ability, redox potentials, and other relevant thermodynamic properties have been demonstrated to be very effective for exploring possible reaction pathways. We seek to identify high-energy intermediates, which may represent a catalytic bottleneck, and low-energy intermediates, which may represent a thermodynamic sink. In this study, working on a well-established Ni-based bioinspired electrocatalyst for H2 production, we performed a detailed kinetic analysis of the catalytic pathways to assess the limitations of our current (standard state) thermodynamic analysis with respect to prediction of optimal catalyst performance. To this end, we developed a microkinetic model based on extensive ab initio simulations. The model was validated against available experimental data, and it reproduces remarkably well the observed turnover rate as a function of the acid concentration and catalytic conditions, providing valuable information on the main factors limiting catalysis. Using this kinetic analysis as a reference, we show that indeed a purely thermodynamic analysis of the possible reaction pathways provides us with valuable information, such as a qualitative picture of the species involved during catalysis, identification of the possible branching points, and the origin of the observed overpotential, which are critical insights for electrocatalyst design. However, a significant limitation of this approach is understanding how these insights relate to rate, which is an equally critical piece of information. Taking our analysis a step further, we show

  19. Three-way (N-way) fusion of brain imaging data based on mCCA+jICA and its application to discriminating schizophrenia.

    Science.gov (United States)

    Sui, Jing; He, Hao; Pearlson, Godfrey D; Adali, Tülay; Kiehl, Kent A; Yu, Qingbao; Clark, Vince P; Castro, Eduardo; White, Tonya; Mueller, Bryon A; Ho, Beng C; Andreasen, Nancy C; Calhoun, Vince D

    2013-02-01

    Multimodal fusion is an effective approach to better understand brain diseases. However, most such instances have been limited to pair-wise fusion; because there are often more than two imaging modalities available per subject, there is a need for approaches that can combine multiple datasets optimally. In this paper, we extended our previous two-way fusion model called "multimodal CCA+joint ICA", to three or N-way fusion, that enables robust identification of correspondence among N data types and allows one to investigate the important question of whether certain disease risk factors are shared or distinct across multiple modalities. We compared "mCCA+jICA" with its alternatives in a 3-way fusion simulation and verified its advantages in both decomposition accuracy and modal linkage detection. We also applied it to real functional Magnetic Resonance Imaging (fMRI)-Diffusion Tensor Imaging (DTI) and structural MRI fusion to elucidate the abnormal architecture underlying schizophrenia (n=97) relative to healthy controls (n=116). Both modality-common and modality-unique abnormal regions were identified in schizophrenia. Specifically, the visual cortex in fMRI, the anterior thalamic radiation (ATR) and forceps minor in DTI, and the parietal lobule, cuneus and thalamus in sMRI were linked and discriminated between patients and controls. One fMRI component with regions of activity in motor cortex and superior temporal gyrus individually discriminated schizophrenia from controls. Finally, three components showed significant correlation with duration of illness (DOI), suggesting that lower gray matter volumes in parietal, frontal, and temporal lobes and cerebellum are associated with increased DOI, along with white matter disruption in ATR and cortico-spinal tracts. Findings suggest that the identified fractional anisotropy changes may relate to the corresponding functional/structural changes in the brain that are thought to play a role in the clinical expression of

  20. Application of Ceria and Lanthana in Catalyst for Cleansing Exhaust Gas of Car

    Institute of Scientific and Technical Information of China (English)

    Yang Chunsheng; Chen Jianhua; Dai Shaojun

    2004-01-01

    The importanCe of rare earths being applied in the catalyst for cleansing the exhaust gas out of car was introduced. The acting mechanism of ceria and lanthana in catalyst and its influencing factors were discussed, and its prospect was forecasted. Pt-Rh precious metals three-way catalyst is widely used for decontaminating the exhaust gas of car now. Ceria and lanthana, which can decrease the content of Pt-Rh and increase the content of Pd in the catalyst, are used as additive in the decontaminating catalyst in order to solve the problem of the supply and demand of Pt and Rh.It is reported that increasing the activity of the coat on catalyst, regulating automatically the ratio of air and fuel, acting as catalyst-accelerator, and improving its properties such as thermal stability and strength may primarily amount for the catalyzing, mechanism of ceria and lanthana. The factors, such as their interaction, additive methods, and effects of cocatalyst ZrO2, CuO, AgO, etc. , will remarkably influence the catalyzing function of ceria and lanthana.

  1. Deactivation of platinum catalysts by oxygen 2. Nature of the catalyst deactivation

    Energy Technology Data Exchange (ETDEWEB)

    Dijkgraaf, P.J.M.; Duisters, H.A.M.; Kuster, B.F.M.; van der Wiele, K. (Univ. of Technology, Eindhoven (Netherlands))

    1988-08-01

    The effect of different start-up procedures on the deactivation of a 5% Pt/C catalyst used for the oxidation of D-gluconate has been investigated. Results have been obtained both in a stirred tank reactor for batch experiments and in an apparatus for continuous oxidation processes. The deactivation of the catalyst is not explicable by formation of platinum oxides. A model is proposed for the deactivation of platinum catalysts by oxygen, based on penetration of oxygen atoms into the platinum lattice.

  2. In situ characterization of cofacial Co(IV) centers in Co4O4 cubane: Modeling the high-valent active site in oxygen-evolving catalysts.

    Science.gov (United States)

    Brodsky, Casey N; Hadt, Ryan G; Hayes, Dugan; Reinhart, Benjamin J; Li, Nancy; Chen, Lin X; Nocera, Daniel G

    2017-03-27

    The Co4O4 cubane is a representative structural model of oxidic cobalt oxygen-evolving catalysts (Co-OECs). The Co-OECs are active when residing at two oxidation levels above an all-Co(III) resting state. This doubly oxidized Co(IV)2 state may be captured in a Co(III)2(IV)2 cubane. We demonstrate that the Co(III)2(IV)2 cubane may be electrochemically generated and the electronic properties of this unique high-valent state may be probed by in situ spectroscopy. Intervalence charge-transfer (IVCT) bands in the near-IR are observed for the Co(III)2(IV)2 cubane, and spectroscopic analysis together with electrochemical kinetics measurements reveal a larger reorganization energy and a smaller electron transfer rate constant for the doubly versus singly oxidized cubane. Spectroelectrochemical X-ray absorption data further reveal systematic spectral changes with successive oxidations from the cubane resting state. Electronic structure calculations correlated to experimental data suggest that this state is best represented as a localized, antiferromagnetically coupled Co(IV)2 dimer. The exchange coupling in the cofacial Co(IV)2 site allows for parallels to be drawn between the electronic structure of the Co4O4 cubane model system and the high-valent active site of the Co-OEC, with specific emphasis on the manifestation of a doubly oxidized Co(IV)2 center on O-O bond formation.

  3. Catalyst for microelectromechanical systems microreactors

    Science.gov (United States)

    Morse, Jeffrey D.; Sopchak, David A.; Upadhye, Ravindra S.; Reynolds, John G.; Satcher, Joseph H.; Gash, Alex E.

    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.

  4. Epoxidation catalyst and process

    Science.gov (United States)

    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.

  5. Design of an effective bifunctional catalyst organotriphosphonic acid-functionalized ferric alginate (ATMP-FA) and optimization by Box-Behnken model for biodiesel esterification synthesis of oleic acid over ATMP-FA.

    Science.gov (United States)

    Liu, Wei; Yin, Ping; Liu, Xiguang; Qu, Rongjun

    2014-12-01

    Biodiesel production has become an intense research area because of rapidly depleting energy reserves and increasing petroleum prices together with environmental concerns. This paper focused on the optimization of the catalytic performance in the esterification reaction of oleic acid for biodiesel production over the bifunctional catalyst organotriphosphonic acid-functionalized ferric alginate ATMP-FA. The reaction parameters including catalyst amount, ethanol to oleic acid molar ratio and reaction temperature have been optimized by response surface methodology (RSM) using the Box-Behnken model. It was found that the reaction temperature was the most significant factor, and the best conversion ratio of oleic acid could reach 93.17% under the reaction conditions with 9.53% of catalyst amount and 8.62:1 of ethanol to oleic acid molar ratio at 91.0 °C. The research results show that two catalytic species could work cooperatively to promote the esterification reaction, and the bifunctional ATMP-FA is a potential catalyst for biodiesel production.

  6. New Catalysts for ROMP

    Institute of Scientific and Technical Information of China (English)

    H. Berke; C. Frech; A. Lhamazares; O. Blacque; H.W. Schmalle; C. Adlhart; P. Chen

    2005-01-01

    @@ 1Introduction Ring Opening Metathesis Polymerization (ROMP) is based on the olefin metathesis reaction, which requires transition metal catalysts. Mainly molybdenum, tungsten and ruthenium based catalysts have up to now been used. The "in-between" metal rhenium was only rarely applied in olefin metathesis reactions, and not at all in ROMP processes.We have found that cationic phosphine substituted dinitrosyl rhenium complexes[1]1a and 1b effectively catalyze ROMP of norbonene, dicyclopentadiene and of cyclooctene. See Fig. 1.

  7. Stability and resistance of nickel catalysts for hydrodeoxygenation

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard; Gardini, Diego; de Carvalho, Hudson W. P.;

    2014-01-01

    of activity. Analysis of the spent catalyst revealed that the adsorption of chlorine on the catalyst was completely reversible, but chlorine had caused sintering of nickel particles. In two experiments, potassium, as either KCl or KNO3, was impregnated on the catalyst prior to testing. In both cases......The long term stability and resistance toward carbon deposition, sulfur, chlorine, and potassium of Ni/ZrO2 as a catalyst for the hydrodeoxygenation (HDO) of guaiacol in 1-octanol (as a model compound system for bio-oil) has been investigated at 250 degrees C and 100 bar in a trickle bed reactor...... setup. Without impurities in the feed good stability of the Ni/ZrO2 catalyst could be achieved over more than 100 h of operation, particularly for a sample prepared with small Ni particles, which minimized carbon deposition. Exposing the catalyst to 0.05 wt% sulfur in the feed resulted in rapid...

  8. On Three Ways to Justify Religious Beliefs

    NARCIS (Netherlands)

    Brümmer, V.

    2001-01-01

    This paper compares the ways in which revealed theology, natural theology and philosophical theology justify religious belief. Revealed theology does so with an appeal to revelation and natural theology with an appeal to reason and perception. It is argued that both are inadequate. Philosophical the

  9. Three Ways to Improve Listening Classes

    Institute of Scientific and Technical Information of China (English)

    邓林竹

    2014-01-01

    Recent years have witnessed numerous studies on how to improve learners’listening comprehension and how to ef-fectively teach listening classes. Despite these efforts, some problems still exist in listening teaching methods in China. In the first part of the essay, three issues in listening classes will be identified. Based on these issues, the second part present three correspond-ing methods of incorporating communicative-based activities, videos and checklists into teaching to improve listening classes. Each method will be justified by relevant theories and literature. A conclusion will be made in the end.

  10. Optimal catalyst curves: Connecting density functional theory calculations with industrial reactor design and catalyst selection

    DEFF Research Database (Denmark)

    Jacobsen, C.J.H.; Dahl, Søren; Boisen, A.

    2002-01-01

    For ammonia synthesis catalysts a volcano-type relationship has been found experimentally. We demonstrate that by combining density functional theory calculations with a microkinetic model the position of the maximum of the volcano curve is sensitive to the reaction conditions. The catalytic ammo......-principle quantum mechanical calculations of gas-surface interactions, reactor design, and catalyst selection has been established for the first time....

  11. Kinetic modeling and transient DRIFTS–MS studies of CO2 methanation over Ru/Al2O3 catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiang; Hong, Yongchun; Shi, Hui; Szanyi, János

    2016-11-01

    CO2 methanation was investigated on 5% and 0.5% Ru/Al2O3 catalysts (Ru dispersions: ~18% and ~40%, respectively) by steady-state kinetic measurements and transient DRIFTS–MS. Methanation rates were higher over 5% Ru/Al2O3 than over 0.5% Ru/Al2O3. The measured activation energies, however, were lower on 0.5% Ru/Al2O3 than on 5% Ru/Al2O3. Transient DRIFTS–MS results demonstrated that direct CO2 dissociation was negligible over Ru. CO2 has to first react with surface hydroxyls on Al2O3 to form bicarbonates, which, in turn, react with adsorbed H on Ru to produce adsorbed formate species. Formates, most likely at the metal/oxide interface, can react rapidly with adsorbed H forming adsorbed CO, only a portion of which is reactive toward adsorbed H, ultimately leading to CH4 formation. The measured kinetics are fully consistent with a Langmuir–Hinshelwood type mechanism in which the H-assisted dissociation of the reactive CO* is the rate-determining step (RDS). The similar empirical rate expressions (rCH4 = kP$0.1\\atop{CO2}$P$0.3-0.5\\atop{H2}$) and DRIFTS–MS results on the two catalysts under both transient and steady-state conditions suggest that the mechanism for CO2 methanation does not change with Ru particle size under the studied experimental conditions. Kinetic modeling results further indicate that the intrinsic activation barrier for the RDS is slightly lower on 0.5% Ru/Al2O3 than on 5% Ru/Al2O3. Due to the presence of unreactive adsorbed CO under reaction conditions, the larger fraction of such surface sites that bind CO too strongly on 0.5% Ru/Al2O3 than on 5% Ru/Al2O3, as revealed by FTIR measurements, is regarded as the main reason for the lower rates for CO2

  12. Correlations between (51)V solid-state NMR parameters and chemical structure of vanadium (V) complexes as models for related metalloproteins and catalysts.

    Science.gov (United States)

    Fenn, Annika; Wächtler, Maria; Gutmann, Torsten; Breitzke, Hergen; Buchholz, Axel; Lippold, Ines; Plass, Winfried; Buntkowsky, Gerd

    2009-12-01

    The parameters describing the quadrupolar and CSA interactions of 51V solid-state MAS NMR investigations of model complexes mimicking vanadoenzymes as well as vanadium containing catalysts and enzyme complexes are interpreted with respect to the chemical structure. The interpretation is based on the data of 15 vanadium complexes including two new complexes with previously unpublished data and 13 complexes with data previously published by us. Correlations between the chemical structure and the 51V solid-state NMR data of this class of compounds have been established. Especially for the isotropic chemical shift delta(iso) and the chemical shift anisotropy delta(sigma), correlations with specific structural features like the coordination number of the vanadium atom, the number of coordinating nitrogens, the number of oxygen atoms and the chemical surrounding of the complex could be established for these compounds. Moreover, quantitative correlations between the solid-state NMR parameters and specific bond angles and bond lengths have been obtained. Our results can be of particular interest for future investigations concerning the structure and the mode of action of related vanadoenzymes and vanadate protein assemblies, including the use of vanadate adducts as transition state analogs for phosphate metabolizing systems.

  13. An Atomic-Scale View of CO and H2 Oxidation on a Pt/Fe3 O4 Model Catalyst.

    Science.gov (United States)

    Bliem, Roland; van der Hoeven, Jessi; Zavodny, Adam; Gamba, Oscar; Pavelec, Jiri; de Jongh, Petra E; Schmid, Michael; Diebold, Ulrike; Parkinson, Gareth S

    2015-11-16

    Metal-support interactions are frequently invoked to explain the enhanced catalytic activity of metal nanoparticles dispersed over reducible metal oxide supports, yet the atomic-scale mechanisms are rarely known. In this report, scanning tunneling microscopy was used to study a Pt1-6/Fe3O4 model catalyst exposed to CO, H2, O2, and mixtures thereof at 550 K. CO extracts lattice oxygen atoms at the cluster perimeter to form CO2, creating large holes in the metal oxide surface. H2 and O2 dissociate on the metal clusters and spill over onto the support. The former creates surface hydroxy groups, which react with the support, ultimately leading to the desorption of water, while oxygen atoms react with Fe from the bulk to create new Fe3O4(001) islands. The presence of the Pt is crucial because it catalyzes reactions that already occur on the bare iron oxide surface, but only at higher temperatures.

  14. Analysis and Comparison of Concept Lattices from the Perspective of Three-Way Decisions%三支决策视角下概念格的分析和比较

    Institute of Scientific and Technical Information of China (English)

    李磊军; 李美争; 解滨; 米据生

    2016-01-01

    基于概念的构造和形式背景的构成,文中从三支决策的视角探究不同概念格之间的内在联系,分别对比不完备形式背景和经典形式背景中的概念格及直觉模糊形式背景和模糊形式背景中的概念格,展现三支决策在概念格理论中的重要价值。通过对比可以看出,相比经典形式背景和模糊形式背景中的概念格,不完备形式背景和直觉模糊形式背景中的概念格体现三支决策思想,具有数据存储所占空间更小,属性约简更简洁等优势。%Based on the construction of formal concepts and the constitution of formal contexts, the inherent connections between different concept lattices are explored from the perspective of three-way decisions. The comparison of the concept lattices in classical formal context and incomplete formal context, as well as in fuzzy formal context and intuitionistic fuzzy formal context, is given, respectively. Then, the important value of three-way decisions in concept lattice theory is shown. Compared with the concept lattices in classical formal context and fuzzy formal context, the concept lattices in incomplete formal context and intuitionistic fuzzy formal context can reflect the idea of three-way decisions, and they have advantages of small data storage requirement, concise attribute reduction, etc.

  15. Modeling Catalyst Preparation: The Structure of Impregnated-Dried Copper Chloride on γ-Alumina at Low Loadings

    NARCIS (Netherlands)

    Louwerse, M.J.; Rothenberg, G.

    2013-01-01

    The structure of uncalcined atomically dispersed copper(II) chloride on gamma-alumina is modeled with Density Functional Theory (DFT). Calculations are performed for the (110), (100), and (111) surfaces at several levels of hydration. The importance of the hydration and the uncertainties in the dehy

  16. Modeling Catalyst Preparation: The Structure of Impregnated-Dried Copper Chloride on γ-Alumina at Low Loadings

    NARCIS (Netherlands)

    Louwerse, M.J.; Rothenberg, G.

    2013-01-01

    The structure of uncalcined atomically dispersed copper(II) chloride on gamma-alumina is modeled with Density Functional Theory (DFT). Calculations are performed for the (110), (100), and (111) surfaces at several levels of hydration. The importance of the hydration and the uncertainties in the dehy

  17. Supported organoiridium catalysts for alkane dehydrogenation

    Science.gov (United States)

    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.

  18. Detection of unintended stress effects based on a metabonomic study in tomato fruits after treatment with carbofuran pesticide. Capabilities of MCR-ALS applied to LC-MS three-way data arrays.

    Science.gov (United States)

    Sánchez Pérez, Isidro; Culzoni, María J; Siano, Gabriel G; Gil García, María D; Goicoechea, Héctor C; Martínez Galera, María

    2009-10-15

    A chemometric strategy based on multivariate curve resolution and alternating least-squares (MCR-ALS) applied to LC-MS three-way data arrays has been developed to perform a metabonomic study in tomato (Lycopersicon esculentum) fruits (cultivar Rambo) following treatment with carbofuran. This methodology has proved to be adequate for the detection of unintended stress effects due to the previous treatment with this pesticide. MCR-ALS was performed on augmented matrices built with the LC-MS three-way data obtained from treated and nontreated samples through the sampling time. The strategy allowed us to obtain the concentration and spectra profiles of the main components (previously estimated with the SVD algorithm) from samples treated with pesticide as well as from blank samples, showing how they vary with time after plants treatment with the pesticide. In addition, a simple resolved mass spectrum was obtained corresponding to the peaks of a particular component in all matrices, thus avoiding ambiguity in the compound identity assignment. Different time profiles were found for some metabolites in treated and nontreated samples, which demonstrate that the presence of pesticide causes changes thorough time in the behavior of certain endogenous tomato metabolites as a result of physiological stress.

  19. Influences of Platinum Precursors and Solution Acidities on REO-Based Catalysts Performances

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Important effects exist between precious metals and rare earths oxides in three-way catalyst, especially the coordinated effects. These effects were studied by using H2PtCl6, Pt(NH3)2(NO2)2 and Pt(OH)2(C2H5ONH2)2 as Pt precursors, and the mixed oxide of (Ce-Zr-La-Pr)O as base material to prepare a series of catalysts, and their performances of the catalysts were studied by TPR and CO pulse titration technologies. The results shown that Pt precursors and their solutions pH values influenced the oxygen storage capabilities, the active metal distribution degrees of the catalysts obviously, and every catalyst prepared by different precursors had an optimal pH values. It indicates that the active metals precursors and their solutions acidities have outstanding influences on the catalysts performances for the mutual effects existing between the active metals and the Rare Earth metal oxides, which results from the mate groups of the precursors and the solution acidity.

  20. Experimental comparison of biomass chars with other catalysts for tar reduction

    NARCIS (Netherlands)

    Abu El-Rub, Z.; Bramer, E.A.; Brem, G.

    2008-01-01

    In this paper the potential of using biomass char as a catalyst for tar reduction is discussed. Biomass char is compared with other known catalysts used for tar conversion. Model tar compounds, phenol and naphthalene, were used to test char and other catalysts. Tests were carried out in a fixed bed

  1. Using degrees of rate control to improve selective n-butane oxidation over model MOF-encapsulated catalysts: sterically-constrained Ag 3 Pd(111)

    Energy Technology Data Exchange (ETDEWEB)

    Dix, Sean T. [Department of Chemical and Biomolecular Engineering; Clemson University; Clemson, USA; Scott, Joseph K. [Department of Chemical and Biomolecular Engineering; Clemson University; Clemson, USA; Getman, Rachel B. [Department of Chemical and Biomolecular Engineering; Clemson University; Clemson, USA; Campbell, Charles T. [Department of Chemistry; University of Washington; Seattle, USA

    2016-01-01

    that highly selectivity oxidation can sometimes be achieved by using a mixture of O2and H2O as the oxidant. This was further demonstrated by DRC analysis of a second microkinetic model based on a related but hypothetical catalyst, where the activation energies for two of the steps were modified.

  2. Mesoporous molecular sieve catalysts

    DEFF Research Database (Denmark)

    Højholt, Karen Thrane

    be used as solid acid catalysts but can also be used as a size-selective matrix. It was shown that it is possible to encapsulate 1-2 nm sized gold nanoparticles by silicalite-1 or ZSM-5 zeolite crystals thereby forming a sintering-stable and substrate size-selective oxidation catalyst. After carrying out...... calcination experiments, both in situ and ex situ indicated that the gold nanoparticles embedded in the crystals were highly stable towards sintering. The catalytic tests proved that the embedded gold nanoparticles were active in selective aldehyde oxidation and were only accessible through the micropores...

  3. Dynamics of Catalyst Nanoparticles

    DEFF Research Database (Denmark)

    Hansen, Thomas Willum; Cavalca, Filippo; Wagner, Jakob Birkedal

    under gas exposure, dynamic phenomena such as sintering and growth can be observed with sub-Ångstrøm resolution. Metal nanoparticles contain the active sites in heterogeneous catalysts, which are important for many industrial applications including the production of clean fuels, chemicals...... and pharmaceuticals, and the cleanup of exhaust from automobiles and stationary power plants. Sintering, or thermal deactivation, is an important mechanism for the loss of catalyst activity. In order to initiate a systematic study of the dynamics and sintering of nanoparticles, various catalytic systems have been...

  4. Aerogel derived catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Reynolds, J. G., LLNL

    1996-12-11

    Aerogels area class of colloidal materials which have high surface areas and abundant mesoporous structure. SiO{sub 2} aerogels show unique physical, optical and structural properties. When catalytic metals are incorporated in the aerogel framework, the potential exists for new and very effective catalysts for industrial processes. Three applications of these metal-containing SiO{sub 2} aerogels as catalysts are briefly reviewed in this paper--NO{sub x} reduction, volatile organic compound destruction, and partial oxidation of methane.

  5. Olefin metathesis catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S.G.; Banks, R.L.

    1986-05-20

    A process is described for preparing a disproportionation catalyst comprising admixing a catalytically effective amount of a calcined and activated catalyst consisting essentially of at least one metal oxide selected from molybdenum oxide and tungsten oxide and a support containing a major proportion of silica or alumina with a promoting amount of a methylating agent selected from the group consisting of dimethyl sulfate, dimethylsulfoxide, trimethyloxonium tetrafluorborate, methyl iodide, and methyl bromide, and subjecting same to inert atmospheric conditions for the methylating agent to promote the activity of the calcined molybdenum and tungsten oxides for the disproportionation of olefins.

  6. Collaboration between primitive cell membranes and soluble catalysts.

    Science.gov (United States)

    Adamala, Katarzyna P; Engelhart, Aaron E; Szostak, Jack W

    2016-03-21

    One widely held model of early life suggests primitive cells consisted of simple RNA-based catalysts within lipid compartments. One possible selective advantage conferred by an encapsulated catalyst is stabilization of the compartment, resulting from catalyst-promoted synthesis of key membrane components. Here we show model protocell vesicles containing an encapsulated enzyme that promotes the synthesis of simple fatty acid derivatives become stabilized to Mg(2+), which is required for ribozyme activity and RNA synthesis. Thus, protocells capable of such catalytic transformations would have enjoyed a selective advantage over other protocells in high Mg(2+) environments. The synthetic transformation requires both the catalyst and vesicles that solubilize the water-insoluble precursor lipid. We suggest that similar modified lipids could have played a key role in early life, and that primitive lipid membranes and encapsulated catalysts, such as ribozymes, may have acted in conjunction with each other, enabling otherwise-impossible chemical transformations within primordial cells.

  7. Conversion of polar and non-polar algae oil lipids to fatty acid methyl esters with solid acid catalysts--A model compound study.

    Science.gov (United States)

    Asikainen, Martta; Munter, Tony; Linnekoski, Juha

    2015-09-01

    Bio-based fuels are becoming more and more important due to the depleting fossil resources. The production of biodiesel from algae oil is challenging compared to terrestrial vegetable oils, as algae oil consists of polar fatty acids, such as phospholipids and glycolipids, as well as non-polar triglycerides and free fatty acids common in vegetable oils. It is shown that a single sulphonated solid acid catalyst can perform the esterification and transesterification reactions of both polar and non-polar lipids. In mild reaction conditions (60-70 °C) Nafion NR50 catalyst produces methyl palmitate (FAME) from the palmitic acid derivatives of di-, and tri-glyceride, free fatty acid, and phospholipid with over 80% yields, with the glycolipid derivative giving nearly 40% yields of FAME. These results demonstrate how the polar and non-polar lipid derivatives of algal oil can be utilised as feedstocks for biodiesel production with a single catalyst in one reaction step.

  8. Knowledge Based Catalyst Design by High Throughput Screening of Model Reactions and Statistical Modelling Conception de catalyseur par criblage à haut débit de réactions modèles et modélisation statistique

    Directory of Open Access Journals (Sweden)

    Morra G.

    2013-08-01

    Full Text Available Material design and synthesis are key steps in the development of catalysts. They are usually based on an empiric and/or theoretical approach. The recently developed high-throughput experimentation can accelerate optimisation of new catalytic formulations by systematic screening in a predefined study domain. This work aims at developing a QSAR (Quantitative Structure Activity Relationship method based on kinetic and mechanistic descriptors for metal and acid catalysis. Physico-chemicalfeatures of approximately sixty bimetallic catalysts have been measured according to their performance in two model reactions: xylene hydrogenation for catalysis on metallic sites and isomerisation of 3,3-dimethyl-l-butene for catalysis on acid sites. These descriptors were finally used to model the performances of around twenty catalysts for a more complex reaction: n-decane dehydrogenation. La définition et la préparation de matériaux sont des étapes clés dans le développement de catalyseurs. Celles-ci peuvent être effectuées de façon empirique et/ou à partir de bases théoriques. Par ailleurs, l’expérimentation à haut débit, technologie récente, permet d’accélérer l’optimisation de formulations catalytiques par exemple par criblage systématique d’un espace d’étude prédéfini. Cet article a pour objet de développer une méthode QSAR (Quantitative Structure Activity Relationship basée sur la recherche de descripteurs cinétiques et mécanistiques, dans le domaine de la catalyse acide et métallique supportée. Des caractéristiques physico-chimiques (descripteurs d’une soixantaine de catalyseurs bimétalliques ont été mesurées suivant leur performance dans deux réactions modèles : l’hydrogénation de ro-xylène pour rendre compte de la catalyse par le métal et l’isomérisation du diméthyl-3,3butène-1 pour la catalyse par les sites acides. Ces descripteurs ont été ensuite mis à profit pour modéliser les performances

  9. Sintering of nickel steam reforming catalysts

    DEFF Research Database (Denmark)

    Sehested, Jens; Larsen, Niels Wessel; Falsig, Hanne;

    2014-01-01

    . In this paper, particle migration and coalescence in nickel steam reforming catalysts is studied. Density functional theory calculations indicate that Ni-OH dominate nickel transport at nickel surfaces in the presence of steam and hydrogen as Ni-OH has the lowest combined energies of formation and diffusion...... compared to other potential nickel transport species. The relation between experimental catalyst sintering data and the effective mass diffusion constant for Ni-OH is established by numerical modelling of the particle migration and coalescence process. Using this relation, the effective mass diffusion...

  10. Deactivation-resistant catalyst for selective catalyst reduction of NOx

    DEFF Research Database (Denmark)

    2011-01-01

    The present invention relates to a catalyst for selective catalytic reduction of NOx in alkali metal containing flue gas using ammonia as reductant, the catalyst comprising a surface with catalytically active sites, wherein the surface is at least partly coated with a coating comprising at least...... one metal oxide. In another aspect the present invention relates to the use of said catalyst and to a method of producing said catalyst. In addition, the present invention relates to a method of treating an catalyst for conferring thereon an improved resistance to alkali poisoning....

  11. Removing lignin model pollutants with BiFeO3-g-C3N4 compound as an efficient visible-light-heterogeneous Fenton-like catalyst.

    Science.gov (United States)

    An, Junjian; Zhang, Guangyan; Zheng, Rongfeng; Wang, Peng

    2016-10-01

    BiFeO3-g-C3N4 nanoscaled composite was prepared with a hydrothermal method and evaluated as a highly efficient photo-Fenton like catalyst under visible light irradiation. The BiFeO3-g-C3N4 composite exhibited much stronger adsorption ability to lignin model pollutant (guaiacol) than that of BiFeO3, which may be due to the higher specific surface area (BiFeO3-g-C3N4: 35.59m(2)/g>BiFeO3: 7.42m(2)/g) and the adsorption form of π-π stack between g-C3N4 and guaiacol. The composite exhibited excellent visible light-Fenton like catalysis activity, being influenced by the solution pH value and the proportions of BiFeO3 and g-C3N4 nanosheets. Under optimal conditions with visible light irradiation, the BiFeO3-g-C3N4 composite yielded fast degradation of guaiacol with an apparent rate constant of 0.0452min(-1), which were 5.21 and 6.80 folds of that achieved by using BiFeO3 and the mixture of BiFeO3 and g-C3N4 nanosheets, respectively. The significantly enhanced visible light-Fenton like catalytic properties of the BiFeO3-g-C3N4 composite in comparison with that of BiFeO3 was attributed to a large surface area, much increased adsorption capacity and the semiconductor coupling effect between BiFeO3 and g-C3N4 in the composite. Copyright © 2016. Published by Elsevier B.V.

  12. Protein Scaffolding for Small Molecule Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Baker, David [Univ. of Washington, Seattle, WA (United States)

    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.

  13. Hydrogenation of xylose to xylitol on sponge nickel catalyst: a study of the process and catalyst deactivation kinetics

    Directory of Open Access Journals (Sweden)

    Mikkola J.-P.

    2003-01-01

    Full Text Available The kinetics of hydrogenation of xylose to xylitol on a sponge nickel catalyst (commonly referred to as Raney Ni catalyst and of catalyst deactivation were studied. Plausible explanations for the decrease in catalytic activity by means of surface studies, nitrogen adsorption and thermogravimetric analyses of the fresh and spent catalysts are presented. The kinetic parameters of the process were estimated by the use of a semi-competitive model, which allows full competition between the organic species and the hydrogen atoms for the adsorption sites on the catalyst surface (competitive case. In the model, a competitiveness factor (alpha is introduced to take into account that even after complete coverage of the surface by the organic species, interstitial sites remain for the adsorption of the hydrogen atoms.

  14. Balance of Nanostructure and Bimetallic Interactions in Pt Model Fuel Cell Catalysts: An in Situ XAS and DFT Study

    Energy Technology Data Exchange (ETDEWEB)

    Friebel, Daniel; Viswanathan, Venkatasubramanian; Miller, Daniel James; Anniyev, Toyli; Ogasawara, Hirohito; Larsen, Ask Hjorth; O' Grady, Christopher P.; Norskov, Jens K.; Nilsson, Anders

    2012-05-31

    We have studied the effect of nanostructuring in Pt monolayer model electrocatalysts on a Rh(111) single-crystal substrate on the adsorption strength of chemisorbed species. In situ high energy resolution fluorescence detection X-ray absorption spectroscopy at the Pt L(3) edge reveals characteristic changes of the shape and intensity of the 'white-line' due to chemisorption of atomic hydrogen (H(ad)) at low potentials and oxygen-containing species (O/OH(ad)) at high potentials. On a uniform, two-dimensional Pt monolayer grown by Pt evaporation in ultrahigh vacuum, we observe a significant destabilization of both H(ad) and O/OH(ad) due to strain and ligand effects induced by the underlying Rh(111) substrate. When Pt is deposited via a wet-chemical route, by contrast, three-dimensional Pt islands are formed. In this case, strain and Rh ligand effects are balanced with higher local thickness of the Pt islands as well as higher defect density, shifting H and OH adsorption energies back toward pure Pt. Using density functional theory, we calculate O adsorption energies and corresponding local ORR activities for fcc 3-fold hollow sites with various local geometries that are present in the three-dimensional Pt islands.

  15. Nanopore and nanoparticle catalysts.

    Science.gov (United States)

    Thomas, J M; Raja, R

    2001-01-01

    The design, atomic characterization, performance, and relevance to clean technology of two distinct categories of new nanocatalysts are described and interpreted. Exceptional molecular selectivity and high activity are exhibited by these catalysts. The first category consists of extended, crystallographically ordered inorganic solids possessing nanopores (apertures, cages, and channels), the diameters of which fall in the range of about 0.4 to about 1.5 nm, and the second of discrete bimetallic nanoparticles of diameter 1 to 2 nm, distributed more or less uniformly along the inner walls of mesoporous (ca. 3 to 10 nm diameter) silica supports. Using the principles and practices of solid-state and organometallic chemistry and advanced physico-chemical techniques for in situ and ex situ characterization, a variety of powerful new catalysts has been evolved. Apart from those that, inter alia, simulate the behavior of enzymes in their specificity, shape selectivity, regio-selectivity, and ability to function under ambient conditions, many of these new nanocatalysts are also viable as agents for effecting commercially significant processes in a clean, benign, solvent-free, single-step fashion. In particular, a bifunctional, molecular sieve nanopore catalyst is described that converts cyclohexanone in air and ammonia to its oxime and caprolactam, and a bimetallic nanoparticle catalyst that selectively converts cyclic polyenes into desirable intermediates. Nanocatalysts in the first category are especially effective in facilitating highly selective oxidations in air, and those in the second are well suited to effecting rapid and selective hydrogenations of a range of organic compounds.

  16. Heterogeneous chromium catalysts

    NARCIS (Netherlands)

    2005-01-01

    The present invention relates to a heterogeneous chromium catalyst system for the polymerisation of ethylene and/or alpha olefins prepared by the steps of: (a) providing a silica-containing support, (b) treating the silica-containing support with a chromium compound to form a chromium-based silica-c

  17. Olefin metathesis and catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S. G.; Banks, R. L.

    1985-05-14

    Olefins are converted into other olefins having different numbers of carbon atoms by contact with a catalyst comprising an inorganic refractory oxide support containing at least one of tungsten oxide and molybdenum oxide and a promoting amount of at least one methylating agent under conditions suitable for the methylating agent compounds to promote the activity of tungsten and molybdenum oxides for the disproportionation reaction.

  18. Deactivation of Oxidation Catalysts

    Science.gov (United States)

    1991-05-01

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

  19. Catalysts for Environmental Remediation

    DEFF Research Database (Denmark)

    Abrams, B. L.; Vesborg, Peter Christian Kjærgaard

    2013-01-01

    The properties of catalysts used in environmental remediation are described here through specific examples in heterogeneous catalysis and photocatalysis. In the area of heterogeneous catalysis, selective catalytic reduction (SCR) of NOx was used as an example reaction with vanadia and tungsta...

  20. Mechanism of general acid-base catalysis in transesterification of an RNA model phosphodiester studied with strongly basic catalysts.

    Science.gov (United States)

    Corona-Martínez, David O; Taran, Olga; Yatsimirsky, Anatoly K

    2010-02-21

    Using 80% vol aqueous DMSO as the reaction medium for transesterification of an RNA model substrate 2-hydroxypropyl 4-nitrophenyl phosphate allows one to observe catalysis in buffer mixtures composed of highly basic components such as guanidines, amidines or alkylamines, which provide up to 10(3)-fold accelerations over the background reaction in the 0.01-0.1 M concentration range. The rate law k(obs) = k(1)[B] + k(2)[B][BH(+)] was established indicating contributions from both simple general base catalysis and the reaction involving concerted action of neutral (B) and protonated (BH(+)) forms of the buffer. The catalytic efficiency of guanidinium and amidinium cations is 10 times larger than that of more acidic ammonium cations. Rate constants k(1) and k(2) obey the Brønsted equations with the slopes 0.77 and 0.69 respectively. Proton inventory for k(2) (B = guanidine) in D(2)O/H(2)O mixtures gives two fractionation factors phi(1) = 0.48 and phi(2) = 1.26 for normal and inverse isotope effects respectively. The former results from the proton transfer to B and the latter from the binding of guanidinium cation to the phosphate group as follows from observation of an inverse solvent isotope effect for the binding of guanidinium and amidinium cations to a phosphodiester anion. The results of kinetic studies together with analysis of transition state stabilization free energies for guanidinium and amidinium cations show that the protonated buffer component acts via electrostatic transition state stabilization rather than proton transfer, which may be possible for a guanidinium assisted hydroxide catalyzed reaction.

  1. Molybdenum sulfide/carbide catalysts

    Science.gov (United States)

    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.

  2. Synthesis of Arylzinc Thiolates Containing Perfluoroalkyl Chains : Model Catalyst Precursors for the Enantioselective Zinc-Mediated 1,2-Addition of Dialkylzincs to Aldehydes in Fluorous Biphase Systems

    NARCIS (Netherlands)

    Koten, G. van; Kleijn, H.; Rijnberg, E.; Jastrzebski, J.T.B.H.

    1999-01-01

    The synthesis of perfluoroalkyl-functionalized arene trimethylsilyl ethers and their conversion to ethylzinc thiolates is described. These compounds have been successfully applied as catalysts in the enantioselective addition of diethylzinc to benzaldehyde. This is the first example of a two-phase o

  3. 基于ANSYS软件三通管应力分布特性分析%The characteristics of stress distribution of three-way pipe based on ANSYS software

    Institute of Scientific and Technical Information of China (English)

    王培林

    2014-01-01

    应用有限元分析软件ANSYS10.0,对三通管应力进行计算分析,获得了内压作用下三通管的应力分布特性,在工程上,可以解决设备开孔部位是否需要加强的问题。%By the finite element analysis software ANSYS10.0, the stress of three-way pipe was calculated and the stress distribution was obtained under the action of internal pressure. It can solve the problem whether the hole position of the equipment needs to be strengthened in the project.

  4. Structure-activity correlations on Rh/Al{sub 2}O{sub 3} and Rh/TiO{sub 2} thin film model catalysts after oxidation and reduction

    Energy Technology Data Exchange (ETDEWEB)

    Rupprechter, G.; Seeber, G.; Goller, H.; Hayek, K. [Leopold-Franzens-Univ. Innsbruck (Austria). Inst. of Physical Chemistry

    1999-08-15

    A study of the effect of different supports on the stability and catalytic activity of Rh nanoparticles is only meaningful if the metal particles are perfectly identical in the catalysts to be compared. The authors have applied epitaxial thin film deposition to produce homogeneous distributions of well-faceted Rh nanocrystals, divided the sample in two, and subsequently supported the metal particles by Al{sub 2}O{sub 3} and TiO{sub 2}. Three corresponding pairs of Rh/Al{sub 2}O{sub 3} and Rh/TiO{sub 2} model catalysts with mean particle sizes of 7.8, 13.3, and 16.7 nm were prepared and activated by different oxidation-reduction treatments at temperatures up to 723 K. The size, morphology, and structure of the metal particles and of the support and the changes upon activation were determined by transmission electron microscopy. Wetting of the support and coalescence of Rh particles were observed to occur upon high-temperature reduction of large (>10 nm) and closely-spaced Rh particles, around 623 K on titania and around 723 K on alumina. Catalysts with smaller Rh particles did not show such pronounced changes. The rate of ring opening of methylcyclobutane at 373 K was measured on the three pairs of Rh/Al{sub 2}O{sub 3} and Rh/TiO{sub 2} model catalysts as a function of the reduction temperature after preoxidation at 723 K. Rh/alumina catalysts exhibited maximum activity after reduction at 523 K due to the formation of low-coordinated sites as shown by electron microscopy. The activity of Rh/titania peaked after reduction at 373 K and decreased almost exponentially with T{sub red} up to 673 K. In the case of Rh/titania, the changes in particle size and microstructure as observed in the electron microscope can only account for part of the kinetic results. The rapid activity decrease in titania-supported Rh particles with increasing T{sub red} is paralleled to an increase in the number of oxygen vacancies and in low-valent Ti cations, on the titania surface. The latter

  5. PILLARED CLAYS AS SUPERIOR CATALYSTS FOR SELECTIVE CATALYTIC REDUCTION OF NITRIC OXIDE

    Energy Technology Data Exchange (ETDEWEB)

    R.Q. Long; N. Tharappiwattananon; W.B. Li; R.T. Yang

    2000-09-01

    Removal of NO{sub x} (NO + NO{sub 2}) from exhaust gases is a challenging subject. V{sub 2}O{sub 5}-based catalysts are commercial catalysts for selective catalytic reduction (SCR) with NH{sub 3} for stationary sources. However, for diesel and lean-burn gasoline engines in vehicles, hydrocarbons would be the preferred reducing agents over NH{sub 3} because of the practical problems associated with the use of NH{sub 3} (i.e., handling and slippage through the reactor). The noble-metal three-way catalysts are not effective under these conditions. The first catalyst found to be active for selective catalytic reduction of NO by hydrocarbons in the presence of excess oxygen was copper exchanged ZSM-5 and other zeolites, reported in 1990 by Iwamoto in Japan and Held et al. in Germany. Although Cu-ZSM-5 is very active and the most intensively studied catalyst, it suffers from severe deactivation in engine tests, mainly due to H{sub 2}O and SO{sub 2}. In this project, we found that ion-exchanged pillared clays and MCM-41 catalysts showed superior SCR activities of NO with hydrocarbon. All Cu{sup 2+}-exchanged pillared clays showed higher SCR activities than Cu-ZSM-5 reported in the literature. In particular, H{sub 2}O and SO{sub 2} only slightly deactivated the SCR activity of Cu-TiO{sub 2}-PILC, whereas severe deactivation was observed for Cu-ZSM-5. Moreover, Pt/MCM-41 provided the highest specific NO reduction rates as compared with other Pt doped catalysts, i.e., Pt/Al{sub 2}O{sub 3}, Pt/SiO{sub 2} and Pt/ZSM-5. The Pt/MCM-41 catalyst also showed a good stability in the presence of H{sub 2}O and SO{sub 2}.

  6. Studies of Heterogeneous Catalyst Selectivity and Stability for Biorefining Applications

    Science.gov (United States)

    O'Neill, Brandon J.

    The conversion of raw resources into value-added end products has long underlain the importance of catalysts in economic and scientific development. In particular, the development of selective and stable heterogeneous catalysts is a challenge that continues to grow in importance as environmental, sociological, and economic concerns have motivated an interest in sustainability and the use of renewable raw materials. Within this context, biomass has been identified as the only realistic source of renewable carbon for the foreseeable future. The development of processes to utilize biomass feedstocks will require breakthroughs in fundamental understanding and practical solutions to the challenges related to selectivity and stability of the catalysts employed. Selectivity is addressed on multiple fronts. First, the selectivity for C-O bond scission reactions of a bifunctional, bimetallic RhRe/C catalyst is investigated. Using multiple techniques, the origin of Bronsted acidity in the catalyst and the role of pretreatment on the activity, selectivity, and stability are explored. In addition, reaction kinetics experiments and kinetic modeling are utilized to understand the role of chemical functional group (i.e. carboxylic acid versus formate ester) in determining the decarbonylation versus decarboxylation selectivity over a Pd/C catalyst. Finally, kinetic studies over Pd/C and Cu/gamma-Al2O3 were performed so that that may be paired with density functional theory calculations and microkinetic modeling to elucidate the elementary reaction mechanism, identify the active site, and provide a basis for future rational catalyst design. Next, the issue of catalyst stability, important in the high-temperature, liquid-phase conditions of biomass processing, is examined, and a method for stabilizing the base-metal nanoparticles of a Cu/gamma-Al2O 3 catalyst using atomic layer deposition (ALD) is developed. This advancement may facilitate the development of biorefining by enabling

  7. Fluorination process using catalysts

    Science.gov (United States)

    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.

  8. Fluorination process using catalyst

    Science.gov (United States)

    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.

  9. Photo catalyst; Ko shokubai

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-07-01

    While titanium oxide is excited by the light, electrons of titanium oxide are taken away by the light energy to form positive holes. Water will be decomposed into hydrogen ion and hydroxy radical (OH) by these positive holes. This hydroxy radical is a strong reactive substance called active oxygen, it decomposes organisms. Besides this photo- catalyst function, the titanium oxide can also make surface of a substance superhydrophilic. The super hydrophilicity results in not forming water drops on the glass surface but spreading all over the surface to prevent a covering of fog on the glass surface. The published patents concerning the photo catalysts were 593 from Jan. 1998 to Jan. 1999. The applicant order is the first TOTO 143, the second Daikin Industry 19, the third Toshiba Raitech, Nitto Denko, Hitachi 17 respectively. (NEDO)

  10. High-Activity Dealloyed Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kongkanand, Anusorn [General Motors LLC, Pontiac, MI (United States)

    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.

  11. Olefin metathesis and catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S. G.; Banks, R. L.

    1985-03-12

    Olefins are converted into other olefins having different numbers of carbon atoms by contact with a catalyst comprising an inorganic refractory material containing at least one of tungsten oxide and molybdenum oxide and a promoting amount of at least one treating agent selected from chlorinated silicon compounds, thionyl chloride, and sulfuryl chloride under conditions suitable for the treating agent to promote the activity of tungsten and molybdenum oxides for the disporoportionation reaction.

  12. Towards a Rational Design of a Continuous-Flow Method for the Acetalization of Crude Glycerol: Scope and Limitations of Commercial Amberlyst 36 and AlF3·3H2O as Model Catalysts

    Directory of Open Access Journals (Sweden)

    Sandro Guidi

    2016-05-01

    Full Text Available The acetalization of six different types of glycerol including pure, wet, and crude-like grade compounds of compositions simulating those of crude glycerols produced by the biodiesel manufacture, was carried out with two model ketones such as acetone and 2-butanone. The reaction was investigated under continuous-flow (CF conditions through a comparative analysis of an already known acetalization catalyst such as Amberlyst 36 (A36, and aluminum fluoride three hydrate (AlF3·3H2O, AF whose use was never previously reported for the synthesis of acetals. At 10 bar and 25 °C, A36 was a highly active catalyst allowing good-to-excellent conversion (85%–97% and selectivity (99% when either pure or wet glycerol was used as a reagent. This catalyst however, proved unsuitable for the CF acetalization of crude-like glycerol (CG since it severely and irreversibly deactivated in a few hours by the presence of low amounts of NaCl (2.5 wt % which is a typical inorganic impurity of raw glycerol from the biorefinery. Higher temperature and pressure (up to 100 °C and 30 bar were not successful to improve the outcome. By contrast, at 10 bar and 100 °C, AF catalyzed the acetalization of CG with both acetone and 2-butanone, yielding stable conversion and productivity up to 78% and 5.6 h−1, respectively. A XRD analysis of fresh and used catalysts proved that the active phase was a solid solution (SS of formula Al2[F1-x(OHx]6(H2Oy present as a component of the investigated commercial AF sample. A hypothesis to explain the role of such SS phase was then formulated based on the Brønsted acidity of OH groups of the solid framework. Overall, the AF catalyst allowed not only a straightforward upgrading of CG to acetals, but also a more cost-efficient protocol avoiding the expensive refining of raw glycerol itself.

  13. Towards a Rational Design of a Continuous-Flow Method for the Acetalization of Crude Glycerol: Scope and Limitations of Commercial Amberlyst 36 and AlF₃·3H₂O as Model Catalysts.

    Science.gov (United States)

    Guidi, Sandro; Noè, Marco; Riello, Pietro; Perosa, Alvise; Selva, Maurizio

    2016-05-18

    The acetalization of six different types of glycerol including pure, wet, and crude-like grade compounds of compositions simulating those of crude glycerols produced by the biodiesel manufacture, was carried out with two model ketones such as acetone and 2-butanone. The reaction was investigated under continuous-flow (CF) conditions through a comparative analysis of an already known acetalization catalyst such as Amberlyst 36 (A36), and aluminum fluoride three hydrate (AlF₃·3H₂O, AF) whose use was never previously reported for the synthesis of acetals. At 10 bar and 25 °C, A36 was a highly active catalyst allowing good-to-excellent conversion (85%-97%) and selectivity (99%) when either pure or wet glycerol was used as a reagent. This catalyst however, proved unsuitable for the CF acetalization of crude-like glycerol (CG) since it severely and irreversibly deactivated in a few hours by the presence of low amounts of NaCl (2.5 wt %) which is a typical inorganic impurity of raw glycerol from the biorefinery. Higher temperature and pressure (up to 100 °C and 30 bar) were not successful to improve the outcome. By contrast, at 10 bar and 100 °C, AF catalyzed the acetalization of CG with both acetone and 2-butanone, yielding stable conversion and productivity up to 78% and 5.6 h(-1), respectively. A XRD analysis of fresh and used catalysts proved that the active phase was a solid solution (SS) of formula Al₂[F1-x(OH)x]₆(H₂O)y present as a component of the investigated commercial AF sample. A hypothesis to explain the role of such SS phase was then formulated based on the Brønsted acidity of OH groups of the solid framework. Overall, the AF catalyst allowed not only a straightforward upgrading of CG to acetals, but also a more cost-efficient protocol avoiding the expensive refining of raw glycerol itself.

  14. Kinetic modeling of hydrogenation and hydro-denitrogenation mechanisms on sulfurated catalysts; Etude par modelisation cinetique des mecanismes d'hydrogenation et d'hydrodesazotation sur catalyseurs sulfures

    Energy Technology Data Exchange (ETDEWEB)

    Penet, H.

    1998-10-23

    Toluene hydrogenation on a NiMo/{gamma}-Al{sub 2}O{sub 3} catalyst was studied at 350 deg. C as a function of the partial pressures of H{sub 2}, H{sub 2}S and NH{sub 3}. This experimental study shows the following facts: the effect of the H{sub 2}S partial pressure on the hydrogenation rate is complex. The order with respect to H{sub 2}S varies between -0.05 and -0.5 as the pressure varies between 0.125 and 3 bar; in the presence of NH{sub 3}, the H{sub 2}S inhibiting effect is enhanced. Kinetic modeling was performed with the Chemkin II/Surface Chemkin II software package. On the basis of the effect of contact time and H{sub 2}S on toluene hydrogenation, the adsorption by heterolytic dissociation of H{sub 2} and H{sub 2}S was selected. H{sub 2} provides hydride species (H{sup -}) attacking the aromatic ring in a first step. Proton addition during the hydrogenation of the first double bond is the limiting step. In the presence of ammonia. the kinetic modeling shows that the catalyst surface is modified and that the displacement of the H{sub 2}S adsorption equilibrium is expected. The NH{sub 3} adsorption mode could not be clearly discriminated between a simple adsorption through coordination and an adsorption through protonation. This model was applied to the hydro-denitrogenation of 2,6-diethyl-aniline at 350 deg. C on NiMo/{gamma}-Al{sub 2}O{sub 3} catalyst and showed that the limitation step is the hydrogenation of the aromatic ring. (author)

  15. A Model gamma-Alumina-Supported Rhenium-Platinum Catalyst Prepared from [Re2Pt(CO)12]: 1. Synthesis and Spectroscopic Characterization.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Fung, A.S.; McDeVitt, M.R.; Tooley, P.A.; Kelley, M.J.; Gates, B.C.

    1993-01-01

    Catalysts supported on -Al2O3 were prepared from [Re2Pt(CO)12], and from Pt (NH3)4(NO3)2 and NH4ReO4. The former samples were characterized by infrared and X-ray photoelectron spectroscopies (XPS) and by temperature-programmed reduction (TPR); the latter were characterized by TPR. [Re2Pt(CO)12] was

  16. Three-Way Decision Clustering Algorithm for Incomplete Data Based on q-Nearest Neighbors%基于q近邻的不完备数据三支决策聚类方法

    Institute of Scientific and Technical Information of China (English)

    苏婷; 于洪

    2016-01-01

    聚类是数据挖掘的重要技术之一,在许多实际应用领域,由于数据获取限制,数据误读,随机噪音等原因会造成大量的缺失数据,形成数据集的不完备性,而传统的聚类方法无法直接对这类数据集进行聚类分析。针对数值型数据,提出了一个基于三支决策的不完备数据聚类方法。首先找到不完备数据对象的q个近邻,使用q个近邻的平均值填充缺失的数据;然后在“完备的”数据集上使用基于密度峰值的聚类方法得到簇划分,对每个簇中含有不确定性的数据对象,使用三支决策的思想将其划分到边界域中。三支决策聚类结果采用区间集形式表示,通常一个簇被划分成正域、负域和边界域部分,可以更好地描述软聚类结果。在UCI数据集和人工数据集上的实验结果展示了算法的有效性。%Clustering is a common technique for data analysis, and has been widely used in many practical areas. However, in many practical applications, there are some reasons to cause the missing values in real data sets such as difficulties and limitations of data acquisition and random noises. Most of clustering methods can’t be used to deal with incomplete data sets for clustering analysis directly. For this reason, this paper proposes a three-way decision clustering algorithm for incomplete data based on q-nearest neighbors. Firstly, the algorithm finds the q-nearest neighbors for an object with missing values, and the missing value is filled by the average value of q-nearest neighbors. Secondly, it uses the clustering method based on density peaks for the complete data set to obtain the clustering result. For the data object with uncertainty in each cluster, it is designed to the boundary region of a cluster using the three-way decision theory. The three-way decision with interval sets naturally partitions a cluster into three regions as the positive region, boundary region

  17. Aqueous-phase catalytic hydrogenation of furfural to cyclopentanol over Cu-Mg-Al hydrotalcites derived catalysts:Model reaction for upgrading of bio-oil

    Institute of Scientific and Technical Information of China (English)

    Minghao; Zhou; Zuo; Zeng; Hongyan; Zhu; Guomin; Xiao; Rui; Xiao

    2014-01-01

    A series of Cu-Mg-Al hydrotalcites derived oxides with a(Cu+Mg)/Al mole ratio of 3 and varied Cu/Mg mole ratio(from 0.07 to 0.30) were prepared by co-precipitation and calcination methods, then they were introduced to the hydrogenation of furfural in aqueous-phase. Effects of Cu/Mg mole ratio, reaction temperature, initial hydrogen pressure, reaction time and catalyst amount on the conversion rate of furfural as well as the selectivity toward desired product cyclopentanol were systematically investigated. The conversion of furfural over calcined hydrotalcite catalyst with a Cu/Mg mole ratio of 0.2 was up to 98.5% when the reaction was carried out under 140 ?C and the initial hydrogen pressure of 4 MPa for 10 h, while the selectivity toward cyclopentanol was up to 94.8%. The catalysts were characterized by XRD and SEM. XRD diffraction of all the samples showed characteristic pattern of hydrotalcite with varied peak intensity as a result of different Cu content. The catalytic activity was improved gradually with the increase of Cu component in the hydrotalcite.

  18. Deactivation by carbon of iron catalysts for indirect liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Bartholomew, C.H.

    1991-01-10

    Although promoted cobalt and iron catalysts for Fischer-Tropsch (FT) synthesis of gasoline feedstock were first developed more than three decades ago, a major technical problem still limiting the commercial use of these catalysts today is carbon deactivation. This report describes recent progress in a fundamental, three-year investigation of carbon formation and its effects on the activity and selectivity of promoted iron catalysts for FT synthesis, the objectives of which are to: determine rates and mechanisms of carbon deactivation of unsupported Fe and Fe/K catalysts during CO hydrogenation over a range of CO concentrations, CO:H{sub 2} ratios, and temperatures; and model the rates of deactivation of the same catalysts in fixed-bed reactors. To accomplish the above objectives, the project is divided into the following tasks: (1) determine the kinetics of reaction and of carbon deactivation during CO hydrogenation on Fe and Fe/K catalysts coated on monolith bodies. (2) Determine the reactivities and types of carbon deposited during reaction on the same catalysts from temperature-programmed-surface-reaction spectroscopy (TPSR) and transmission electron microscopy (TEM). Determine the types of iron carbides formed at various temperatures and H{sub 2}/CO ratios using x-ray diffraction and Moessbauer spectroscopy. (3) Develop mathematical deactivation models which include heat and mass transport contributions for FT synthesis is packed-bed reactors. Progress to date is described. 48 refs., 3 figs., 1 tab.

  19. Catalyst systems and uses thereof

    Science.gov (United States)

    Ozkan, Umit S.; Holmgreen, Erik M.; Yung, Matthew M.

    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.

  20. Development of GREET Catalyst Module

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhichao [Argonne National Lab. (ANL), Argonne, IL (United States); Benavides, Pahola T. [Argonne National Lab. (ANL), Argonne, IL (United States); Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States); Cronauer, Donald C. [Argonne National Lab. (ANL), Argonne, IL (United States)

    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

    Energy Technology Data Exchange (ETDEWEB)

    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. Privileged chiral ligands and catalysts

    CERN Document Server

    Zhou, Qi-Lin

    2011-01-01

    This ultimate ""must have"" and long awaited reference for every chemist working in the field of asymmetric catalysis starts with the core structure of the catalysts, explaining why a certain ligand or catalyst is so successful. It describes in detail the history, the basic structural characteristics, and the applications of these ""privileged catalysts"". A novel concept that gives readers a much deeper insight into the topic.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  4. Effect of vanadium on the deactivation of FCC catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Roncolatto, R.E.; Lam, Y.L. [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas. Div. de Catalisadores]. E-mail: roncolatto@cenpes.petrobras.com.br; y12@cenpes.petrobras.com.br

    1998-06-01

    This work provides concrete evidence that causes the destruction of the zeolite in the FCC catalysts by a mechanism of acid attack or solid-solid transformation, as well as additional dealumination of the zeolite framework in the presence of steam and at high temperature. While these effects resulted in the reduction in crystallinity (zeolite Y content), specific area and unit cell size of the Y zeolite as the amount of vanadium in the catalysts increased, the reduction in activity was the most pronounced. The differences in these behaviors were interpreted and the model can be used for better catalyst formulation or screening. (author)

  5. EFFECT OF VANADIUM ON THE DEACTIVATION OF FCC CATALYSTS

    Directory of Open Access Journals (Sweden)

    Roncolatto R.E

    1998-01-01

    Full Text Available This work provides concrete evidence that vanadium causes the destruction of the zeolite in the FCC catalysts by a mechanism of acid attack or solid-solid transformation, as well as additional dealumination of the zeolite framework in the presence of steam and at high temperature. While these effects resulted in the reduction in crystallinity (zeolite Y content, specific area and unit cell size of the Y zeolite as the amount of vanadium in the catalysts increased, the reduction in activity was the most pronounced. The differences in these behaviors were interpreted and the model can be used for better catalyst formulation or screening.

  6. Three-way, three-period, crossover bioequivalence study of single oral dose of three brands of 300 mg phenytoin sodium tablets marketed in India, on healthy Indian human volunteers

    Directory of Open Access Journals (Sweden)

    Maulik S Doshi

    2013-01-01

    Full Text Available Objective: To compare the bioavailability of two brands of phenytoin sodium tablets available in the Indian market using Eptoin TM as the reference. Materials and Methods: A randomized, assessor-blind, three-way crossover design study was carried out over a period of 6 months after approval from the Institutional Review Board (IRB. Twenty-two healthy male participants received a single oral 300 mg oral tablet of either of the formulations with a 2-week washout. Blood samples were collected predose and at regular intervals postdose. Plasma phenytoin levels were estimated by high-performance liquid chromatography. Calculation of C max , AUC 0-t , and AUC 0-∞ was done by the linear trapezoidal rule and 90-110% margin (90% confidence interval (CI was used to assess bioequivalence. Results: Twenty volunteers completed the study. It was seen that the log-transformed values of C max , AUC 0-t , and AUC 0-∞ of the test formulations were not within the specified limits. Conclusion: Bioinequivalence of available phenytoin brands indicates that switching brands could lead to variations in blood concentrations and thus impact safety and efficacy. If a brand switch is done for any reason, stringent drug-level monitoring is advised.

  7. Low-Temperature CO Oxidation on CuO/CeO2 Catalyst Prepared by Sol-Gel Method%溶胶-凝胶法制备CeO2负载CuO低温CO氧化催化剂

    Institute of Scientific and Technical Information of China (English)

    郑修成; 黄唯平; 张守民; 王淑荣; 吴世华

    2003-01-01

    Ceria is widely used as a promoter in "three-way catalysts" (TWC). The promotion effect of ceria was originally supposed to be in the structural aspects and chemical ones. Precious metals are widely used for exhaust gas emission control. However, because the high cost of precious metals and their sensitivity to sulfur poisoning, attention has been given to nonprecious metal catalysts such as copper oxide.

  8. REACTOR FILLED WITH CATALYST MATERIAL, AND CATALYST THEREFOR

    NARCIS (Netherlands)

    Sie, S.T.

    1995-01-01

    Abstract of WO 9521691 (A1) Described is a reactor (1) at least partially filled with catalyst granules (11), which is intended for catalytically reacting at least one gas and at least one liquid with each other. According to the invention the catalyst granules (11) are collected in agglomerates

  9. Polymer-Supported Raney Nickel Catalysts for Sustainable Reduction Reactions.

    Science.gov (United States)

    Jiang, Haibin; Lu, Shuliang; Zhang, Xiaohong; Dai, Wei; Qiao, Jinliang

    2016-01-01

    Green is the future of chemistry. Catalysts with high selectivity are the key to green chemistry. Polymer-supported Raney catalysts have been found to have outstanding performance in the clean preparation of some chemicals. For example, a polyamide 6-supported Raney nickel catalyst provided a 100.0% conversion of n-butyraldehyde without producing any detectable n-butyl ether, the main byproduct in industry, and eliminated the two main byproducts (isopropyl ether and methyl-iso-butylcarbinol) in the hydrogenation of acetone to isopropanol. Meanwhile, a model for how the polymer support brought about the elimination of byproducts is proposed and confirmed. In this account the preparation and applications of polymer-supported Raney catalysts along with the corresponding models will be reviewed.

  10. Polymer-Supported Raney Nickel Catalysts for Sustainable Reduction Reactions

    Directory of Open Access Journals (Sweden)

    Haibin Jiang

    2016-06-01

    Full Text Available Green is the future of chemistry. Catalysts with high selectivity are the key to green chemistry. Polymer-supported Raney catalysts have been found to have outstanding performance in the clean preparation of some chemicals. For example, a polyamide 6-supported Raney nickel catalyst provided a 100.0% conversion of n-butyraldehyde without producing any detectable n-butyl ether, the main byproduct in industry, and eliminated the two main byproducts (isopropyl ether and methyl-iso-butylcarbinol in the hydrogenation of acetone to isopropanol. Meanwhile, a model for how the polymer support brought about the elimination of byproducts is proposed and confirmed. In this account the preparation and applications of polymer-supported Raney catalysts along with the corresponding models will be reviewed.

  11. Computationally Probing the Performance of Hybrid, Heterogeneous, and Homogeneous Iridium-Based Catalysts for Water Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    García-Melchor, Max [SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford CA (United States); Vilella, Laia [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST),Tarragona (Spain); Departament de Quimica, Universitat Autonoma de Barcelona, Barcelona (Spain); López, Núria [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Tarragona (Spain); Vojvodic, Aleksandra [SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park CA (United States)

    2016-04-29

    An attractive strategy to improve the performance of water oxidation catalysts would be to anchor a homogeneous molecular catalyst on a heterogeneous solid surface to create a hybrid catalyst. The idea of this combined system is to take advantage of the individual properties of each of the two catalyst components. We use Density Functional Theory to determine the stability and activity of a model hybrid water oxidation catalyst consisting of a dimeric Ir complex attached on the IrO2(110) surface through two oxygen atoms. We find that homogeneous catalysts can be bound to its matrix oxide without losing significant activity. Hence, designing hybrid systems that benefit from both the high tunability of activity of homogeneous catalysts and the stability of heterogeneous systems seems feasible.

  12. Mechanochemistry, catalysis, and catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Butyagin, P.Yu.

    1987-07-01

    The physical basis of mechanochemistry and the reasons for the initiation and acceleration of chemical reactions upon the mechanical treatment of solids have been considered. The phenomenon of mechanical catalysis has been described in the example case of the oxidation of CO on oxide surfaces, and the nature of the active sites and the laws governing the mechanically activated chemisorption of gases on cleavage and friction surfaces of solids have been examined. The possibilities of the use of the methods of mechanochemistry in processes used to prepare catalysts have been analyzed in examples of decomposition reactions of inorganic compounds and solid-phase synthesis.

  13. Catalyst for the purification of exhaust gases of internal combustion engines

    Energy Technology Data Exchange (ETDEWEB)

    Bozon, A.; Koberstein, E.; Lakatos, E.; Pletka, H.; Volker, H.

    1981-10-13

    A three-way catalyst is described for the purification of automobile exhaust gases formed of an active substance of platinum and rhodium and possibly base metal(S) at a certain weight ratio between the two noble metals and at a certain atomic ratio between the noble and the base metal, which are precipitated onto active aluminum oxide containing certain quantities of CeO2, ZrO2 and Fe2O3, and whereby the catalyst is obtained by impregnating active aluminum oxide, possibly stabilized with alkaline earth metal, with a solution of cerium, zirconium and iron salt which is thereupon calcined in air at 500 degrees-700 degrees C. And then treated after application of impregnation of salts of the active substance components in a gas current containing hydrogen at temperatures below 650 degrees C.

  14. JV 58-Effects of Biomass Combustion on SCR Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Bruce C. Folkedahl; Christopher J. Zygarlicke; Joshua R. Strege; Donald P. McCollor; Jason D. Laumb; Lingbu Kong

    2006-08-31

    A portable slipstream selective catalytic reduction (SCR) reactor was installed at a biomass cofired utility boiler to examine the rates and mechanisms of catalyst deactivation when exposed to biomass combustion products. The catalyst was found to deactivate at a much faster rate than typically found in a coal-fired boiler, although this may have been the result of high ash loading rather than a general property of biomass combustion. Deactivation was mainly the result of alkali and alkaline-earth sulfate formation and growth in catalyst pores, apparently caused by alkaline-earth ash deposition on or near the pore sites. The high proportion of biomass in the fuel contributed to elevated levels of alkali and alkaline-earth material in the ash when compared to coal ash, and these higher levels provided more opportunity for sulfate formation. Based on laboratory tests, neither catalyst material nor ammonia contributed measurably to ash mass gains via sulfation. A model constructed using both field and laboratory data was able to predict catalyst deactivation of catalysts under subbituminous coal firing but performed poorly at predicting catalyst deactivation under cofiring conditions. Because of the typically higher-than coal levels of alkali and alkaline-earth elements present in biomass fuels that are available for sulfation at typical SCR temperatures, the use of SCR technology and biomass cofiring needs to be carefully evaluated prior to implementation.

  15. Dispersed catalysts for co-processing and coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Bockrath, B.; Parfitt, D.; Miller, R. [Pittsburgh Energy Technology Center, PA (United States)

    1995-12-31

    The basic goal is to improve dispersed catalysts employed in the production of clean fuels from low value hydrocarbons. The immediate objective is to determine how the properties of the catalysts may be altered to match the demands placed on them by the properties of the feedstock, the qualities of the desired end products, and the economic constraints put upon the process. Several interrelated areas of the application of dispersed catalysts to co-processing and coal conversion are under investigation. The first involves control of the selectivity of MoS{sub 2} catalysts for HDN, HDS, and hydrogenation of aromatics. A second area of research is the development and use of methods to evaluate dispersed catalysts by means of activity and selectivity tests. A micro-flow reactor has been developed for determining intrinsic reactivities using model compounds, and will be used to compare catalysts prepared in different ways. Micro-autoclaves will also be used to develop data in batch experiments at higher partial pressures of hydrogen. The third area under investigation concerns hydrogen spillover reactions between MoS{sub 2} catalysts and carbonaceous supports. Preliminary results obtained by monitoring H{sub 2}/D{sub 2} exchange reactions with a pulse-flow microreactor indicate the presence of spillover between MoS{sub 2} and a graphitic carbon. A more complete study will be made at a later stage of the project. Accomplishments and conclusions are discussed.

  16. Sulfur tolerant zeolite supported platinum catalysts for aromatics hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Bergem, Haakon

    1997-12-31

    The increased demand for transportation fuels at the expence of heavier fuel oil has forced the refinery industry to expand their conversion capacity with hydrotreating as one of the key processes. A shift towards more diesel powered vehicles along with tightening fuel regulations demanding cleaner fuels has lead to increasing interest in catalytic processes for the manufacturing of such environmentally acceptable fuels. This provides the motivation for this thesis. Its main objective was to study possible catalysts active for desulfurization, hydrogenation, and ring-opening of aromatics all in the presence of sulfur. A close examination of the physical properties and kinetical behaviour of the chosen catalysts has been performed. A high pressure reactor setup was designed and built for activity measurements. Zeolite supported platinum catalysts were prepared and both the metal and acid functions were characterized utilizing various experimental techniques. Hydrogenation of toluene was used as a model reaction and the effect of sulfur adsorption on the activity and kinetic behaviour of the catalysts was investigated. The catalyst samples showed hydrogenation activities comparable to a commercial Pt/Al2O3 catalyst. There were no clear differences in the effect of the various sulfur compounds studied. Platinum supported on zeolite Y gave considerably more sulfur tolerant catalysts compared to Al2O3 as support. 155 refs., 58 figs., 36 tabs.

  17. Growth of single-walled carbon nanotubes on a Co-Mo-MgO supported catalyst by the CVD of methane in a fixed bed reactor: Model setting and parameter estimation

    Science.gov (United States)

    Izadi, Nosrat; Rashidi, Ali Morad; Horri, Bahman Amini; Mosoudi, Mohamad Reza; Bozorgzadeh, Hamid Reza; Zeraatkar, Ahmad

    2011-06-01

    In this work methane was decomposed to hydrogen and carbon to determine its kinetic behavior during reaction over a Co-Mo-MgO supported catalyst using the CVD (Chemical Vapor Deposition) technique. Decomposition of methane molecules was performed in a continuous fixed bed reactor to obtain data to simulate methane decomposition in a gas phase heterogeneous media. The products and reactants of reaction were analyzed by molecular sieve column followed by GC-analysis of the fractions to determine the amount of product converted or reactant consumed. The synthesis of single-walled carbon nanotubes was performed at atmospheric pressure, different temperatures and reactant concentrations. The experimental data analyzed to suggest the formula for calculation of the initial specific reaction rate of the carbon nanotubes synthesis, were fitted by several mathematical models derived from different mechanisms based on Longmuir-hinshelwood expression. The suggested mechanism according to dissociation adsorption of methane seems to explain the catalytic performance in the range of operating conditions studied. The apparent activation energy for the growth of SWNTs was estimated according to Arrhenius equation. The as grown SWNTs products were characterized by SEM, TEM and Raman spectroscopy after purification. The catalyst deactivation was found to be dependent on the time, reaction temperature and partial pressure of methane and indicated that the reaction of deactivation can be modeled by a simple apparent second order of reaction.

  18. In-situ characterization of heterogeneous catalysts

    CERN Document Server

    Rodriguez, Jose A; Chupas, Peter J

    2013-01-01

    Helps researchers develop new catalysts for sustainable fuel and chemical production Reviewing the latest developments in the field, this book explores the in-situ characterization of heterogeneous catalysts, enabling readers to take full advantage of the sophisticated techniques used to study heterogeneous catalysts and reaction mechanisms. In using these techniques, readers can learn to improve the selectivity and the performance of catalysts and how to prepare catalysts as efficiently as possible, with minimum waste. In-situ Characterization of Heterogeneous Catalysts feat

  19. Crystal structure of a DNA catalyst.

    Science.gov (United States)

    Ponce-Salvatierra, Almudena; Wawrzyniak-Turek, Katarzyna; Steuerwald, Ulrich; Höbartner, Claudia; Pena, Vladimir

    2016-01-14

    Catalysis in biology is restricted to RNA (ribozymes) and protein enzymes, but synthetic biomolecular catalysts can also be made of DNA (deoxyribozymes) or synthetic genetic polymers. In vitro selection from synthetic random DNA libraries identified DNA catalysts for various chemical reactions beyond RNA backbone cleavage. DNA-catalysed reactions include RNA and DNA ligation in various topologies, hydrolytic cleavage and photorepair of DNA, as well as reactions of peptides and small molecules. In spite of comprehensive biochemical studies of DNA catalysts for two decades, fundamental mechanistic understanding of their function is lacking in the absence of three-dimensional models at atomic resolution. Early attempts to solve the crystal structure of an RNA-cleaving deoxyribozyme resulted in a catalytically irrelevant nucleic acid fold. Here we report the crystal structure of the RNA-ligating deoxyribozyme 9DB1 (ref. 14) at 2.8 Å resolution. The structure captures the ligation reaction in the post-catalytic state, revealing a compact folding unit stabilized by numerous tertiary interactions, and an unanticipated organization of the catalytic centre. Structure-guided mutagenesis provided insights into the basis for regioselectivity of the ligation reaction and allowed remarkable manipulation of substrate recognition and reaction rate. Moreover, the structure highlights how the specific properties of deoxyribose are reflected in the backbone conformation of the DNA catalyst, in support of its intricate three-dimensional organization. The structural principles underlying the catalytic ability of DNA elucidate differences and similarities in DNA versus RNA catalysts, which is relevant for comprehending the privileged position of folded RNA in the prebiotic world and in current organisms.

  20. STUDY ON THE CATALYTIC OXIDATIVE DESULFURIZATION OF MODEL GASOLINE OVER NIOBIC ACID CATALYST%酸处理铌酸催化模拟汽油氧化脱硫的研究

    Institute of Scientific and Technical Information of China (English)

    孙裕苹; 沈健

    2011-01-01

    以二苯并噻吩的异辛烷溶液为模拟油、过氧化氢为氧化剂,在密闭钢制反应釜反应器中,分别考察以水洗铌酸、硝酸处理铌酸、硝酸及磷酸处理铌酸为催化剂时的催化氧化脱硫性能.结果表明,硝酸及磷酸处理铌酸催化剂具有较高的催化活性和再生性能,在催化剂用量为5%、反应温度为60℃、反应时间为3h、氧化剂H2 O2与硫摩尔比为3、剂油体积比为1时,脱硫率可达96.34%.%Using dibenzothiophene containing isooctane as model oil and hydrogen peroxide as oxi-dant,the effect of three niobic acid catalysts (treated by water,nitric acid and nitric acid/phosphoric acid respectively) on the catalytic performance of oxidative desulfurization was investigated by a steel bomb reactor. Test results showed that niobic acid treated by nitric acid and phosphoric acid exhibited the best catalytic activity and stability among the three catalysts. Under the conditions of a catalyst dosage of 5% ,a reaction temperature of 60 t ,a reaction time of 3 h,a H2O2/S molar ratio of 3 and solvent to oil volume ratio of l,the desulfurization rate reached 96. 34%.

  1. Study and modelling of deactivation by coke in catalytic reforming of hydrocarbons on Pt-Sn/Al{sub 2}O{sub 3} catalyst; La microbalance inertielle: etude et modelisation cinetique de la desactivation par le coke en reformage catalytique des hydrocarbures sur catalyseur Pt-Sn/Al{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Mathieu-Deghais, S.

    2004-07-01

    Catalytic reforming is the refining process that produces gasoline with a high octane number. During a reforming operation, undesired side reactions promote the formation of carbon deposits (coke) on the surface of the catalyst. As the reactions proceed, the coke accumulation leads to a progressive decrease of the catalyst activity and to a change in its selectivity. Getting this phenomenon under control is interesting to optimize the industrial plants. This work aims to improve the comprehension and the modeling of coke formation and its deactivating effect on reforming reactions, while working under conditions chosen within a range as close as possible to the industrial conditions of the regenerative process. The experimental study is carried out with a micro unit that is designed to observe simultaneously the coke formation and its influence on the catalyst activity. A vibrational microbalance reactor (TEOM - Tapered Element Oscillating Microbalance) is used to provide continuous monitoring of coke. On-line gas chromatography is used to observe the catalyst activity and selectivity as a function of the coke content. The coking experiments are performed on a fresh Pt-Sn/alumina catalyst, with mixtures of hydrocarbon molecules of 7 carbon atoms as hydrocarbon feeds. The coking tests permitted to highlight the operating parameters that may affect the amount of coke, and to identify the hydrocarbon molecules that behave as coke intermediate. A kinetic model for coke formation could be developed through the compilation of these results. The catalytic activity analysis permitted to point out the coke effect on both of the active phases of the catalyst, to construct a simplified reforming kinetic model that simulates the catalyst activity under the reforming conditions, and to quantify deactivation via deactivation functions. (author)

  2. Characterization of pore network structure in catalyst layers of polymer electrolyte fuel cells

    OpenAIRE

    El Hannach, Mohamed; Soboleva, Tatyana; Malek, Kourosh; Franco, Alejandro A.; Prat, Marc; Pauchet, Joël; Holdcroft, Steven

    2014-01-01

    International audience; We model and validate the effect of ionomer content and Pt nanoparticles on nanoporous structure of catalyst layers in polymer electrolyte fuel cells. By employing Pore network modeling technique and analytical solutions, we analyze and reproduce experimental N2-adsorption isotherms of carbon, Pt/ carbon and catalyst layers with various ionomer contents. The porous catalyst layer structures comprise of Ketjen Black carbon, Pt and Nafion ionomer. The experimental pore s...

  3. Uniqueness of three-mode factor models with sparse cores : The 3x3x3 case

    NARCIS (Netherlands)

    Kiers, H.A.L.; ten Berge, J.M.F.; Rocci, R

    1997-01-01

    Three-Mode Factor Analysis (3MFA) and PARAFAC are methods to describe three-way data. Both methods employ models with components for the three modes of a three-way array; the 3MFA model also uses a three-way core array for linking all components to each other. The use of the core array makes the 3MF

  4. Nonproductive events in ring-closing metathesis using ruthenium catalysts.

    Science.gov (United States)

    Stewart, Ian C; Keitz, Benjamin K; Kuhn, Kevin M; Thomas, Renee M; Grubbs, Robert H

    2010-06-30

    The relative TONs of productive and nonproductive metathesis reactions of diethyl diallylmalonate are compared for eight different ruthenium-based catalysts. Nonproductive cross metathesis is proposed to involve a chain-carrying ruthenium methylidene. A second more-challenging substrate (dimethyl allylmethylallylmalonate) that forms a trisubstituted olefin product is used to further delineate the effect of catalyst structure on the relative efficiencies of these processes. A steric model is proposed to explain the observed trends.

  5. Catalyst design for biorefining.

    Science.gov (United States)

    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.

  6. Latent catalyst; Senzaisei shokubai

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2000-03-01

    Epoxy resin, an important function material to support such main industries as electric and electronic devices, automobiles, civil engineering, and building construction, is demanded of development of single liquid type resin having excellent quick hardening performance and storage stability. This requirement comes from environmental problems with an intention of saving energies and reducing resin wastes. The Company, using freely its independent phase separation technology that controls molecular structure of catalysts, developed a latent catalyst having excellent storage stability and high-temperature quick hardening performance. Its major features may be summarized as follows: (1) excellent storage stability at room temperature keeping the product stable for 2.5 months or longer (2 days in conventional products); (2) quick hardening performance hardening the resin in seven seconds at 150 degrees C (equivalent to conventional products); and (3) excellent insulation performance of hardened resin at 140 degrees C of 7 times 10 {sup 13} (ohm) (center dot) cm (2 times 10 {sup 12} (ohm) (center dot) cm in conventional products) (translated by NEDO)

  7. Ethylene Polymerization Using Improved Polyethylene Catalyst%改进的催化剂的乙烯聚合动力学研究

    Institute of Scientific and Technical Information of China (English)

    朱孝恒; 郭子芳; 岑为; 毛炳权

    2011-01-01

    The study concerns the use of MgCl2-supported high-activity Ziegler-Natta catalysts for the polymerization of ethylene. In particular, two types of catalysts were investigated, which were N-catalyst (BRICI) and improved polyethylene catalyst. The effects of catalyst structure on kinetic behavior were examined. The distribution of active centers in these catalysts was investigated by energy dispersive analysis by X-rays (EDAX), and morphologies of catalyst particles and polymer products were examined by scanning electron microscope (SEM). Hydrogen response and copolymerization performance were investigated and compared with the two catalysts. The results were correlated with the kinetic behavior of the two catalysts and appropriate models for polymer particle growth were presented. The improved polyethylene catalyst showed higher activity, better hydrogen response and copolymerization performance.

  8. A rare case of a three way complex variant positive Philadelphia translocation involving chromosome (9;11;22)(q34;p15;q11) in chronic myeloid leukemia: A case report

    Science.gov (United States)

    Asif, Muhammad; Hussain, Abrar; Rasool, Mahmood

    2016-01-01

    The t(9;22)(q34;q11) translocation is present in 90–95% of patients with chronic myeloid leukemia (CML). Variant complex translocations have been observed in 5–8% of CML patients, in which a third chromosome other than (9;22) is involved. Imatinib mesylate is the first line breakpoint cluster region-Abelson gene (BCR/ABL)-targeted oral therapy for CML, and may produce a complete response in 70–80% of CML patients in the chronic phase. In the present study, a bone marrow sample was used for conventional cytogenetic analysis, and the fluorescence in situ hybridization (FISH) test was used for BCR/ABL gene detection. A hematological analysis was also performed to determine the white blood cell (WBC) count, red blood cell count, hemoglobin levels, packed and mean cell volumes, mean corpuscular hemoglobin, mean corpuscular hemoglobin concentration and platelet values of the patient. The hematological analysis of the patient indicated the increased WBC of 186.5×103 cells/µl, and decreased hemoglobin levels of 11.1 g/dl. The FISH test revealed that 67% cells demonstrated BCR/ABL gene translocation. The patient was treated with 400 mg imatinib mesylate daily, and was monitored at various intervals over a 6-month period. The present study reports the rare case of a patient that demonstrates a three-way Philadelphia chromosome-positive translocation involving 46XY,t(9;11;22)(q34;p15;q11)[10], alongside CML in the chronic phase. The translocation was analyzed using cytogenetic and FISH tests. PMID:27602125

  9. Application of Three-way Laryngeal Mask Airway to Painless Fiberoptic Bronchoscopy under Intravenous Anesthesia%三通喉罩在无痛纤维支气管镜检查中的应用

    Institute of Scientific and Technical Information of China (English)

    刘文佩; 高国一; 刘平华

    2013-01-01

    目的:探讨三通喉罩在无痛纤维支气管镜检查中的安全性和可行性。方法:选择年龄65岁以下,ASAⅠ~Ⅱ级患者,按照自愿的原则分为静脉全麻组(IA)和局麻组(LA)。局麻组术前30 min肌注鲁米那100 mg+阿托品0.5 mg,检查前经环甲膜穿刺注射2%利多卡因3 mL做表麻。静脉全麻组静脉快速诱导后插入TLMA,插入成功后,TLMA标准端口连接麻醉机,纤支镜从直管带密封口置入进行检查、活检。记录麻醉前(T0)、纤支镜过声门即刻(T1)、纤支镜探查/活检时(T2)、术毕5 min(T3)各时间点的SBP、DBP、HR和SPO2;记录检查中发生低氧事件的情况、检查时间、苏醒时间。结果:19例无痛纤支镜顺利完成,患者术中循环平稳, SPO2变化于正常范围内,无呛咳、体动、低氧等不良事件,与局麻组比较差异有统计学意义(P<0.05),静脉全麻组患者和内镜医师满意度高。结论:TLMA应用于无痛纤支镜检查安全可靠、效果满意,能同时满足麻醉医师和内镜医师对气道的管理需要,具有临床应用价值。%Objective: To investigate the safety and feasibility of three-way laryngeal mask airway used in painless fibreoptic bronchoscopy. Methods: Patients aged under 65 years old and ASAⅠ~Ⅱ were divided into intravenous anesthesia group (IA,n=19)and local anesthesia group (LA,n=20)according to the principle of voluntary. Patients in group LA were intramuscular injection with luminal 100 mg and atropine 0.5 mg 30 minites before operation. Then 3 mL lidocaine was injected via cricothyroid membrane pre-operation. Patients in group IA were inserted with three-way laryngeal mask airway after rapid induction of anesthesia. SBP, DBP, HR, and SPO2 were recorded at the moments in pre-anesthesia(T0), fibreoptic bronchoscopy through the glottis(T1), perform a biopsy(T2), 5 minutes after-operation(T3). The hypoxic events, check time and

  10. Uncertainty evaluation of fluid dynamic models and validation by gamma ray transmission measurements of the catalyst flow in a FCC cold pilot unity

    Energy Technology Data Exchange (ETDEWEB)

    Teles, Francisco A.S.; Santos, Ebenezer F.; Dantas, Carlos C., E-mail: francisco.teles@ufpe.br [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Centro de Tecnologia e Geociencias. Departamento de Energia Nuclear; Melo, Silvio B., E-mail: sbm@cin.ufpe.br [Universidade Federal de Pernambuco (CIN/UFPE), Recife, PE (Brazil). Centro de Informatica; Santos, Valdemir A. dos, E-mail: vas@unicap.br [Universidade Catolica de Pernambuco (UNICAP), Recife, PE (Brazil). Dept. de Quimica; Lima, Emerson A.O., E-mail: emathematics@gmail.com [Universidade de Pernambuco (POLI/UPE), Recife, PE (Brazil). Escola Politecnica

    2013-07-01

    In this paper, fluid dynamics of Fluid Catalytic Cracking (FCC) process is investigated by means of a Cold Flow Pilot Unit (CFPU) constructed in Plexiglas to visualize operational conditions. Axial and radial catalyst profiles were measured by gamma ray transmission in the riser of the CFPU. Standard uncertainty was evaluated in volumetric solid fraction measurements for several concentrations at a given point of axial profile. Monitoring of the pressure drop in riser shows a good agreement with measured standard uncertainty data. A further evaluation of the combined uncertainty was applied to volumetric solid fraction equation using gamma transmission data. Limit condition of catalyst concentration in riser was defined and simulation with random numbers provided by MATLAB software has tested uncertainty evaluation. The Guide to the expression of Uncertainty in Measurement (GUM) is based on the law of propagation of uncertainty and on the characterization of the quantities measured by means of either a Gaussian distribution or a t-distribution, which allows measurement uncertainty to be delimited by means of a confidence interval. A variety of supplements to GUM are being developed, which will progressively enter into effect. The first of these supplements [3] describes an alternative procedure for the calculation of uncertainties: the Monte Carlo Method (MCM).MCM is an alternative to GUM, since it performs a characterization of the quantities measured based on the random sampling of the probability distribution functions. This paper also explains the basic implementation of the MCM method in MATLAB. (author)

  11. A versatile elevated-pressure reactor combined with an ultrahigh vacuum surface setup for efficient testing of model and powder catalysts under clean gas-phase conditions

    Energy Technology Data Exchange (ETDEWEB)

    Morfin, Franck; Piccolo, Laurent [Institut de recherches sur la catalyse et l' environnement de Lyon (IRCELYON), UMR 5256 CNRS and Université Lyon 1, 2 avenue Albert Einstein, F-69626 Villeurbanne (France)

    2013-09-15

    A small-volume reaction cell for catalytic or photocatalytic testing of solid materials at pressures up to 1000 Torr has been coupled to a surface-science setup used for standard sample preparation and characterization under ultrahigh vacuum (UHV). The reactor and sample holder designs allow easy sample transfer from/to the UHV chamber, and investigation of both planar and small amounts of powder catalysts under the same conditions. The sample is heated with an infrared laser beam and its temperature is measured with a compact pyrometer. Combined in a regulation loop, this system ensures fast and accurate temperature control as well as clean heating. The reaction products are automatically sampled and analyzed by mass spectrometry and/or gas chromatography (GC). Unlike previous systems, our GC apparatus does not use a recirculation loop and allows working in clean conditions at pressures as low as 1 Torr while detecting partial pressures smaller than 10{sup −4} Torr. The efficiency and versatility of the reactor are demonstrated in the study of two catalytic systems: butadiene hydrogenation on Pd(100) and CO oxidation over an AuRh/TiO{sub 2} powder catalyst.

  12. Electrochemical Catalyst-Support Effects and Their Stabilizing Role for IrOx Nanoparticle Catalysts during the Oxygen Evolution Reaction.

    Science.gov (United States)

    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.

  13. Stereospecific olefin polymerization catalysts

    Science.gov (United States)

    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.

  14. 一种软计算混合策略在多相催化剂建模与预测中的应用%Modeling and Forecasting for Heterogeneous Catalysts Using Soft Computing Hybrid Strategy

    Institute of Scientific and Technical Information of China (English)

    韩晓霞; 谢珺; 韩晓明; 谢刚

    2012-01-01

    This paper presents a new soft computing hybrid strategy of Cl heterogeneous catalyst modeling and forecasting methodology, for reducing both high temporal costs and financial costs, and accelerating the industrialization process of dimethyl ether (DME) synthesis. In this soft computing approach, a novel machine learning algorithm, namely support vector regression, can well solve the small sample, high dimension, nonlinear and local minimizing of practical problems, and has been utilized for developing catalytic kinetic models. The hyper-parameter selection of SVR model adopts heuristic global optimization algorithm, that is,chaotic particle swarm optimization algorithm (CPSO) , to improve the SVR model in prediction precision and generalization ability. The main advantage of the new strategy is its ability to,for unknown or difficultly available reaction mechanism,model by a small history sample space, so as to avoid the blindness and chance in traditional trial-and-error catalyst research and development process. Through two different modeling methods and three different SVR super parameter optimization strategies in the comparative study on Cu-Zn-Al-Zr dimethyl ether catalyst component, the new strategy was found to be a promising development direction in the heterogeneous catalysts modeling and forecasting.%为了减少发现新的碳一多相催化剂的时间、降低消耗,加速二甲醚合成工业化进程,提出一种新的软计算混合策略并应用于碳一多相催化剂建模与预测研究.支持向量回归机(Support Vector Regression,SVR)作为一种新的机器学习算法,能较好地解决小样本、高维、非线性和局部极小点等实际问题,在混合策略中被用于多相催化剂组分模型的开发.SVR模型的超参数选择采用启发式全局优化搜索算法——自适应混沌粒子群算法来提高SVR模型的预测精度和泛化能力.新策略的主要优势是在反应机理未知或难以获取的情况下,

  15. Studies on Macro—kinetics of Gas Phase Polymerization of Butadiene with Rare—earch Catalyst

    Institute of Scientific and Technical Information of China (English)

    FANGDonyu; SUNJianzhong; 等

    2002-01-01

    The study of the kinetics of gas phase polymerization of butadiene with heterogeneous catalyst based on neodymium(Nd) was carried out.The effects of reaction temperature,reaction pressure,dispersing medium, and types of catalyst on kinetics of polymerization were investigated .A kinetic model with two kinds of active sites was proposed.The results show that the effects of the reaction temperature and the types of dispersing medium and catalyst on the kinetic performance of polymerization are significant,and that the combined model of first and second order decay of active site of catalyst can be used to describe the phenomena.

  16. Physico-Chemical and Structural Properties of DeNOx and SO2 Oxidation Catalysts

    DEFF Research Database (Denmark)

    Masters, Stephen Grenville; Oehlers, Cord; Nielsen, Kurt;

    1996-01-01

    Commercial catalysts for NOx removal and SO2 oxidation and their model systems have been investigated by spectroscopic, thermal, electrochemical and X-ray methods. Structural information on the vanadium complexes and compounds as well as physico-chemical properties for catalyst model systems have...... been obtained. The results are discussed in relation to proposed reaction mechanisms....

  17. Catalyst support effects on hydrogen spillover

    Science.gov (United States)

    Karim, Waiz; Spreafico, Clelia; Kleibert, Armin; Gobrecht, Jens; Vandevondele, Joost; Ekinci, Yasin; van Bokhoven, Jeroen A.

    2017-01-01

    Hydrogen spillover is the surface migration of activated hydrogen atoms from a metal catalyst particle, on which they are generated, onto the catalyst support. The phenomenon has been much studied and its occurrence on reducible supports such as titanium oxide is established, yet questions remain about whether hydrogen spillover can take place on nonreducible supports such as aluminium oxide. Here we use the enhanced precision of top-down nanofabrication to prepare controlled and precisely tunable model systems that allow us to quantify the efficiency and spatial extent of hydrogen spillover on both reducible and nonreducible supports. We place multiple pairs of iron oxide and platinum nanoparticles on titanium oxide and aluminium oxide supports, varying the distance between the pairs from zero to 45 nanometres with a precision of one nanometre. We then observe the extent of the reduction of the iron oxide particles by hydrogen atoms generated on the platinum using single-particle in situ X-ray absorption spectromicroscopy applied simultaneously to all particle pairs. The data, in conjunction with density functional theory calculations, reveal fast hydrogen spillover on titanium oxide that reduces remote iron oxide nanoparticles via coupled proton-electron transfer. In contrast, spillover on aluminium oxide is mediated by three-coordinated aluminium centres that also interact with water and that give rise to hydrogen mobility competing with hydrogen desorption; this results in hydrogen spillover about ten orders of magnitude slower than on titanium oxide and restricted to very short distances from the platinum particle. We anticipate that these observations will improve our understanding of hydrogen storage and catalytic reactions involving hydrogen, and that our approach to creating and probing model catalyst systems will provide opportunities for studying the origin of synergistic effects in supported catalysts that combine multiple functionalities.

  18. Bridging the pressure gap: In situ atomic-level investigations of model platinum catalyst surfaces under reaction conditions by scanning tunneling microscopy

    Energy Technology Data Exchange (ETDEWEB)

    McIntyre, B.J.

    1994-05-01

    Results of this thesis show that STM measurements can provide information about the surfaces and their adsorbates. Stability of Pt(110) under high pressures of H2, O2, and CO was studied (Chap. 4). In situ UHV and high vacuum experiments were carried out for sulfur on Pt(111) (Chap.5). STM studies of CO/S/Pt(111) in high CO pressures showed that the Pt substrate undergoes a stacking-fault-domain reconstruction involving periodic transitions from fcc to hcp stacking of top-layer atoms (Chap.6). In Chap.7, the stability of propylene on Pt(111) and the decomposition products were studied in situ with the HPSTM. Finally, in Chap.8, results are presented which show how the Pt tip of the HPSTM was used to locally rehydrogenate and oxidize carbonaceous clusters deposited on the Pt(111) surface; the Pt tip acted as a catalyst after activation by short voltage pulses.

  19. Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

    KAUST Repository

    Merle, Nicolas

    2017-09-25

    A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

  20. Impeded solid state reactions and transformations in ceramic catalysts supports and catalysts

    Directory of Open Access Journals (Sweden)

    Ernő E. Kiss

    2012-12-01

    Full Text Available Impeded chemical reactions and impeded polymorphous transformation in materials are discussed, as desired effects, for stabilization of ceramic catalyst supports and ceramic based catalysts. This paper gives a short overview about the possibilities of slowing down the aging processes in ceramic catalyst supports and catalysts. Special attention is given to alumina and titania based catalysts.

  1. Restrictive liquid-phase diffusion and reaction in bidispersed catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.Y.; Seader, J.D. (Utah Univ., Salt Lake City, UT (United States). Dept. of Chemical Engineering); Tsai, C.H.; Massoth, F.E. (Utah Univ., Salt Lake City, UT (United States). Dept. of Fuels Engineering)

    1991-08-01

    In this paper, the effect of bidispersed pore-size distribution on liquid-phase diffusion and reaction in NiMo/Al{sub 2}O{sub 3} catalysts is investigated by applying two bidispersed-pore-structure models, the random-pore model and a globular-structure model, to extensive experimental data, which were obtained from sorptive diffusion measurements at ambient conditions and catalytic reaction rate measurements on nitrogen-containing compounds. Transport of the molecules in the catalysts was found to be controlled by micropore diffusion, in accordance with the random-pore model, rather than macropore diffusion as predicted by the globular-structure model. A qualitative criterion for micropore-diffusion control is proposed: relatively small macroporosity and high catalyst pellet density. Since most hydrotreating catalysts have high density, diffusion in these types of catalysts may be controlled by micropore diffusion. Accordingly, it is believed in this case that increasing the size of micropores may be more effective to reduce intraparticle diffusion resistance than incorporating macropores alone.

  2. Amorphous Nickel Based Alloy Catalysts and Magnetically Stabilized Bed Hydrogenation Technology

    Institute of Scientific and Technical Information of China (English)

    MuXuhong; ZongBaoning; 等

    2002-01-01

    Amorphous nickel based alloy catalysts(denoted as the SRNA series catalysts)were prepared via rapid quenching method followed by alkali leaching and other activation procedures.The physicochemical characterizations show that nickel,the active component in these catalysts,exists in the amorphous state,and the catalyst particles possess many nanosized voids leading to large surface area(the highest is 145m2/g).The evaluation results in some model reactions show that the SRNA series catalysts have 2 to 4 times higher activity and selectivity than conventional Raney Ni catalyst for the hydrogenation of compounds with unsatur-ated functional groups.At present,the SRNA series catalysts have been successfully used in hydrogenation of glucose,hydrogenation of pharmaceutical intermediates and purification of caprolactam.In order to use these catalysts efficiently,a magnetically stabilized bed(MSB) technology has been developed by combining the ferromagnetic property of the catalyst with the good mass transfer characteristics of MSB.The demonstration unit of MSB hydrogenation technology has been set up and has kept running for 2800 hours.The results show that,after running 2800 hours,the catalyst still retained good activity; meanwhile,the hydrogenation effi-ciency had been improved 10 times in comparison with the traditional CSTR process.

  3. Recent Progress on Molecular Modeling of Ethylene Polymerization/Oligomerization Catalyzed by Chromium-Based Catalysts%铬系催化乙烯配位聚合/齐聚分子模拟研究进展

    Institute of Scientific and Technical Information of China (English)

    刘振; 程瑞华; 何雪莲; 田洲; 刘柏平

    2014-01-01

    Phillips chromium-based catalysts are widely used in industrial production of polyethylene andα-olefins through ethylene selective oligomerization. Recently, molecular modeling has been playing more and more important role in understanding the mechanism of ethylene polymerization and selective trimerization. From this point of view, the active site transformation from polymerization to metathesis during the induction period of the Phillips catalyst, the effect of Ti-modification on the Phillips catalyst, the transformation from ethylene polymerization to selective trimerization of the Cr(III) 2-EH/PIBAO/DME system, and the effect of deprotonation and Cr oxidation states in the Cr-SNS system on the ethylene selective trimerization were reviewed. A much profound mechanistic understanding has been achieved through combination of molecular modeling with experiments.%针对工业中广泛应用的 Phillips 铬系乙烯聚合催化剂和铬系乙烯选择性齐聚催化体系,从分子模拟角度对近期相关研究进展进行综述。主要介绍了分子模拟在 Phillips 铬系催化剂诱导期内乙烯聚合活性中心向乙烯易位活性中心转换机理、Ti改性Phillips铬系催化剂的乙烯聚合行为、Cr(III)2-EH/PIBAO/DME体系乙烯聚合和三聚转换机理以及 Cr-SNS 体系去质子化对乙烯三聚活性的影响等方面的研究进展。通过计算机分子模拟和实验手段相结合,可以获得对催化反应机理更为深刻的认识,从而为新型催化剂的设计与开发提供理论指导。

  4. New hydrocracking catalysts increase throughput, run length

    Energy Technology Data Exchange (ETDEWEB)

    Huizinga, T. [Shell Internationale Petroleum Mij., The Hague (Netherlands); Theunissen, J.M.H. [Rayong Refinery Co. Ltd., Rayong (Thailand); Minderhoud, H.; Veen, R. van [Koninklijke/Shell-Lab., Amsterdam (Netherlands)

    1995-06-26

    An improved, second-stage hydrocracking catalyst has been developed by combining stabilized Y zeolites with amorphous silica alumina cracking components. A commercial application of this catalyst, along with a new, first-stage zeolitic hydrocracking catalyst, resulted in increased unit throughput and cycle length. The paper discusses the hydrocracking process, first-stage catalysts, second-stage catalysts, hydrogenation process, commercial results, and product properties.

  5. Biomass processing over gold catalysts

    CERN Document Server

    Simakova, Olga A; Murzin, Dmitry Yu

    2014-01-01

    The book describes the valorization of biomass-derived compounds over gold catalysts. Since biomass is a rich renewable feedstock for diverse platform molecules, including those currently derived from petroleum, the interest in various transformation routes has become intense. Catalytic conversion of biomass is one of the main approaches to improving the economic viability of biorefineries.  In addition, Gold catalysts were found to have outstanding activity and selectivity in many key reactions. This book collects information about transformations of the most promising and important compounds derived from cellulose, hemicelluloses, and woody biomass extractives. Since gold catalysts possess high stability under oxidative conditions, selective oxidation reactions were discussed more thoroughly than other critical reactions such as partial hydrogenation, acetalization, and isomerization. The influence of reaction conditions, the role of the catalyst, and the advantages and disadvantages of using gold are pre...

  6. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Chunshan, Song; Kirby, S.; Schmidt, E. [Pennsylvania State Univ., University Park, PA (United States)] [and others

    1995-12-31

    The objective of this project is to explore bimetallic dispersed catalysts for more efficient coal liquefaction. Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting various aromatic units and the reactions of various oxygen functional groups. This paper describes recent results on (1) hydrodeoxygenation of O-containing polycyclic model compounds using novel organometallic catalyst precursors; and (2) activity and selectivity of dispersed Fe catalysts from organometallic and inorganic precursors for hydrocracking of 4-(1-naphthylmethyl) bibenzyl. The results showed that some iron containing catalysts have higher activity in the sulfur-free form, contrary to conventional wisdom. Adding sulfur to Fe precursors with Cp-ligands decreased the activity of the resulting catalyst. This is in distinct contrast to the cases with iron pentacarbonyl and superfine Fe{sub 2}O{sub 3}, where S addition increased their catalytic activity substantially. A positive correlation between sulfur addition and increased activity can be seen, but a reversed trend between Fe cluster size and hydrocracking conversion could be observed, for carbonyl-type Fe precursors. It is apparent that the activity and selectivity of Fe catalysts for NMBB conversion depends strongly on both the type of ligand environment, the oxidation state and the number of intermetal bonds in the molecular precursor.

  7. Ruthenium olefin metathesis catalysts featuring unsymmetrical N-heterocyclic carbenes.

    Science.gov (United States)

    Paradiso, Veronica; Bertolasi, Valerio; Costabile, Chiara; Grisi, Fabia

    2016-01-14

    New ruthenium Grubbs' and Hoveyda-Grubbs' second generation catalysts bearing N-alkyl/N-isopropylphenyl N-heterocyclic carbene (NHC) ligands with syn or anti backbone configuration were obtained and compared in model olefin metathesis reactions. Different catalytic efficiencies were observed depending on the size of the N-alkyl group (methyl or cyclohexyl) and on the backbone configuration. The presence of an N-cyclohexyl substituent determined the most significant reactivity differences between catalysts with syn or anti phenyl groups on the backbone. In particular, anti catalysts proved highly efficient, especially in the ring-closing metathesis (RCM) of encumbered diolefins, while syn catalysts showed low efficiency in the RCM of less hindered diolefins. This peculiar behavior, rationalized through DFT studies, was found to be related to the high propensity of these catalysts to give nonproductive metathesis events. Enantiopure anti catalysts were also tested in asymmetric metathesis reactions, where moderate enantioselectivities were observed. The steric and electronic properties of unsymmetrical NHCs with the N-cyclohexyl group were then evaluated using the corresponding rhodium complexes. While steric factors proved unimportant for both syn and anti NHCs, a major electron-donating character was found for the unsymmetrical NHC with anti phenyl substituents on the backbone.

  8. CATALYSTS FOR HIGH CETANE ETHERS AS DIESEL FUELS

    Energy Technology Data Exchange (ETDEWEB)

    Kamil Klier; Richard G. Herman; Heock-Hoi Kwon; James G. C. Shen; Qisheng Ma; Robert A. Hunsicker; Andrew P. Butler; Scott J. Bollinger

    2003-03-01

    A tungstena-zirconia (WZ) catalyst has been investigated for coupling methanol and isobutanol to unsymmetrical ethers, i.e. methyl isobutyl ether (MIBE) and compared with earlier studied sulfated-zirconia (SZ) and Nafion-H catalysts. In all cases, the ether synthesis mechanism is a dual site S{sub N}2 process involving competitive adsorption of reactants on proximal acid sites. At low reaction temperatures, methylisobutylether (MIBE) is the predominant product. However, at temperatures >135 C the WZ catalyst is very good for dehydration of isobutanol to isobutene. The surface acid sites of the WZ catalyst and a Nafion-H catalyst were diagnosed by high resolution X-ray photoelectron spectroscopy (XPS) of N 1s shifts after adsorption of amines. Using pyridine, ethylenediamine, and triethylamine, it is shown that WZ has heterogeneous strong Broensted acid sites. Theoretical study located the transition state of the alcohol coupling reaction on proximal Broensted acid sites and accounted well for XPS core-level shifts upon surface acid-base interactions. While computations have not been carried out with WZ, it is shown that the SZ catalyst is a slightly stronger acid than CF{sub 3}SO{sub 3}H (a model for Nafion-H) by 1.3-1.4 kcal/mol. A novel sulfated zirconia catalyst having proximal strong Broensted acid sites was synthesized and shown to have significantly enhanced activity and high selectivity in producing MIBE or isobutene from methanol/isobutanol mixtures. The catalyst was prepared by anchoring 1,2-ethanediol bis(hydrogen sulfate) salt precursor onto zirconium hydroxide, followed by calcination to remove the -(CH{sub 2}CH{sub 2})- bridging residues.

  9. Intermediate Ethanol Blends Catalyst Durability Program

    Energy Technology Data Exchange (ETDEWEB)

    West, Brian H; Sluder, Scott; Knoll, Keith; Orban, John; Feng, Jingyu

    2012-02-01

    In the summer of 2007, the U.S. Department of Energy (DOE) initiated a test program to evaluate the potential impacts of intermediate ethanol blends (also known as mid-level blends) on legacy vehicles and other engines. The purpose of the test program was to develop information important to assessing the viability of using intermediate blends as a contributor to meeting national goals for the use of renewable fuels. Through a wide range of experimental activities, DOE is evaluating the effects of E15 and E20 - gasoline blended with 15% and 20% ethanol - on tailpipe and evaporative emissions, catalyst and engine durability, vehicle driveability, engine operability, and vehicle and engine materials. This report provides the results of the catalyst durability study, a substantial part of the overall test program. Results from additional projects will be reported separately. The principal purpose of the catalyst durability study was to investigate the effects of adding up to 20% ethanol to gasoline on the durability of catalysts and other aspects of the emissions control systems of vehicles. Section 1 provides further information about the purpose and context of the study. Section 2 describes the experimental approach for the test program, including vehicle selection, aging and emissions test cycle, fuel selection, and data handling and analysis. Section 3 summarizes the effects of the ethanol blends on emissions and fuel economy of the test vehicles. Section 4 summarizes notable unscheduled maintenance and testing issues experienced during the program. The appendixes provide additional detail about the statistical models used in the analysis, detailed statistical analyses, and detailed vehicle specifications.

  10. Need for optimizing catalyst loading for achieving affordable microbial fuel cells.

    Science.gov (United States)

    Singh, Inderjeet; Chandra, Amreesh

    2013-08-01

    Microbial fuel cell (MFC) technology is a promising technology for electricity production together with simultaneous water treatment. Catalysts play an important role in deciding the MFC performance. In most reports, effect of catalyst - both type and quantity is not optimized. In this paper, synthesis of nanorods of MnO2-catalyst particles for application in Pt-free MFCs is reported. The effect of catalyst loading i.e., weight ratio, with respect to conducting element and binder has been optimized by employing large number of combinations. Using simple theoretical model, it is shown that too high (or low) concentration of catalysts result in loss of MFC performance. The operation of MFC has been investigated using domestic wastewater as source of bio-waste for obtaining real world situation. Maximum power density of ∼61 mW/m(2) was obtained when weight ratio of catalyst and conducting species was 1:1. Suitable reasons are given to explain the outcomes.

  11. Performance of Pd/CeO_2-ZrO_2-Al_2O_3 catalyst for motorcycle

    Institute of Scientific and Technical Information of China (English)

    ZHAO Ming; CHEN Shanhu; ZHANG Xiaoyu; GONG Maochu; CHEN Yaoqiang

    2009-01-01

    The Pd-only catalysts for motorcycle were prepared by impregnating CeO_2-ZrO_2-Al_2O_3 and CeO_2-ZrO_2+Al_2O_3 with PdCl_2 aque-ous solution and characterized by X-ray diffraction (XRD), oxygen storage capacity (OSC) and H_2-temperature-programmed reduction (H_2-TPR) methods. The XRD result indicated that the CeO_2-ZrO_2-Al_2O_3 compound prepared by co-precipitation formed a single solid solu-tion and had good thermal stability, and Pd phase was not observed in all catalysts. The TPR results showed that the reduction temperature of Pd/CeO_2-ZrO_2-Al_2O_3 catalyst was lower than that of Pd/CeO_2-ZrO_2+Al_2O_3 catalyst whether they were fresh or aged catalysts. The Pd/CeO_2-ZrO_2-Al_2O_3 exhibited high three-way catalytic activity at low temperature, high thermal stability, and wide working window, sug-gesting a great potential for applications.

  12. Performance of Pd/CeO2-ZrO2-Al2O3 catalyst for motorcycle

    Institute of Scientific and Technical Information of China (English)

    ZHAO; Ming; CHEN; Shanhu; ZHANG; Xiaoyu; GONG; Maochu; CHE

    2009-01-01

    The Pd-only catalysts for motorcycle were prepared by impregnating CeO2-ZrO2-Al2O3 and CeO2-ZrO2+Al2O3 with PdCl2 aque-ous solution and characterized by X-ray diffraction (XRD), oxygen storage capacity (OSC) and H2-temperature-programmed reduction (H2-TPR) methods. The XRD result indicated that the CeO2-ZrO2-Al2O3 compound prepared by co-precipitation formed a single solid solu-tion and had good thermal stability, and Pd phase was not observed in all catalysts. The TPR results showed that the reduction temperature of Pd/CeO2-ZrO2-Al2O3 catalyst was lower than that of Pd/CeO2-ZrO2+Al2O3 catalyst whether they were fresh or aged catalysts. The Pd/CeO2-ZrO2-Al2O3 exhibited high three-way catalytic activity at low temperature, high thermal stability, and wide working window, sug-gesting a great potential for applications.

  13. The innovation catalysts.

    Science.gov (United States)

    Martin, Roger L

    2011-06-01

    A few years ago the software development company Intuit realized that it needed a new approach to galvanizing customers. The company's Net Promoter Score was faltering, and customer recommendations of new products were especially disappointing. Intuit decided to hold a two-day, off-site meeting for the company's top 300 managers with a focus on the role of design in innovation. One of the days was dedicated to a program called Design for Delight. The centerpiece of the day was a PowerPoint presentation by Intuit founder Scott Cook, who realized midway through that he was no Steve Jobs: The managers listened dutifully, but there was little energy in the room. By contrast, a subsequent exercise in which the participants worked through a design challenge by creating prototypes, getting feedback, iterating, and refining, had them mesmerized. The eventual result was the creation of a team of nine design-thinking coaches--"innovation catalysts"--from across Intuit who were made available to help any work group create prototypes, run experiments, and learn from customers. The process includes a "painstorm" (to determine the customer's greatest pain point), a "soljam" (to generate and then winnow possible solutions), and a "code-jam" (to write code "good enough" to take to customers within two weeks). Design for Delight has enabled employees throughout Intuit to move from satisfying customers to delighting them.

  14. Hydrocarbon conversion catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Hoek, A.; Huizinga, T.; Maxwell, I.E.

    1989-08-15

    This patent describes a process for hydrocracking hydrocarbon oils into products of lower average molecular weight and lower average boiling point. It comprises contacting a hydrocarbon oil at a temperature between 250{sup 0}C and 500{sup 0}C and a pressure up to 300 bar in the presence of hydrogen with a catalyst consisting essentially of a Y zeolite modified to have a unit cell size below 24.35A, a water absorption capacity (at 25{sup 0}C and a rho/rho/sub o/ value of 0.2) of at least 8% by weight of the zeolite and a pore volume of at least 0.25 ml/g wherein between 10% and 60% of the total pore volume is made up of pores having a diameter of at least 8 nm; an alumina binder and at least one hydrogenation component selected from the group consisting of a Group VI metal, a Group VIII metal and mixtures thereof.

  15. Effect of catalyst pretreatment on the olefin metathesis catalyzed by alumina-supported (9%) rhenium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, J.C.

    1979-01-01

    A kinetic model was developed to express the time-on-stream profile of the activity during catalyst break-in and deactivation. The catalyst surface is in geometric and energetic heterogeneity. Partial catalyst reduction is a prerequisite step for olefin metathesis. The metathesis activity may be affected by the coordination number and the type of ligands associated with the sites on the catalyst. The deactivation is proposed due to deposition of residues on the active sites, and to sintering, etc. A dispersion pretreatment increased activity. Oxygen is an activator. The hydrogen reduction at 500/sup 0/C causes partial but permanent loss of activity.

  16. Atomic-scale investigation of the interaction of organic molecules with MoS2-based hydrotreating model catalysts

    DEFF Research Database (Denmark)

    Salazar Moreira, Norberto José

    2017-01-01

    the presence of the reduced MoOx phase impedes the MoS2 growth and leads to rather stable amorphous oxysulfide phases. The sulfidation in H2S atmosphere of molybdenum metal and bimetallic cobalt-molybdenum clusters deposited on Au(111) facilitate instead the formation of well-dispersed MoS2 and Co-promoted Mo...... is reduced to 50%. The reduction of the nanoparticles in H2 reveals a variety of possible active sites which indicates that the catalysts are now present in their active states for HDS reactions.These active sites are shown to be reactive with some of the typical sulfur heterocyclic compounds present in real...... study of the adsorption sites for these sulfur and nitrogen-containing molecules is present in this thesis.In summary, the research in this PhD thesis elucidates some of the fundamental questions regarded to the understanding of the active structures, preferable adsorption sites and deactivation origin...

  17. WATER-GAS SHIFT KINETICS OVER IRON OXIDE CATALYSTS AT MEMBRANE REACTOR CONDITIONS

    Energy Technology Data Exchange (ETDEWEB)

    Carl R.F. Lund

    2002-08-02

    The kinetics of water-gas shift were studied over ferrochrome catalysts under conditions with high carbon dioxide partial pressures, such as would be expected in a membrane reactor. The catalyst activity is inhibited by increasing carbon dioxide partial pressure. A microkinetic model of the reaction kinetics was developed. The model indicated that catalyst performance could be improved by decreasing the strength of surface oxygen bonds. Literature data indicated that adding either ceria or copper to the catalyst as a promoter might impart this desired effect. Ceria-promoted ferrochrome catalysts did not perform any better than unpromoted catalyst at the conditions tested, but copper-promoted ferrochrome catalysts did offer an improvement over the base ferrochrome material. A different class of water-gas shift catalyst, sulfided CoMo/Al{sub 2}O{sub 3} is not affected by carbon dioxide and may be a good alternative to the ferrochrome system, provided other constraints, notably the requisite sulfur level and maximum temperature, are not too limiting. A model was developed for an adiabatic, high-temperature water-gas shift membrane reactor. Simulation results indicate that an excess of steam in the feed (three moles of water per mole of CO) is beneficial even in a membrane reactor as it reduces the rate of adiabatic temperature rise. The simulations also indicate that much greater improvement can be attained by improving the catalyst as opposed to improving the membrane. Further, eliminating the inhibition by carbon dioxide will have a greater impact than will increasing the catalyst activity (assuming inhibition is still operative). Follow-up research into the use of sulfide catalysts with continued kinetic and reactor modeling is suggested.

  18. Nature of nitrogen specie in coke and their role in NOx formation during FCC catalyst regeneration.

    NARCIS (Netherlands)

    Babych, Igor V.; Seshan, Kulathuiyer; Lefferts, Leonardus

    2005-01-01

    NOx emission during the regeneration of coked fluid catalytic cracking (FCC) catalysts is an environmental problem. In order to follow the route to NOx formation and try to find ways to suppress it, a coked industrial FCC catalyst has been prepared using model N-containing compounds, e.g., pyridine,

  19. Catalytic Cracking of Palm Oil Over Zeolite Catalysts: Statistical Approach

    Directory of Open Access Journals (Sweden)

    F. A. A. Twaiq and S. Bhatia

    2012-08-01

    Full Text Available The catalytic cracking of palm oil was conducted in a fixed bed micro-reactor over HZSM-5, zeolite ? and ultrastable Y (USY zeolite catalysts. The objective of the present investigation was to study the effect of cracking reaction variables such as temperature, weight hourly space velocity, catalyst pore size and type of palm oil feed of different molecular weight on the conversion, yield of hydrocarbons in gasoline boiling range and BTX aromatics in the organic liquid product.  Statistical Design of Experiment (DOE with 24 full factorial design was used in experimentation at the first stage.  The nonlinear model and Response Surface Methodology (RSM were utilized in the second stage of experimentation to obtain the optimum values of the variables for maximum yields of hydrocarbons in gasoline boiling range and aromatics.  The HZSM-5 showed the best performance amongst the three catalysts tested.  At 623 K and WHSV of 1 h-1, the highest experimental yields of gasoline and aromatics were 28.3 wt.% and 27 wt.%, respectively over the HZSM-5 catalyst.  For the same catalyst, the statistical model predicted that the optimum yield of gasoline was 28.1 wt.% at WHSV of 1.75 h-1 and 623 K.  The predicted optimum yield of gasoline was 25.5 wt.% at 623 K and WHSV of 1 h-1.KEY WORDS: Catalytic Cracking, Palm Oil, Zeolite, Design Of Experiment, Response Surface Methodology.

  20. Non-noble metal fuel cell catalysts

    CERN Document Server

    Chen, Zhongwei; Zhang, Jiujun

    2014-01-01

    Written and edited by a group of top scientists and engineers in the field of fuel cell catalysts from both industry and academia, this book provides a complete overview of this hot topic. It covers the synthesis, characterization, activity validation and modeling of different non-noble metal and metalfree electrocatalysts for the reduction of oxygen, as well as their integration into acid or alkaline polymer exchange membrane (PEM) fuel cells and their performance validation, while also discussing those factors that will drive fuel cell commercialization. With its well-structured app

  1. Amorphous Nickel Based Alloy Catalysts and Magnetically Stabilized Bed Hydrogenation Technology

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Amorphous nickel based alloy catalysts (denoted as the SRNA series catalysts) were prepared viarapid quenching method followed by alkali leaching and other activation procedures. The physicochemicalcharacterizations show that nickel, the active component in these catalysts, exists in the amorphous state, andthe catalyst particles possess many nanosized voids leading to large surface area (the highest is 145m2/g). Theevaluation results in some model reactions show that the SRNA series catalysts have 2 to 4 times higheractivity and selectivity than conventional Raney Ni catalyst for the hydrogenation of compounds with unsatur-ated functional groups. At present, the SRNA series catalysts have been successfully used in hydrogenation ofglucose, hydrogenation of pharmaceutical intermediates and purification of caprolactam. In order to use thesecatalysts efficiently, a magnetically stabilized bed (MSB) technology has been developed by combining theferromagnetic property of the catalyst with the good mass transfer characteristics of MSB. The demonstrationunit of MSB hydrogenation technology has been set up and has kept running for 2800 hours. The results showthat, after running 2800 hours, the catalyst still retained good activity; meanwhile, the hydrogenation effi-ciency had been improved 10 times in comparison with the traditional CSTR process.

  2. Amorphous Nickel Based Alloy Catalysts and Magnetically Stabilized Bed Hydrogenation Technology

    Institute of Scientific and Technical Information of China (English)

    Mu Xuhong; Zong Baoning; Meng Xiangkun; Min Enze

    2002-01-01

    Amorphous nickel based alloy catalysts (denoted as the SRNAseries catalysts) were prepared viarapid quenching method followed by alkali leaching and other activation procedures. The physicochemicalcharacterizations show that nickel, the active component in these catalysts, exists in the amorphous state, andthe catalyst particles possess many nanosized voids leading to large surface area (the highest is 145m2/g). Theevaluation results in some model reactions show that the SRNA series catalysts have 2 to 4 times higheractivity and selectivity than conventional Raney Ni catalyst for the hydrogenation of compounds with unsatur-ated functional groups. At present, the SRNA series catalysts have been successfully used in hydrogenation ofglucose, hydrogenation of pharmaceutical intermediates and purification of caprolactam. In order to use thesecatalysts efficiently, a magnetically stabilized bed (MSB) technology has been developed by combining theferromagnetic property of the catalyst with the good mass transfer characteristics of MSB. The demonstrationunit of MSB hydrogenation technology has been set up and has kept running for 2800 hours. The results showthat, after running 2800 hours, the catalyst still retained good activity; meanwhile, the hydrogenation effi-ciency had been improved 10 times in comparison with the traditional CSTR process.

  3. Regeneration of Hydrotreating and FCC Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    CM Wai; JG Frye; JL Fulton; LE Bowman; LJ Silva; MA Gerber

    1999-09-30

    Hydrotreating, hydrocracking, and fluid catalytic cracking (FCC) catalysts are important components of petroleum refining processes. Hydrotreating and hydrocracking catalysts are used to improve the yield of high-quality light oil fractions from heavier crude oil and petroleum feedstocks containing high levels of impurities. FCC catalysts improve the yield of higher octane gasoline from crude oil. Residuum hydrotreating and cracking catalysts are susceptible to irreversible deactivation caused by adsorption of sulfur and by metals impurities, such as vanadium and nickel. The gradual buildup of these impurities in a hydrotreating catalyst eventually plugs the pores and deactivates it. Nickel and vanadium adversely affect the behavior of cracking catalysts, reducing product yield and quality. Replacing deactivated catalysts represents a significant cost in petroleum refining. Equally important are the costs and potential liabilities associated with treating and disposing spent catalysts. For example, recent US Environmental Protection Agency rulings have listed spent hydrotreating and hydrorefining catalysts as hazardous wastes. FCC catalysts, though more easily disposed of as road-base or as filler in asphalt and cement, are still an economic concern mainly because of the large volumes of spent catalysts generated. New processes are being considered to increase the useful life of catalysts or for meeting more stringent disposal requirements for spent catalysts containing metals. This report discusses a collaborative effort between Pacific Northwest National Laboratory (PNNL) and Phillips Petroleum, Inc., to identify promising chemical processes for removing metals adhered to spent hydrodesulfurization (HDS, a type of hydrotreating catalyst) and FCC catalysts. This study, conducted by PNNL, was funded by the US Department of Energy's Bartlesville Project Office. Fresh and spent catalysts were provided by Phillips Petroleum. The FCC catalyst was a rare

  4. SELECTIVE CATALYTIC REDUCTION (SCR OF NO BY AMMONIA OVER V2O5/TiO2 CATALYST IN A CATALYTIC FILTER MEDIUM AND HONEYCOMB REACTOR: A KINETIC MODELING STUDY

    Directory of Open Access Journals (Sweden)

    M. Nahavandi

    2015-12-01

    Full Text Available Abstract The present study addresses a numerical modeling and simulation based on the available knowledge of SCR kinetics for prediction of NO conversion over a V2O3/TiO3 catalyst through a catalytic filter medium and honeycomb reactor. After introducing the NH3-SCR system with specific operational criteria, a reactor model was developed to evaluate the effect of various operating parameters such as flue gas temperature, velocity, NH3/NO molar ratio, etc., on the SCR process. Computational investigations were performed based on the proposed model and optimum operational conditions were identified. Simulation results indicate that SCR performance is substantially under the effects of reactant concentration and operating temperature, so that the concentration of unreacted ammonia emitted from reactor discharge (ammonia slip increases significantly at NH3/NO ratios of more than 1.14 and operating temperatures less than 360 ºC and 300 ºC, respectively, in the catalytic filter medium and honeycomb reactor. The results also show that there are three sections in NO conversion variation versus changing temperature and the required conversion with a maximum of almost 87% and low level of ammonia slip can be achieved at the NH3/NO ratio of 1 and temperature range of 240–360 ºC in both reactors.

  5. Formic acid oxidation at platinum-bismuth catalysts

    Directory of Open Access Journals (Sweden)

    Popović Ksenija Đ.

    2015-01-01

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

  6. Catalyst containing oxygen transport membrane

    Science.gov (United States)

    Christie, Gervase Maxwell; Wilson, Jamie Robyn; van Hassel, Bart Antonie

    2012-12-04

    A composite oxygen transport membrane having a dense layer, a porous support layer and an intermediate porous layer located between the dense layer and the porous support layer. Both the dense layer and the intermediate porous layer are formed from an ionic conductive material to conduct oxygen ions and an electrically conductive material to conduct electrons. The porous support layer has a high permeability, high porosity, and a high average pore diameter and the intermediate porous layer has a lower permeability and lower pore diameter than the porous support layer. Catalyst particles selected to promote oxidation of a combustible substance are located in the intermediate porous layer and in the porous support adjacent to the intermediate porous layer. The catalyst particles can be formed by wicking a solution of catalyst precursors through the porous support toward the intermediate porous layer.

  7. Catalyst containing oxygen transport membrane

    Energy Technology Data Exchange (ETDEWEB)

    Lane, Jonathan A.; Wilson, Jamie R.; Christie, Gervase Maxwell; Petigny, Nathalie; Sarantopoulos, Christos

    2017-02-07

    A composite oxygen transport membrane having a dense layer, a porous support layer and an intermediate porous layer located between the dense layer and the porous support layer. Both the dense layer and the intermediate porous layer are formed from an ionic conductive material to conduct oxygen ions and an electrically conductive material to conduct electrons. The porous support layer has a high permeability, high porosity, and a microstructure exhibiting substantially uniform pore size distribution as a result of using PMMA pore forming materials or a bi-modal particle size distribution of the porous support layer materials. Catalyst particles selected to promote oxidation of a combustible substance are located in the intermediate porous layer and in the porous support adjacent to the intermediate porous layer. The catalyst particles can be formed by wicking a solution of catalyst precursors through the porous support toward the intermediate porous layer.

  8. Olefins metathesis, synthesis and properties of homogeneous models of the Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3} catalyst; Methathese des olefines, synthese et proprietes des modeles homogenes du catalyseur Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Doledec, G.

    1999-10-05

    The aim of this work was to synthesize and to study homogeneous models of the rhenium oxide on alumina catalyst in order to better understand the influence of the alumina environment over the activity in olefin metathesis. A series of aluminium complexes (ArO){sub 2}Al-Y have been synthesised, where ArO is a 4-substituted-2,6-di-tert-butyl-phenoxy, or (ArO){sub 2} is a CH{sub 2{sup -}} or S-ortho bridged-4,4'-di-tert-butyl-di-phenoxy, and Y is an alkyl or chlorine ligand. The reaction of (ArO){sub 2}Al-Cl with AgReO{sub 4} led to new complexes (ArO){sub 2}Al-OReO{sub 3} (A). These complexes exhibit a low to moderate activity in metathesis of 2-pentene (TOF = 0,5 min{sup -1} at 25 deg. C in a toluene solution). Complexes (ArO){sub 2}Al-R (R = iBu, Et) react with Re{sub 2}O{sub 7} in THF or dioxane giving type B complexes including oligomeric linkages like O{sub 3}Re-[Al(OAr)-O){sub 2}-ReO{sub 3}. They show a fairly high activity in the metathesis of 2-pentene, with TOF values as high as 100 min{sup -1}. As far as we know, these are the most active rhenium-based homogeneous metathesis catalysts. Complexes type A may be converted into type B complexes upon reaction with (ArO){sub 2}Al-R in an ether solvent. The high activity of B complexes is tentatively related to the Al-O-Al linkages that are molecular in the homogeneous models or present at the surface of the alumina in the heterogeneous catalyst. These results bear out again the role of the Lewis acidity in these catalysts. We used (ArO){sub 2}Al-R complexes to modify the heterogenous catalyst. It appears that it is an excellent way to reduce the rhenium loading without any loss of activity. (author)

  9. deNOx catalysts for biomass combustion

    DEFF Research Database (Denmark)

    Kristensen, Steffen Buus

    industrial reference catalyst, after impregnation of 225 mole potassium/g of catalyst. A catalyst plate was synthesised using 20 wt.% sepiolite mixed with nano catalyst, supported by a SiO2-fibre mesh. Realistic potassium poisoning was performed on the catalyst plate, by exposure in a potassium aerosol...... for 632 hours at 350 C. Owing to physical blocking of potassium by sepiolite fibres the composite catalyst showed a further increase in potassium resistance compared with the unsupported catalyst. Finally a refined mechanism was proposed for the nano particle SCR catalyst explaining insitu FTIR...... observation done on the system. Most importantly it indicated that the V=O bond did not break during the SCR reaction, suggesting that another oxygen is responsible for the activity of the active vanadia site....

  10. Novel Fischer-Tropsch catalysts. [DOE patent

    Science.gov (United States)

    Vollhardt, K.P.C.; Perkins, P.

    Novel compounds are described which are used as improved Fischer-Tropsch catalysts particularly for the conversion of CO + H/sub 2/ to gaseous and liquid hydrocarbons at milder conditions than with prior catalysts.

  11. Rhenium Nanochemistry for Catalyst Preparation

    Directory of Open Access Journals (Sweden)

    Vadim G. Kessler

    2012-08-01

    Full Text Available The review presents synthetic approaches to modern rhenium-based catalysts. Creation of an active center is considered as a process of obtaining a nanoparticle or a molecule, immobilized within a matrix of the substrate. Selective chemical routes to preparation of particles of rhenium alloys, rhenium oxides and the molecules of alkyltrioxorhenium, and their insertion into porous structure of zeolites, ordered mesoporous MCM matrices, anodic mesoporous alumina, and porous transition metal oxides are considered. Structure-property relationships are traced for these catalysts in relation to such processes as alkylation and isomerization, olefin metathesis, selective oxidation of olefins, methanol to formaldehyde conversion, etc.

  12. Quick Guide to Flash Catalyst

    CERN Document Server

    Elmansy, Rafiq

    2011-01-01

    How do you transform user interface designs created in Photoshop or Illustrator into interactive web pages? It's easier than you think. This guide shows you how to use Adobe Flash Catalyst to create interactive UIs and website wireframes for Rich Internet Applications-without writing a single line of code. Ideal for web designers, this book introduces Flash Catalyst basics with detailed step-by-step instructions and screenshots that illustrate every part of the process. You'll learn hands-on how to turn your static design or artwork into working user interfaces that can be implemented in Fla

  13. Paraffin Alkylation Using Zeolite Catalysts in a slurry reactor: Chemical Engineering Principles to Extend Catalyst Lifetime

    NARCIS (Netherlands)

    Jong, K.P. de; Mesters, C.M.A.M.; Peferoen, D.G.R.; Brugge, P.T.M. van; Groot, C. de

    1996-01-01

    The alkylation of isobutane with 2-butene is carried out using a zeolitic catalyst in a well stirred slurry reactor. Whereas application of fixed bed technology using a solid acid alkylation catalyst has in the led to catalysts lifetimes in the range of minutes, in this work we report catalyst

  14. Catalyst Deactivation Simulation Through Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst

    Directory of Open Access Journals (Sweden)

    Istadi Istadi

    2011-11-01

    Full Text Available Major problem in CO2 reforming of methane (CORM process is coke formation which is a carbonaceous residue that can physically cover active sites of a catalyst surface and leads to catalyst deactivation. A key to develop a more coke-resistant catalyst lies in a better understanding of the methane reforming mechanism at a molecular level. Therefore, this paper is aimed to simulate a micro-kinetic approach in order to calculate coking rate in CORM reaction. Rates of encapsulating and filamentous carbon formation are also included. The simulation results show that the studied catalyst has a high activity, and the rate of carbon formation is relatively low. This micro-kinetic modeling approach can be used as a tool to better understand the catalyst deactivation phenomena in reaction via carbon deposition. Copyright © 2011 BCREC UNDIP. All rights reserved.(Received: 10th May 2011; Revised: 16th August 2011; Accepted: 27th August 2011[How to Cite: I. Istadi, D.D. Anggoro, N.A.S. Amin, and D.H.W. Ling. (2011. Catalyst Deactivation Simulation Through Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2: 129-136. doi:10.9767/bcrec.6.2.1213.129-136][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.2.1213.129-136 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/1213 ] | View in  |  

  15. On-line regeneration of hydrodesulfurization catalyst

    Science.gov (United States)

    Preston, Jr., John L.

    1980-01-01

    A hydrotreating catalyst is regenerated as it concurrently hydrotreats a hydrocarbon fuel by introducing a low concentration of oxygen into the catalyst bed either continuously or periodically. At low oxygen concentrations the carbon deposits on the catalyst are burned off without harming the catalyst and without significantly affecting the hydrotreating process. In a preferred embodiment the hydrotreating process is hydrodesulfurization, and regenerating is done periodically with oxygen concentrations between 0.1 and 0.5 volume percent.

  16. Hydride mobility in trinuclear sulfido clusters with the core [Rh3(μ-H)(μ3-S)2]: molecular models for hydrogen migration on metal sulfide hydrotreating catalysts.

    Science.gov (United States)

    Jiménez, M Victoria; Lahoz, Fernando J; Lukešová, Lenka; Miranda, José R; Modrego, Francisco J; Nguyen, Duc H; Oro, Luis A; Pérez-Torrente, Jesús J

    2011-07-11

    The treatment of [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{M(μ-Cl)(diolef)}(2)] (diolef=diolefin) in the presence of NEt(3) affords the hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(diolef){P(OPh)(3)}(4)] (diolef=1,5-cyclooctadiene (cod) for 1, 2,5-norbornadiene (nbd) for 2, and tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5,7-triene (tfb) for 3) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(cod){P(OPh)(3)}(4)] (4). Cluster 1 can be also obtained by treating [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{Rh(μ-OMe)(cod)}(2)], although the main product of the reaction with [{Ir(μ-OMe)(cod)}(2)] was [RhIr(2)(μ-H)(μ(3)-S)(2)(cod)(2){P(OPh)(3)}(2)] (5). The molecular structures of clusters 1 and 4 have been determined by X-ray diffraction methods. The deprotonation of a hydrosulfido ligand in [{Rh(μ-SH)(CO)(PPh(3))}(2)] by [M(acac)(diolef)] (acac=acetylacetonate) results in the formation of hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(CO)(2) (diolef)(PPh(3))(2)] (diolef=cod for 6, nbd for 7) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(CO)(2)(cod)(PPh(3))(2)] (8). Clusters 1-3 and 5 exist in solution as two interconverting isomers with the bridging hydride ligand at different edges. Cluster 8 exists as three isomers that arise from the disposition of the PPh(3) ligands in the cluster (cis and trans) and the location of the hydride ligand. The dynamic behaviour of clusters with bulky triphenylphosphite ligands, which involves hydrogen migration from rhodium to sulfur with a switch from hydride to proton character, is significant to understand hydrogen diffusion on the surface of metal sulfide hydrotreating catalysts.

  17. Mechanistic insight into sonochemical biodiesel synthesis using heterogeneous base catalyst.

    Science.gov (United States)

    Choudhury, Hanif A; Chakma, Sankar; Moholkar, Vijayanand S

    2014-01-01

    The beneficial effect of ultrasound on transesterification reaction is well known. Heterogeneous (or solid) catalysts for biodiesel synthesis have merit that they do not contaminate the byproduct of glycerol. In this paper, we have attempted to identify the mechanistic features of ultrasound-enhanced biodiesel synthesis with the base-catalyst of CaO. A statistical design of experiments (Box-Behnken) was used to identify the influence of temperature, alcohol to oil molar ratio and catalyst loading on transesterification yield. The optimum values of these parameters for the highest yield were identified through Response Surface Method (with a quadratic model) and ANOVA. These values are: temperature=62 °C, molar ratio=10:1 and catalyst loading=6 wt.%. The activation energy was determined as 82.3 kJ/mol, which is higher than that for homogeneous catalyzed system (for both acidic and basic catalyst). The experimental results have been analyzed vis-à-vis simulations of cavitation bubble dynamics. Due to 3-phase heterogeneity of the system, the yield was dominated by intrinsic kinetics, and the optimum temperature for the highest yield was close to boiling point of methanol. At this temperature, the influence of cavitation bubbles (in terms of both sonochemical and sonophysical effect) is negligible, and ultrasonic micro-streaming provided necessary convection in the system. The influence of all parameters on the reaction system was found to be strongly inter-dependent.

  18. Deactivation by carbon of iron catalysts for indirect liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Bartholomew, C H

    1991-02-14

    Progress is reported for a four-year fundamental investigation of carbon formation and its effects on the activity and selectivity of promoted iron catalysts for FT synthesis, the objectives of which were to (1) determine rates and mechanisms of carbon deactivation of unsupported Fe and Fe/K catalysts during CO hydrogenation and (2) model the global rates of deactivation at the surface of the catalyst for the same catalysts. A computer-automated reactor system to be used in the kinetic and deactivation studies was designed, constructed and tested. Kinetic data for CO hydrogenation on unsupported, unpromoted iron, 99% Fe/1% Al{sub 2}O{sub 3}, and K-promoted 99% Fe/1% Al{sub 2}O{sub 3} catalysts were obtained as functions of temperature, reactant particle pressures and time. The activity/selectivity and kinetic data are consistent with those previously reported for supported, unpromoted and promoted iron. Two kinds of deactivation were observed during FT synthesis on these samples: (1) loss of surface area after reduction of unsupported, unpromoted iron at 400{degree}C and (2) loss of activity with time due to carbon deposition, especially in the case of K-promoted 99% Fe/1% A1{sub 2}O{sub 3}. Deactivation rate data were obtained for CO hydrogenation on promoted Fe as a function of time, temperature, and H{sub 2}/CO ratio. 50 refs., 24 figs., 5 tabs.

  19. Using articulation and inscription as catalysts for reflection: Design principles for reflective inquiry

    Science.gov (United States)

    Loh, Ben Tun-Bin

    2003-07-01

    The demand for students to engage in complex student-driven and information-rich inquiry investigations poses challenges to existing learning environments. Students are not familiar with this style of work, and lack the skills, tools, and expectations it demands, often forging blindly forward in the investigation. If students are to be successful, they need to learn to be reflective inquirers, periodically stepping back from an investigation to evaluate their work. The fundamental goal of my dissertation is to understand how to design learning environments to promote and support reflective inquiry. I have three basic research questions: how to define this mode of work, how to help students learn it, and understanding how it facilitates reflection when enacted in a classroom. I take an exploratory approach in which, through iterative cycles of design, development, and reflection, I develop principles of design for reflective inquiry, instantiate those principles in the design of a software environment, and test that software in the context of classroom work. My work contributes to the understanding of reflective inquiry in three ways: First, I define a task model that describes the kinds of operations (cognitive tasks) that students should engage in as reflective inquirers. These operations are defined in terms of two basic tasks: articulation and inscription, which serve as catalysts for externalizing student thinking as objects of and triggers for reflection. Second, I instantiate the task model in the design of software tools (the Progress Portfolio). And, through proof of concept pilot studies, I examine how the task model and tools helped students with their investigative classroom work. Finally, I take a step back from these implementations and articulate general design principles for reflective inquiry with the goal of informing the design of other reflective inquiry learning environments. There are three design principles: (1) Provide a designated work space

  20. Efficient epoxidation of propene using molecular catalysts

    DEFF Research Database (Denmark)

    Markovits, Iulius I. E.; Anthofer, Michael H.; Kolding, Helene

    2014-01-01

    The epoxidation of propene is performed in homogeneous phase using various molecular catalysts and H2O2 or tert-butyl hydroperoxide as oxidants. A comparison between some molybdenum catalysts and methyltrioxorhenium (MTO) shows that the well known Re catalyst is the best among the examined...