WorldWideScience

Sample records for catalytic oxidation reactions

  1. Process of forming catalytic surfaces for wet oxidation reactions

    Science.gov (United States)

    Jagow, R. B. (Inventor)

    1977-01-01

    A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

  2. Reaction pathways for catalytic gas-phase oxidation of glycerol over mixed metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Suprun, W.; Glaeser, R.; Papp, H. [Leipzig Univ. (Germany). Inst. of Chemical Technology

    2011-07-01

    Glycerol as a main by-product from bio-diesel manufacture is a cheap raw material with large potential for chemical or biochemical transformations to value-added C3-chemicals. One possible way of glycerol utilization involves its catalytic oxidation to acrylic acid as an alternative to petrochemical routes. However, this catalytic conversion exhibits various problems such as harsh reaction conditions, severe catalyst coking and large amounts of undesired by-products. In this study, the reaction pathways for gas-phase conversion of glycerol over transition metal oxides (Mo, V und W) supported on TiO{sub 2} and SiO{sub 2} were investigated by two methods: (i) steady state experiments of glycerol oxidation and possible reactions intermediates, i.e., acrolein, 3-hydroxy propionaldehyde and acetaldehyde, and (ii) temperature-programmed surface reaction (TPSR) studies of glycerol conversion in the presence and in the absence of gas-phase oxygen. It is shown that the supported W-, V and Mo-oxides possess an ability to catalyze the oxidation of glycerol to acrylic acid. These investigations allowed us to gain a deeper insight into the reaction mechanism. Thus, based on the obtained results, three possible reactions pathways for the selective oxidation of glycerol to acrylic acid on the transition metal-containing catalysts are proposed. The major pathways in presence of molecular oxygen are a fast successive destructive oxidation of glycerol to CO{sub x} and the dehydration of glycerol to acrolein which is a rate-limiting step. (orig.)

  3. A consistent reaction scheme for the selective catalytic reduction of nitrogen oxides with ammonia

    DEFF Research Database (Denmark)

    Janssens, Ton V.W.; Falsig, Hanne; Lundegaard, Lars Fahl;

    2015-01-01

    For the first time, the standard and fast selective catalytic reduction of NO by NH3 are described in a complete catalytic cycle, that is able to produce the correct stoichiometry, while only allowing adsorption and desorption of stable molecules. The standard SCR reaction is a coupling of the ac......For the first time, the standard and fast selective catalytic reduction of NO by NH3 are described in a complete catalytic cycle, that is able to produce the correct stoichiometry, while only allowing adsorption and desorption of stable molecules. The standard SCR reaction is a coupling...... of the activation of NO by O2 with the fast SCR reaction, enabled by the release of NO2. According to the scheme, the SCR reaction can be divided in an oxidation of the catalyst by NO + O2 and a reduction by NO + NH3; these steps together constitute a complete catalytic cycle. Furthermore both NO and NH3...... spectroscopy (FTIR). A consequence of the reaction scheme is that all intermediates in fast SCR are also part of the standard SCR cycle. The calculated activation energy by density functional theory (DFT) indicates that the oxidation of an NO molecule by O2 to a bidentate nitrate ligand is rate determining...

  4. Learning the Fundamentals of Kinetics and Reaction Engineering with the Catalytic Oxidation of Methane

    Science.gov (United States)

    Cybulskis, Viktor J.; Smeltz, Andrew D.; Zvinevich, Yury; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.

    2016-01-01

    Understanding catalytic chemistry, collecting and interpreting kinetic data, and operating chemical reactors are critical skills for chemical engineers. This laboratory experiment provides students with a hands-on supplement to a course in chemical kinetics and reaction engineering. The oxidation of methane with a palladium catalyst supported on…

  5. Catalytic hydrocarbon reactions over supported metal oxides. Progress report, April 1, 1994--January 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1995-01-31

    Oxide catalysis plays a central role in hydrocarbon processing and improvements in catalytic activity or selectivity are of great technological importance because these improvements will translate directly into more efficient utilization of hydrocarbon supplies and lower energy consumption in separation processes. An understanding of the relationships between surface structure and catalytic properties is needed to describe and improve oxide catalysts. Our approach has been to prepare supported oxides that have a specific structure and oxidation state and then employ these structures in reaction studies. Our current research program is focused on studying the fundamental relationships between structure and reactivity for two important reactions that are present in many oxide-catalyzed processes, partial oxidation and carbon-carbon bond formation. Oxide catalysis can be a complex process with both metal cation and oxygen anions participating in the chemical reactions. From an energy perspective carbon-carbon bond formation is particularly relevant to CO hydrogenation in isosynthesis. Hydrogenolysis and hydrogenation form the basis for heteroatom removal in fuels processing. Understanding the catalysis of these processes (and others) requires isolating reaction steps in the overall cycle and determining how structure and composition influence the individual reaction steps. Specially designed oxides, such as we use, permit one to study some of the steps in oxidation, carbon-carbon coupling and heteroatom removal catalysis. During the course of our studies we have: (1) developed methods to form and stabilize various Mo and W oxide structures on silica; (2) studied C-H abstraction reactions over the fully oxidized cations; (3) studied C-C bond coupling by methathesis and reductive coupling of aldehydes and ketones over reduced cation structures; and (4) initiated a study of hydrogenation and hydrogenolysis over reduced cation structures.

  6. Catalytic hydrocarbon reactions over supported metal oxides. Final report, August 1, 1986--July 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1995-10-20

    Oxide catalysis plays a central role in hydrocarbon processing and improvements in catalytic activity or selectivity are of great technological importance because these improvements will translate directly into more efficient utilization of hydrocarbon supplies and lower energy consumption in separation processes. An understanding of the relationships between surface structure and catalytic properties is needed to describe and improve oxide catalysts. The approach has been to prepare supported oxides that have a specific structure and oxidation state and then employ these structures in reaction studies. The current research program is focused on studying the fundamental relationships between structure and reactivity for two important reactions that are present in many oxide-catalyzed processes, partial oxidation and carbon-carbon bond formation. During the course of these studies the author has: (1) developed methods to form and stabilize various Mo and W oxide structures on silica; (2) studied C-H abstraction reactions over the fully oxidized cations; (3) studied C-C bond coupling by metathesis and reductive coupling of aldehydes and ketones over reduced cation structures; and (4) initiated a study of hydrogenation and hydrogenolysis over reduced cation structures.

  7. Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

    2015-01-01

    ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

  8. A New Reaction for Kinetic Spetrophotometric Determination of Trace Ruthenium--Catalytic Oxidation of Methyl Green by Bromate

    Institute of Scientific and Technical Information of China (English)

    ZHOU Zhi-rong; XU Qiong; XIONG Yan; WEI Jia-wen

    2006-01-01

    A sensitive catalytic spectrophotometric method for the determination of ruthenium (Ⅲ) has been developed, based on its catalytic effect on the oxidation reaction of methyl green with potassium bromate in acid solution medium at 100 ℃. The above reaction is followed spectrophotometrically by measuring the decrease in the absorbance at 625 nm for the catalytic reaction of methyl green. The calibration curve for the recommended reaction-rate method was linear in the concentration range over 0.00-0.80 μg/L and the detection limit of the method for Ru (Ⅲ) is 0.006μg/L. Almost no foreign ions interfered in the determination at less than 25-fold concentration of Ru (Ⅲ). The method is highly sensitive, more selective and very stable, and has been successfully applied for the determination of trace ruthenium in some ores and metallurgy products.

  9. STUDIES ON THE CATALYTIC REACTION OF NITROGEN OXIDE ON METAL MODIFIED ACTIVATED CARBON FIBERS

    Institute of Scientific and Technical Information of China (English)

    FU Ruowen; DU Xiuying; LIN Yuansheng; XU Hao; HU Yiongjun

    2003-01-01

    The catalytic reaction of NO with CO and decomposition of NO over metal modified ACFs were investigated and compared with other carriers supported catalysts. It is demonstrated that Pd/ACF and Pd/Cu/ACF have high catalytic activity for the reaction of NO/CO, while Pt/ACF.Pt/Cu/ACF and Co/Cu/ACF have very Iow catalytic activity in similar circumstance. Pd-modified ACF possesses high catalytic decomposition of NO at 300 ℃. Pd/CB and Pd/GAC present good catalytic decomposition ability for NO only at low flowrate. Pd/G, Pd/ZMS and Pd/A however, do not show any catalytic activity for NO decomposition even at 400 ℃. Catalytic temperature, NO flowrate and loading of metal components affect the decomposition rate of NO. The coexistence of Cu with Pd on Cu/Pd/ACF leads to crystalline of palladium to more unperfected so as to that increase the catalytic activity.

  10. TiO2-sludge carbon enhanced catalytic oxidative reaction in environmental wastewaters applications.

    Science.gov (United States)

    Athalathil, Sunil; Erjavec, Boštjan; Kaplan, Renata; Stüber, Frank; Bengoa, Christophe; Font, Josep; Fortuny, Agusti; Pintar, Albin; Fabregat, Azael

    2015-12-30

    The enhanced oxidative potential of sludge carbon/TiO2 nano composites (SNCs), applied as heterogeneous catalysts in advanced oxidation processes (AOPs), was studied. Fabrification of efficient SNCs using different methods and successful evaluation of their catalytic oxidative activity is reported for the first time. Surface modification processes of hydrothermal deposition, chemical treatment and sol-gel solution resulted in improved catalytic activity and good surface chemistry of the SNCs. The solids obtained after chemical treatment and hydrothermal deposition processes exhibit excellent crystallinity and photocatalytic activity. The highest photocatalytic rate was obtained for the material prepared using hydrothermal deposition technique, compared to other nanocomposites. Further, improved removal of bisphenol A (BPA) from aqueous phase by means of catalytic ozonation and catalytic wet air oxidation processes is achieved over the solid synthesized using chemical treatment method. The present results demonstrate that the addition of TiO2 on the surface of sludge carbon (SC) increases catalytic oxidative activity of SNCs. The latter produced from harmful sludge materials can be therefore used as cost-effective and efficient sludge derived catalysts for the removal of hazardous pollutants. PMID:26223014

  11. Catalytic ammonia oxidation to nitrogen (I) oxide

    OpenAIRE

    MASALITINA NATALIYA YUREVNA; SAVENKOV ANATOLIY SERGEEVICH

    2015-01-01

    The process of synthesis of nitrous oxide by low-temperature catalytical oxidation of NH has been investigated for organic synthesis. The investigation has been carried out by the stage separation approach with NH oxidation occurring in several reaction zones, which characterized by different catalytic conditions. The selectivity for N₂O was 92–92,5 % at the ammonia conversion of 98–99.5 % in the optimal temperature range.

  12. Preparation of porous paper composites with ruthenium hydroxide and catalytic alcohol oxidation in a multiphase gas–liquid–solid reaction

    International Nuclear Information System (INIS)

    Highlights: • Flexible and porous paper-structured Ru(OH)x catalysts were prepared successfully. • Ru(OH)x catalysts were dispersed on the ceramic fiber networks of paper composites. • Catalytic oxidation of benzyl alcohol proceeded efficiently in three-phase reactions. • Paper catalysts exhibited much higher performance than conventional solid catalysts. - Abstract: In situ synthesis of ruthenium hydroxide catalysts on a microporous fiber-network structure of ceramic paper composites was achieved. The efficient catalytic oxidation of alcohol was investigated in a heterogeneous, multiphase gas–liquid–solid reaction. A simple papermaking technique and subsequent immersion in a ruthenium chloride solution allowed us to fabricate novel-concept microstructured catalysts. The paper-structured catalysts possess micropores ca. 30 μm in diameter with high porosity of ca. 90%. They exhibited much higher catalytic efficiency in the O2-mediated oxidation in toluene of benzyl alcohol to benzaldehyde in a fixed bed external loop reactor, as compared with conventional pellet- and bead-type solid catalysts. This excellent catalytic effect is possibly attributed to the porous paper composite microstructure like microreactors

  13. Preparation of porous paper composites with ruthenium hydroxide and catalytic alcohol oxidation in a multiphase gas–liquid–solid reaction

    Energy Technology Data Exchange (ETDEWEB)

    Homma, Taichi [Department of Agro-Environmental Sciences, Graduate School of Bioresource and Bioenvironmental Sciences, and Biotron Application Center, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Processing Development Research Laboratory, Kao Corporation, 2606 Akabane, Ichikai-machi, Haga-gun, Tochigi 321-3497 (Japan); Kitaoka, Takuya, E-mail: tkitaoka@agr.kyushu-u.ac.jp [Department of Agro-Environmental Sciences, Graduate School of Bioresource and Bioenvironmental Sciences, and Biotron Application Center, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan)

    2014-05-01

    Highlights: • Flexible and porous paper-structured Ru(OH){sub x} catalysts were prepared successfully. • Ru(OH){sub x} catalysts were dispersed on the ceramic fiber networks of paper composites. • Catalytic oxidation of benzyl alcohol proceeded efficiently in three-phase reactions. • Paper catalysts exhibited much higher performance than conventional solid catalysts. - Abstract: In situ synthesis of ruthenium hydroxide catalysts on a microporous fiber-network structure of ceramic paper composites was achieved. The efficient catalytic oxidation of alcohol was investigated in a heterogeneous, multiphase gas–liquid–solid reaction. A simple papermaking technique and subsequent immersion in a ruthenium chloride solution allowed us to fabricate novel-concept microstructured catalysts. The paper-structured catalysts possess micropores ca. 30 μm in diameter with high porosity of ca. 90%. They exhibited much higher catalytic efficiency in the O{sub 2}-mediated oxidation in toluene of benzyl alcohol to benzaldehyde in a fixed bed external loop reactor, as compared with conventional pellet- and bead-type solid catalysts. This excellent catalytic effect is possibly attributed to the porous paper composite microstructure like microreactors.

  14. The effect of noble metals on catalytic methanation reaction over supported Mn/Ni oxide based catalysts

    OpenAIRE

    Wan Azelee Wan Abu Bakar; Rusmidah Ali; Nurul Shafeeqa Mohammad

    2015-01-01

    Carbon dioxide (CO2) in sour natural gas can be removed using green technology via catalytic methanation reaction by converting CO2 to methane (CH4) gas. Using waste to wealth concept, production of CH4 would increase as well as creating environmental friendly approach for the purification of natural gas. In this research, a series of alumina supported manganese–nickel oxide based catalysts doped with noble metals such as ruthenium and palladium were prepared by wetness impregnation method. T...

  15. Reaction Mechanism for the Formation of Nitrogen Oxides (NO x ) During Coke Oxidation in Fluidized Catalytic Cracking Units

    KAUST Repository

    Chaparala, Sree Vidya

    2015-06-11

    Fluidized catalytic cracking (FCC) units in refineries process heavy feedstock obtained from crude oil distillation. While cracking feed, catalysts get deactivated due to coke deposition. During catalyst regeneration by burning coke in air, nitrogen oxides (NOx) are formed. The increase in nitrogen content in feed over time has resulted in increased NOx emissions. To predict NOx concentration in flue gas, a reliable model for FCC regenerators is needed that requires comprehensive understanding and accurate kinetics for NOx formation. Based on the nitrogen-containing functional groups on coke, model molecules are selected to study reactions between coke-bound nitrogen and O2 to form NO and NO2 using density functional theory. The reaction kinetics for the proposed pathways are evaluated using transition state theory. It is observed that the addition of O2 on coke is favored only when the free radical is present on the carbon atom instead of nitrogen atom. Thus, NOx formation during coke oxidation does not result from the direct attack by O2 on N atoms of coke, but from the transfer of an O atom to N from a neighboring site. The low activation energies required for NO formation indicate that it is more likely to form than NO2 during coke oxidation. The favorable pathways for NOx formation that can be used in FCC models are identified. Copyright © 2015 Taylor & Francis Group, LLC.

  16. Effect of diluent and reaction parameter on selective oxidation of propane over MoVTeNb catalyst using nanoflow catalytic reactor

    Institute of Scientific and Technical Information of China (English)

    Restu Kartiko Widi; Sharifah Bee Abdul Hamid; Robert Schl(o)gl

    2008-01-01

    The selective oxidation of propane to acrylic acid over an MoVTeNb mixed oxide catalyst, dried and calcined before reaction has been studied using high-throughput instrumentation, which is called nanoflow catalytic reactor. The effects of catalyst dilution on the catalytic performance of the MoVTeNb mixed oxide catalyst in selective oxidation of propane to acrylic acid were also investigated. The effects of some reaction parameters, such as gas hourly space velocity (GHSV) and reaction temperature, for selective oxidation of propane to acrylic acid over diluted MoVTeNb catalyst have also been studied. The configuration of the nanoflow is shown to be suitable for screen catalytic performance, and its operating conditions were mimicked closely to conventional laboratory as well as to industrial conditions. The results obtained provided very good reproducibility and it showed that preparation methods as well as reaction parameters can play significant roles in catalytic performance of these catalysts.

  17. Study of the dynamics of the MoO2-Mo2C system for catalytic partial oxidation reactions

    Science.gov (United States)

    Cuba Torres, Christian Martin

    On a global scale, the energy demand is largely supplied by the combustion of non-renewable fossil fuels. However, their rapid depletion coupled with environmental and sustainability concerns are the main drivers to seek for alternative energetic strategies. To this end, the sustainable generation of hydrogen from renewable resources such as biodiesel would represent an attractive alternative solution to fossil fuels. Furthermore, hydrogen's lower environmental impact and greater independence from foreign control make it a strong contender for solving this global problem. Among a wide variety of methods for hydrogen production, the catalytic partial oxidation offers numerous advantages for compact and mobile fuel processing systems. For this reaction, the present work explores the versatility of the Mo--O--C catalytic system under different synthesis methods and reforming conditions using methyl oleate as a surrogate biodiesel. MoO2 exhibits good catalytic activity and exhibits high coke-resistance even under reforming conditions where long-chain oxygenated compounds are prone to form coke. Moreover, the lattice oxygen present in MoO2 promotes the Mars-Van Krevelen mechanism. Also, it is introduced a novel beta-Mo2C synthesis by the in-situ formation method that does not utilize external H2 inputs. Herein, the MoO 2/Mo2C system maintains high catalytic activity for partial oxidation while the lattice oxygen serves as a carbon buffer for preventing coke formation. This unique feature allows for longer operation reforming times despite slightly lower catalytic activity compared to the catalysts prepared by the traditional temperature-programmed reaction method. Moreover, it is demonstrated by a pulse reaction technique that during the phase transformation of MoO2 to beta-Mo2C, the formation of Mo metal as an intermediate is not responsible for the sintering of the material wrongly assumed by the temperature-programmed method.

  18. CFD modeling of reaction and mass transfer through a single pellet:Catalytic oxidative coupling of methane

    Institute of Scientific and Technical Information of China (English)

    Siavash Seyednej adian; Nakisa Yaghobi; Ramin Maghrebi; Leila Vafajoo

    2011-01-01

    In this study a mathematical model of a small scale single pellet for the oxidative coupling of methane (OCM) over titanite pervoskité isdeveloped.The method is based on a computational fluid dynamics (CFD) code which known as Fluent may be adopted to model the reactions that take place inside the porous catalyst pellet.The steady state single pellet model is coupled with a kinetic model and the intra-pellet concentration profiles of species are provided.Subsequent to achieving this goal,a nonlinear reaction network consisting of nine catalytic reactions and one gas phase reaction as an external program is successfully implemented to CFD-code as a reaction term in solving the equations.This study is based on the experimental design which is conducted in a differential reactor with a Sn/BaTiO3 catalyst (7-8 mesh) at atmospheric pressure,GHSV of 12000 h-1,ratio of methane to oxygen of 2,and three different temperatures of 1023,1048 and 1073 K.The modeling results such as selectivity and conversion at the pellet exit are in good agreement with the experimental data.Therefore,it is suggested that to achieve high yield in OCM process the modeling of the single pellet should be considered as the heart of catalytic fixed bed reactor.

  19. The selective catalytic reduction (SCR) of NO with NH3 at vanadium oxide catalysts: Adsorption, diffusion, reaction

    International Nuclear Information System (INIS)

    The selective catalytic reduction (SCR) of NOx with NH3 over vanadium based metal-oxide (VOx) catalysts has been proven to be one of the most effective NOx reduction processes. Even though it is widely used in commercial applications details of the reaction mechanism are still under debate. Experiments show that adsorption, diffusion, and reactions with NO and (de)hydrogenation processes at the VOx surface contribute elementary steps. These processes are examined in theoretical studies employing density-functional theory together with gradient corrected functionals. The VOx substrate is modeled by clusters cut out from the ideal V2O5(010) surface where peripheral oxygen bonds are saturated by hydrogen. Apart from the perfect oxide surface also differently reduced surfaces are considered by introducing oxygen vacancies. NH3 is found to interact only weakly with the perfect V2O5(010) surface. In the presence of OH groups (Broensted acid sites) NH3 can form a surface NH4+ species. NH3 can also interact with the surface near oxygen vacancies, adsorbing at vanadium centers of lower coordination (Lewis acid sites). In contrast, NO interacts much more weakly with the surface. Further, simultaneous NO, NH3 adsorption and SCR reaction scenarios at Broensted and Lewis acid sites are examined. They result in different reaction paths and intermediates as will be discussed in detail.

  20. Reaction phenomena of catalytic partial oxidation of methane under the impact of carbon dioxide addition and heat recirculation

    International Nuclear Information System (INIS)

    The reaction phenomena of CPOM (catalytic partial oxidation of methane) in a Swiss-roll reactor are studied numerically where a rhodium-based catalyst bed is embedded at the center of the reactor. CO2 is added into the feed gas and excess enthalpy recovery is performed to evaluate their influences on CPOM performance. In the study, the mole ratio of O2 to CH4 (O2/CH4 ratio) is fixed at 0.5 and the mole ratio of CO2 to O2 (CO2/O2 ratio) is in the range of 0–2. The results reveal that CO2 addition into the influent has a slight effect on methane combustion, but significantly enhances dry reforming and suppresses steam reforming. The reaction extents of steam reforming and dry reforming in CPOM without heat recovery and CO2 addition are in a comparable state. Once CO2 is added into the feed gas, the dry reforming is enhanced, thereby dominating CH4 consumption. Compared to the reactor without excess enthalpy recovery, heat recirculation drastically increases the maximum reaction temperature and CH4 conversion in the catalyst bed; it also intensifies the H2 selectivity, H2 yield, CO2 conversion, and syngas production rate. The predictions indicate that the heat recirculation is able to improve the syngas formation up to 45%. - Highlights: • Catalytic partial oxidation of methane with CO2 addition and heat recovery is studied. • CO2 addition has a slight effect on methane combustion. • CO2 addition significantly enhances dry reforming and suppresses steam reforming. • Dry reforming dominates CH4 consumption when CO2 addition is large. • Heat recirculation can improve the syngas formation up to 45%

  1. Catalytic Radical Domino Reactions in Organic Synthesis

    Science.gov (United States)

    Sebren, Leanne J.; Devery, James J.; Stephenson, Corey R.J.

    2014-01-01

    Catalytic radical-based domino reactions represent important advances in synthetic organic chemistry. Their development benefits synthesis by providing atom- and step-economical methods to complex molecules. Intricate combinations of radical, cationic, anionic, oxidative/reductive, and transition metal mechanistic steps result in cyclizations, additions, fragmentations, ring-expansions, and rearrangements. This Perspective summarizes recent developments in the field of catalytic domino processes. PMID:24587964

  2. Spectrophotometric reaction rate method for the determination of osmium by its catalytic effect on the oxidation of gallocyanine by bromate.

    Science.gov (United States)

    Ensafi, A A; Shamss-E-Sollari, E

    1994-10-01

    A simple kinetic spectrophotometric method was developed for the determination of osmium. The method is based on the catalytic effect of osmium as osmium tetroxide on the oxidation of gallocyanine by bromate at pH 7. The reaction is monitored spectrophotometrically by measuring the decreasing absorbance of gallocyanine at 620 nm by the fixed-time method. A detection limit of 0.01 ng/ml and linear calibration curve from 0.1 to 100 and from 100 to 1200 ng/ml Os(VIII) is reported. The relative standard deviation for 0.0100 microg/ml Os(VIII) is 0.8% (N = 10). The method is free from most interferences. Osmium in synthetic samples is determined by this method, with satisfactory results. PMID:18966116

  3. Characterization of catalytic supports based in mixed oxides for control reactions of NO and N2O

    International Nuclear Information System (INIS)

    The catalytic supports Al2O3, La2O3 and Al2O3-La2O3 were prepared by the Precipitation and Coprecipitation techniques. The catalytic supports Al2O3, La2O3 and Al2O3-La2O3 were characterized by several techniques to determine: texture (Bet), crystallinity (XRD), chemical composition (Sem)(Ftir) and it was evaluated their total acidity by reaction with 2-propanol. The investigation will be continued with the cobalt addition and this will be evaluated for its catalytic activity in control reactions of N O and N2O. (Author)

  4. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    Vivek V Ranade

    2014-03-01

    Catalytic reactions are ubiquitous in chemical and allied industries. A homogeneous or heterogeneous catalyst which provides an alternative route of reaction with lower activation energy and better control on selectivity can make substantial impact on process viability and economics. Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is discussed. Some examples where performance enhancement was realized by catalyst design, appropriate choice of reactor, better injection and dispersion strategies and recent advances in process intensification/ multifunctional reactors are discussed to illustrate the approach.

  5. The effect of noble metals on catalytic methanation reaction over supported Mn/Ni oxide based catalysts

    Directory of Open Access Journals (Sweden)

    Wan Azelee Wan Abu Bakar

    2015-09-01

    Full Text Available Carbon dioxide (CO2 in sour natural gas can be removed using green technology via catalytic methanation reaction by converting CO2 to methane (CH4 gas. Using waste to wealth concept, production of CH4 would increase as well as creating environmental friendly approach for the purification of natural gas. In this research, a series of alumina supported manganese–nickel oxide based catalysts doped with noble metals such as ruthenium and palladium were prepared by wetness impregnation method. The prepared catalysts were run catalytic screening process using in-house built micro reactor coupled with Fourier Transform Infra Red (FTIR spectroscopy to study the percentage CO2 conversion and CH4 formation analyzed by GC. Ru/Mn/Ni(5:35:60/Al2O3 calcined at 1000 °C was found to be the potential catalyst which gave 99.74% of CO2 conversion and 72.36% of CH4 formation at 400 °C reaction temperature. XRD diffractogram illustrated that the supported catalyst was in polycrystalline with some amorphous state at 1000 °C calcination temperature with the presence of NiO as active site. According to FESEM micrographs, both fresh and used catalysts displayed spherical shape with small particle sizes in agglomerated and aggregated mixture. Nitrogen Adsorption analysis revealed that both catalysts were in mesoporous structures with BET surface area in the range of 46–60 m2/g. All the impurities have been removed at 1000 °C calcination temperature as presented by FTIR, TGA–DTA and EDX data.

  6. Structural and catalytic properties of a novel vanadium containing solid core mesoporous silica shell catalysts for gas phase oxidation reaction

    Indian Academy of Sciences (India)

    N Venkatathri; Vijayamohanan K Pillai; A Rajini; M Nooka Raju; I A K Reddy

    2013-01-01

    A novel vanadium containing solid core mesoporous silica shell catalyst was synthesized with different Si/V ratios by sol-gel method under neutral conditions. The synthesized materials were characterized by various techniques and gas phase diphenyl methane oxidation reaction. The mesoporosity combined with microporosity are formed by incorporation of octadecyltrichloro silane and triethylamine in the catalyst and it was found out from E-DAX and BET—surface area analysis. The material was found to be nanocrystalline. Vanadium is present as V4+ species in as-synthesized samples and convert to V5+ on calcination. Most of the vanadium is present in tetrahedral or square pyramidal environment. Incorporation of vanadium in silica framework was confirmed by 29Si MAS NMR analysis. Among the various vanadium containing solid core mesoporous silica shell catalysts, the Si/V =100 ratio exhibited maximum efficiency towards diphenyl methane to benzophenone gas phase reaction. The optimum condition required for maximum conversion and selectivity was found out from the catalytic studies.

  7. Catalytic Fehling's Reaction: An Efficient Aerobic Oxidation of Aldehyde Catalyzed by Copper in Water.

    Science.gov (United States)

    Liu, Mingxin; Li, Chao-Jun

    2016-08-26

    The first example of homogeneous copper-catalyzed aerobic oxidation of aldehydes is reported. This method utilizes atmospheric oxygen as the sole oxidant, proceeds under extremely mild aqueous conditions, and covers a wide range of various functionalized aldehydes. Chromatography is generally not necessary for product purification. PMID:27505714

  8. Robust non-carbon titanium nitride nanotubes supported Pt catalyst with enhanced catalytic activity and durability for methanol oxidation reaction

    International Nuclear Information System (INIS)

    By the combination of solvothermal alcoholysis and post-nitriding method, titanium nitride nanotubes (TiN NTs), with high surface area, hollow and interior porous structure are prepared successfully and used at a support for Pt nanoparticles. The TiN NTs supported Pt (Pt/TiN NTs) catalyst displays enhanced activity and durability towards methanol oxidation reaction (MOR) compared with the commercial Pt/C (E-TEK) catalyst. X ray diffraction (XRD), nitrogen adsorption/desorption, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements are performed to investigate the physicochemical properties of the synthesized catalyst. SEM and TEM images reveal that the wall of the TiN NTs is porous and Pt nanoparticles supported on the dendritic TiN nanocrystals exhibit small size and good dispersion. Effects of inherent corrosion-resistant, tubular and porous nanostructures and electron transfer due to the strong metal–support interactions of TiN NTs contribute to the enhanced catalytic activity and stability of Pt/TiN NTs towards the MOR

  9. The Synthesis, Characterization and Catalytic Reaction Studies of Monodisperse Platinum Nanoparticles in Mesoporous Oxide Materials

    Energy Technology Data Exchange (ETDEWEB)

    Rioux, Robert M. [Univ. of California, Berkeley, CA (United States)

    2006-01-01

    A catalyst design program was implemented in which Pt nanoparticles, either of monodisperse size and/or shape were synthesized, characterized and studied in a number of hydrocarbon conversion reactions. The novel preparation of these materials enables exquisite control over their physical and chemical properties that could be controlled (and therefore rationally tuned) during synthesis. The ability to synthesize rather than prepare catalysts followed by thorough characterization enable accurate structure-function relationships to be elucidated. This thesis emphasizes all three aspects of catalyst design: synthesis, characterization and reactivity studies. The precise control of metal nanoparticle size, surface structure and composition may enable the development of highly active and selective heterogeneous catalysts.

  10. Catalytic Chemistry on Oxide Nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Asthagiri, Aravind; Dixon, David A.; Dohnalek, Zdenek; Kay, Bruce D.; Rodriquez, Jose A.; Rousseau, Roger J.; Stacchiola, Dario; Weaver, Jason F.

    2016-05-29

    Metal oxides represent one of the most important and widely employed materials in catalysis. Extreme variability of their chemistry provides a unique opportunity to tune their properties and to utilize them for the design of highly active and selective catalysts. For bulk oxides, this can be achieved by varying their stoichiometry, phase, exposed surface facets, defect, dopant densities and numerous other ways. Further, distinct properties from those of bulk oxides can be attained by restricting the oxide dimensionality and preparing them in the form of ultrathin films and nanoclusters as discussed throughout this book. In this chapter we focus on demonstrating such unique catalytic properties brought by the oxide nanoscaling. In the highlighted studies planar models are carefully designed to achieve minimal dispersion of structural motifs and to attain detailed mechanistic understanding of targeted chemical transformations. Detailed level of morphological and structural characterization necessary to achieve this goal is accomplished by employing both high-resolution imaging via scanning probe methods and ensemble-averaged surface sensitive spectroscopic methods. Three prototypical examples illustrating different properties of nanoscaled oxides in different classes of reactions are selected.

  11. Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1992-02-03

    This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.

  12. Biomimetic, Catalytic Oxidation in Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    Shun-lchi Murahashi

    2005-01-01

    @@ 1Introduction Oxidation is one of the most fundamental reactions in organic synthesis. Owing to the current need to develop forward-looking technology that is environmentally acceptable with respect many aspects. The most attractive approaches are biomimetic oxidation reactions that are closely related to the metabolism of living things. The metabolisms are governed by a variety of enzymes such as cytochrome P-450 and flavoenzyme.Simulation of the function of these enzymes with simple transition metal complex catalyst or organic catalysts led to the discovery of biomimetic, catalytic oxidations with peroxides[1]. We extended such biomimetic methods to the oxidation with molecular oxygen under mild conditions.

  13. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel

    2014-01-01

    This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

  14. Effect of calcination temperature on structural properties and catalytic activity in oxidation reactions of LaNiO3 perovskite prepared by Pechini method

    Institute of Scientific and Technical Information of China (English)

    K.Rida; M.A.Pe(n)a; E.Sastre; A.Martínez-Arias

    2012-01-01

    The study presented the preparation of the perovskite oxide LaNiO3 by the complex citrate method,paying particular attention to evolution of its formation from the amorphous precursor with varied calcination temperatures.The products obtained after heat treatment under air between 200 and 800 ℃ were characterized by X-ray diffraction (XRD),thermogravimetric and differential thermal analysis (TG-DTA),Fourier transform infrared spectroscopy (FTIR),SBET measurements and X-ray photoelectron spectroscopy (XPS).The results showed the formation of a single phase with perovskite structure from ca.550 ℃.Tests on the two catalytic oxidation reactions of C3H6 and CO over the system calcined between mentioned temperatures were examined on the basis of characterization results and showed that optimum catalytic properties for such reactions were achieved for the perovskite calcined at 600 ℃.In turn,correlations between redox and catalytic properties were established on the basis of thermogravimetric temperature programmed reduction (TPR) analysis.

  15. Catalytic methanation reaction over alumina supported cobalt oxide doped noble metal oxides for the purification of simulated natural gas

    Institute of Scientific and Technical Information of China (English)

    Wan Azelee Wan Abu Bakar; Rusmidah Ali; Abdul Aziz Abdul Kadir; Salmiah Jamal Mat Rosid; Nurul Shafeeqa Mohammad

    2012-01-01

    A series of alumina supported cobalt oxide based catalysts doped with noble metals such as ruthenium and platinum were prepared by wet impregnation method.The variables studied were difference ratio and calcination temperatures.Pt/Co( 10∶90 )/Al2O3 catalyst calcined at 700 ℃ was found to be the best catalyst which able to convert 70.10% of CO2 into methane with 47% of CH4 formation at maximum temperature studied of 400 ℃.X-ray diffraction analysis showed that this catalyst possessed the active site Co3O4 in face-centered cubic and PtO2 in the orthorhombic phase with Al2O3 existed in the cubic phase.According to the FESEM micrographs,both fresh and spent Pt/Co( 10∶90)/Al2O3 catalysts displayed small particle size with undefined shape.Nitrogen Adsorption analysis showed that 5.50% reduction of the total surface area for the spent Pt/Co( 10∶90)/Al2O3 catalyst.Meanwhile,Energy Dispersive X-ray analysis (EDX) indicated that Co and Pt were reduced by 0.74% and 0.14% respectively on the spent Pt/Co( 10∶90)/Al2O3catalyst.Characterization using FT-IR and TGA-DTA analysis revealed the existence of residual nitrate and hydroxyl compounds on the Pt/Co( 10∶90)/Al2O3 catalyst.

  16. Studies of the Catalytic Activity and Deactivation of Calcined Layered Double Hydroxides in the Reaction of Ethanol with Propylene Oxide

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The reaction of ethanol with propylene oxide over calcined layered double hydroxides(CLDH) was investigated. The results show that CLDH has a good activity and a good selectivity, but the activity and the selectivity of CLDH decrease when CLDH reforms LDH- the so called "memory effect". The influence of the "memory effect" on the CLDH returning to LDH was studied by the hydration reaction. It is shown that the "memory effect" is not complete, and the decreases of the Mg/Al molar ratio of LDH and the crystallite size due to the increase of the hydration reaction time result in the drop of the activity and the selectivity.Keyworcds Ethanol, Propylene oxide, Calcined layered double hydroxide, "Memory effect", Hydration

  17. Elementary steps of the catalytic NO{sub x} reduction with NH{sub 3}: Cluster studies on reaction paths and energetics at vanadium oxide substrate

    Energy Technology Data Exchange (ETDEWEB)

    Gruber, M.; Hermann, K. [Inorganic Chemistry Department, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany)

    2013-12-28

    We consider different reaction scenarios of the selective catalytic reduction (SCR) of NO in the presence of ammonia at perfect as well as reduced vanadium oxide surfaces modeled by V{sub 2}O{sub 5}(010) without and with oxygen vacancies. Geometric and energetic details as well as reaction paths are evaluated using extended cluster models together with density-functional theory. Based on earlier work of adsorption, diffusion, and reaction of the different surface species participating in the SCR we confirm that at Brønsted acid sites (i.e., OH groups) of the perfect oxide surface nitrosamide, NH{sub 2}NO, forms a stable intermediate. Here adsorption of NH{sub 3} results in NH{sub 4} surface species which reacts with gas phase NO to produce the intermediate. Nitrosamide is also found as intermediate of the SCR near Lewis acid sites of the reduced oxide surface (i.e., near oxygen vacancies). However, here the adsorbed NH{sub 3} species is dehydrogenated to surface NH{sub 2} before it reacts with gas phase NO to produce the intermediate. The calculations suggest that reaction barriers for the SCR are overall higher near Brønsted acid sites of the perfect surface compared with Lewis acid sites of the reduced surface, examined for the first time in this work. The theoretical results are consistent with experimental findings and confirm the importance of surface reduction for the SCR process.

  18. Preparation and Catalytic Oxidation Activity on 2-mercaptoethanol of a Novel Catalytic Cellulose Fibres

    Institute of Scientific and Technical Information of China (English)

    YAO Yu-yuan; LI Ying-jie; CHEN Wen-xing; Lü Wang-yang; Lü Su-fang; XU Min-hong; LIU Fan

    2007-01-01

    Cobalt tetra(N-carbonylacylic) aminophthalocyanine was supported on cellulose fibres by graft reaction to obtain a novel polymer catalyst, catalytic cellulose fibres (CCF),and the optimal supporting conditions were pH = 6, 80℃,t = 120 min. The catalytic oxidation activity of CCF towards oxidation of 2-mereaptoethanol (MEA) in aqueous solution was investigated. The experimental results demonstrated that CCF had good catalytic oxidation activity on MEA at room temperature, causing no secondary pollution and remaining efficient for the repetitive tests with no obvious decrease of catalytic activity.

  19. Composite polymer/oxide hollow fiber contactors: versatile and scalable flow reactors for heterogeneous catalytic reactions in organic synthesis.

    Science.gov (United States)

    Moschetta, Eric G; Negretti, Solymar; Chepiga, Kathryn M; Brunelli, Nicholas A; Labreche, Ying; Feng, Yan; Rezaei, Fateme; Lively, Ryan P; Koros, William J; Davies, Huw M L; Jones, Christopher W

    2015-05-26

    Flexible composite polymer/oxide hollow fibers are used as flow reactors for heterogeneously catalyzed reactions in organic synthesis. The fiber synthesis allows for a variety of supported catalysts to be embedded in the walls of the fibers, thus leading to a diverse set of reactions that can be catalyzed in flow. Additionally, the fiber synthesis is scalable (e.g. several reactor beds containing many fibers in a module may be used) and thus they could potentially be used for the large-scale production of organic compounds. Incorporating heterogeneous catalysts in the walls of the fibers presents an alternative to a traditional packed-bed reactor and avoids large pressure drops, which is a crucial challenge when employing microreactors.

  20. Synthesis and Characterization of Graphene and Graphene Oxide Based Palladium Nanocomposites and Their Catalytic Applications in Carbon-Carbon Cross-Coupling Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Minjae [Kunsan National Univ., Gunsan (Korea, Republic of); Kim, Bohyun; Lee, Yuna; Kim, Beomtae; Park, Joon B. [Chonbuk National Univ., Jeonju (Korea, Republic of)

    2014-07-15

    We have developed an efficient method to generate highly active Pd and PdO nanoparticles (NPs) dispersed on graphene and graphene oxide (GO) by an impregnation method combined with thermal treatments in H{sub 2} and O{sub 2} gas flows, respectively. The Pd NPs supported on graphene (Pd/G) and the PdO NPs supported on GO (PdO/GO) demonstrated excellent carbon-carbon cross-coupling reactions under a solvent-free, environmentally-friendly condition. The morphological and chemical structures of PdO/GO and Pd/G were fully characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). We found that the remarkable reactivity of the Pd/G and PdO/GO catalysts toward the cross-coupling reaction is attributed to the high degree of dispersion of the Pd and PdO NPs while the oxidative states of Pd and the oxygen functionalities of graphene oxide are not critical for their catalytic performance.

  1. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J.; Koljonen, T. [VTT Energy, Espoo (Finland)

    1996-12-31

    In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)

  2. Catalytic reaction in confined flow channel

    Energy Technology Data Exchange (ETDEWEB)

    Van Hassel, Bart A.

    2016-03-29

    A chemical reactor comprises a flow channel, a source, and a destination. The flow channel is configured to house at least one catalytic reaction converting at least a portion of a first nanofluid entering the channel into a second nanofluid exiting the channel. The flow channel includes at least one turbulating flow channel element disposed axially along at least a portion of the flow channel. A plurality of catalytic nanoparticles is dispersed in the first nanofluid and configured to catalytically react the at least one first chemical reactant into the at least one second chemical reaction product in the flow channel.

  3. Catalytic ozonation not relying on hydroxyl radical oxidation: A selective and competitive reaction process related to metal-carboxylate complexes

    KAUST Repository

    Zhang, Tao

    2014-01-01

    Catalytic ozonation following non-hydroxyl radical pathway is an important technique not only to degrade refractory carboxylic-containing organic compounds/matter but also to avoid catalyst deactivation caused by metal-carboxylate complexation. It is unknown whether this process is effective for all carboxylates or selective to special molecule structures. In this work, the selectivity was confirmed using O3/(CuO/CeO2) and six distinct ozone-resistant probe carboxylates (i.e., acetate, citrate, malonate, oxalate, pyruvate and succinate). Among these probe compounds, pyruvate, oxalate, and citrate were readily degraded following the rate order of oxalate>citrate>pyruvate, while the degradation of acetate, malonate, and succinate was not promoted. The selectivity was independent on carboxylate group number of the probe compounds and solution pH. Competitive degradation was observed for carboxylate mixtures following the preference order of citrate, oxalate, and finally pyruvate. The competitive degradation was ascribed to competitive adsorption on the catalyst surface. It was revealed that the catalytically degradable compounds formed bidentate chelating or bridging complexes with surface copper sites of the catalyst, i.e., the active sites. The catalytically undegradable carboxylates formed monodentate complexes with surface copper sites or just electrostatically adsorbed on the catalyst surface. The selectivity, relying on the structure of surface metal-carboxylate complex, should be considered in the design of catalytic ozonation process. © 2013 Elsevier B.V.

  4. Synthesis of ceramic catalytic system based on CuO/CeO2 for preferential oxidation reaction of CO

    International Nuclear Information System (INIS)

    The aim this is work is to develop catalysts based on CuO/CeO2 by means two different types of synthesis methods: combustion synthesis and Pechini. CuO/CeO2 catalysts were synthesized with 0.5 mol of CuO for both synthesis methods used. The catalysts were characterized by XRD with the Rietveld refinement, EDX and textural analysis by the BET method. The results show that both methods of synthesis led to the formation of catalysts with segregated phases formed on the structures of the obtained materials, such segregated phases were formed by the presence of catalytic active species CuO and these phases had different characteristics depending on the type of method synthesis used. Small differences were observed in the evaluation of textural characteristics of the catalysts developed in this work according to the synthesis method employed. (author)

  5. Magnetic gold nanocatalyst (nanocat-Fe–Au): catalytic applications for the oxidative esterification and hydrogen transfer reactions

    Science.gov (United States)

    An efficient and sustainable protocol is described for the oxidative esterification of aldehydes and the reduction of aromatic nitro compounds that uses magnetically separable and reusable maghemite-supported gold nanocatalyst (nanocat-Fe-Au) under mild conditions. The complex ch...

  6. Electrochemical Promotion of Catalytic Reactions Using

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bjerrum, Niels; Cleemann, Lars Nilausen;

    2007-01-01

    This paper presents the results of a study on electrochemical promotion (EP) of catalytic reactions using Pt/C/polybenzimidazole(H3PO4)/Pt/C fuel cell performed by the Energy and Materials Science Group (Technical University of Denmark) during the last 6 years[1-4]. The development of our...

  7. From Catalytic Reaction Networks to Protocells

    Science.gov (United States)

    Kaneko, Kunihiko

    2013-12-01

    In spite of recent advances, there still remains a large gape between a set of chemical reactions and a biological cell. Here we discuss several theoretical efforts to fill in the gap. The topics cover (i) slow relaxation to equilibrium due to glassy behavior in catalytic reaction networks (ii) consistency between molecule replication and cell growth, as well as energy metabolism (iii) control of a system by minority molecules in mutually catalytic system, which work as a carrier of genetic information, and leading to evolvability (iv) generation of a compartmentalized structure as a cluster of molecules centered around the minority molecule, and division of the cluster accompanied by the replication of minority molecule (v) sequential, logical process over several states from concurrent reaction dynamics, by taking advantage of discreteness in molecule number.

  8. Ubiquitous "glassy" relaxation in catalytic reaction networks

    OpenAIRE

    Awazu, Akinori; Kaneko, Kunihiko

    2009-01-01

    Study of reversible catalytic reaction networks is important not only as an issue for chemical thermodynamics but also for protocells. From extensive numerical simulations and theoretical analysis, slow relaxation dynamics to sustain nonequlibrium states are commonly observed. These dynamics show two types of salient behaviors that are reminiscent of glassy behavior: slow relaxation along with the logarithmic time dependence of the correlation function and the emergence of plateaus in the rel...

  9. Electrochemical promotion of sulfur dioxide catalytic oxidation

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bandur, Viktor; Cappeln, Frederik Vilhelm;

    2000-01-01

    The effect of electrochemical polarization on the catalytic SO2 oxidation in the molten V2O5-K2S2O7 system has been studied using a gold working electrode in the temperature range 400-460 degrees C. A similar experiment has been performed with the industrial catalyst VK-58. The aim of the present...... investigation was to study a possible non-Faradaic electrochemical promotion of the liquid-phase catalytic reaction. It has been shown that there are two negative potential promotion areas with maximum effects at approximately -0.1 and -0.2 V, and one positive potential promotion area with the maximum effect...... caused by the negative charge on the electrode. The Faradaic part of the promoting effect under positive polarization has been explained as the electrochemical pushing of the V(V) V(IV) equilibrium in the direction of V(V) formation. It has also been shown that when using the industrial VK-58 catalyst...

  10. Ubiquitous ``glassy'' relaxation in catalytic reaction networks

    Science.gov (United States)

    Awazu, Akinori; Kaneko, Kunihiko

    2009-10-01

    Study of reversible catalytic reaction networks is important not only as an issue for chemical thermodynamics but also for protocells. From extensive numerical simulations and theoretical analysis, slow relaxation dynamics to sustain nonequlibrium states are commonly observed. These dynamics show two types of salient behaviors that are reminiscent of glassy behavior: slow relaxation along with the logarithmic time dependence of the correlation function and the emergence of plateaus in the relaxation-time course. The former behavior is explained by the eigenvalue distribution of a Jacobian matrix around the equilibrium state that depends on the distribution of kinetic coefficients of reactions. The latter behavior is associated with kinetic constraints rather than metastable states and is due to the absence of catalysts for chemicals in excess and the negative correlation between two chemical species. Examples are given and generality is discussed with relevance to bottleneck-type dynamics in biochemical reactions as well.

  11. Catalytic oxidation of CS2 over atmospheric particles and oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The catalytic oxidization of CS2 over atmospheric particles and some oxide catalysts was explored through FT-IR, MS and a fixed-bed stainless steel reactor. The results show that at mospheric particles and some oxide catalysts exhibited considerable oxidizing activities for CS2 at ambient temperature. The reaction products are mainly COS and elemental sulfur, even CO2 on some catalysts. Among the catalysts, CaO has the strongest catalytic activity for oxidizing CS2. Fe2O3 is weaker than CaO. The catalytic activity for AI2O3 reduces considerably compared with the former two catalysts, and SiO2 the weakest. Atmospheric particle samples' catalytic activity is be tween Fe2O3's and AI2O3's. The atmospheric particle sample collected mainly consists of Ca(AI2Si2O8)· 4H2O, which is also the main component of cement. COS, the main product, is formed by the catalytic oxidization of CS2 with adsorbed “molecular” oxygen over the catalysts' surfaces. The concentration of adsorbed oxygen over catalysts' surfaces may be the key factor contributed to the oxidizing activity. It is indicated that CS2 could be catalytically oxidized over at mospheric particles, which induced that this reaction may be another important source of atmos pheric COS from CS2.

  12. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.

  13. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG; XiaoMing

    2001-01-01

    Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.  ……

  14. Electro Catalytic Oxidation (ECO) Operation

    Energy Technology Data Exchange (ETDEWEB)

    Morgan Jones

    2011-03-31

    The power industry in the United States is faced with meeting many new regulations to reduce a number of air pollutants including sulfur dioxide, nitrogen oxides, fine particulate matter, and mercury. With over 1,000 power plants in the US, this is a daunting task. In some cases, traditional pollution control technologies such as wet scrubbers and SCRs are not feasible. Powerspan's Electro-Catalytic Oxidation, or ECO{reg_sign} process combines four pollution control devices into a single integrated system that can be installed after a power plant's particulate control device. Besides achieving major reductions in emissions of sulfur dioxide (SO{sub 2}), nitrogen oxides (NOx), fine particulate matter (PM2.5) and mercury (Hg), ECO produces a highly marketable fertilizer, which can help offset the operating costs of the process system. Powerspan has been operating a 50-MW ECO commercial demonstration unit (CDU) at FirstEnergy Corp.'s R.E. Burger Plant near Shadyside, Ohio, since February 2004. In addition to the CDU, a test loop has been constructed beside the CDU to demonstrate higher NOx removal rates and test various scrubber packing types and wet ESP configurations. Furthermore, Powerspan has developed the ECO{reg_sign}{sub 2} technology, a regenerative process that uses a proprietary solvent to capture CO{sub 2} from flue gas. The CO{sub 2} capture takes place after the capture of NOx, SO{sub 2}, mercury, and fine particulate matter. Once the CO{sub 2} is captured, the proprietary solution is regenerated to release CO{sub 2} in a form that is ready for geological storage or beneficial use. Pilot scale testing of ECO{sub 2} began in early 2009 at FirstEnergy's Burger Plant. The ECO{sub 2} pilot unit is designed to process a 1-MW flue gas stream and produce 20 tons of CO{sub 2} per day, achieving a 90% CO{sub 2} capture rate. The ECO{sub 2} pilot program provided the opportunity to confirm process design and cost estimates, and prepare for large

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

    Science.gov (United States)

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

    2013-01-01

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

  16. Modelling of non-catalytic reactions in a gas-solid trickle flow reactor: dry, regenerative flue gas desulphurization using a silica-supported copper oxide sorbent

    OpenAIRE

    Kiel, J.H.A.; De Prins, W.; Swaaij, van, W.P.M.

    1992-01-01

    A one-dimensional, two-phase dispersed plug flow model has been developed to describe the steady-state performance of a relatively new type of reactor, the gas-solid trickle flow reactor (GSTFR). In this reactor, an upward-flowing gas phase is contacted with as downward-flowing dilute solids phase over an inert packing. The model is derived from the separate mass heat balances for both the gas and (porous) solids phases for the case of a non-catalytic gas-solid reaction, which is first-order ...

  17. Recent Advances on Electro-Oxidation of Ethanol on Pt- and Pd-Based Catalysts: From Reaction Mechanisms to Catalytic Materials

    OpenAIRE

    Ye Wang; Shouzhong Zou; Wen-Bin Cai

    2015-01-01

    The ethanol oxidation reaction (EOR) has drawn increasing interest in electrocatalysis and fuel cells by considering that ethanol as a biomass fuel has advantages of low toxicity, renewability, and a high theoretical energy density compared to methanol. Since EOR is a complex multiple-electron process involving various intermediates and products, the mechanistic investigation as well as the rational design of electrocatalysts are challenging yet essential for the desired complete oxidation to...

  18. Catalytic oxidation of dimethyl ether

    Energy Technology Data Exchange (ETDEWEB)

    Zelenay, Piotr; Wu, Gang; Johnston, Christina M.; Li, Qing

    2016-05-10

    A composition for oxidizing dimethyl ether includes an alloy supported on carbon, the alloy being of platinum, ruthenium, and palladium. A process for oxidizing dimethyl ether involves exposing dimethyl ether to a carbon-supported alloy of platinum, ruthenium, and palladium under conditions sufficient to electrochemically oxidize the dimethyl ether.

  19. Including lateral interactions into microkinetic models of catalytic reactions

    DEFF Research Database (Denmark)

    Hellman, Anders; Honkala, Johanna Karoliina

    2007-01-01

    In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three...

  20. Catalytic conversion of methane: Carbon dioxide reforming and oxidative coupling

    KAUST Repository

    Takanabe, Kazuhiro

    2012-01-01

    Natural gas conversion remains one of the essential technologies for current energy needs. This review focuses on the mechanistic aspects of the development of efficient and durable catalysts for two reactions, carbon dioxide reforming and the oxidative coupling of methane. These two reactions have tremendous technological significance for practical application in industry. An understanding of the fundamental aspects and reaction mechanisms of the catalytic reactions reviewed in this study would support the design of industrial catalysts. CO 2 reforming of methane utilizes CO 2, which is often stored in large quantities, to convert as a reactant. Strategies to eliminate carbon deposition, which is the major problem associated with this reaction, are discussed. The oxidative coupling of methane directly produces ethylene in one reactor through a slightly exothermic reaction, potentially minimizing the capital cost of the natural gas conversion process. The focus of discussion in this review will be on the attainable yield of C 2 products by rigorous kinetic analyses.

  1. Catalytic combustion over high temperature stable metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Berg, M. [TPS Termiska Processer AB, Nykoeping (Sweden)

    1996-12-31

    This thesis presents a study of the catalytic effects of two interesting high temperature stable metal oxides - magnesium oxide and manganese substituted barium hexa-aluminate (BMA) - both of which can be used in the development of new monolithic catalysts for such applications. In the first part of the thesis, the development of catalytic combustion for gas turbine applications is reviewed, with special attention to alternative fuels such as low-BTU gas, e.g. produced in an air blown gasifier. When catalytic combustion is applied for such a fuel, the primary advantage is the possibility of decreasing the conversion of fuel nitrogen to NO{sub x}, and achieving flame stability. In the experimental work, MgO was shown to have a significant activity for the catalytic combustion of methane, lowering the temperature needed to achieve 10 percent conversion by 270 deg C compared with homogeneous combustion.The reaction kinetics for methane combustion over MgO was also studied. It was shown that the heterogeneous catalytic reactions were dominant but that the catalytically initiated homogeneous gas phase reactions were also important, specially at high temperatures. MgO and BMA were compared. The latter showed a higher catalytic activity, even when the differences in activity decreased with increasing calcination temperature. For BMA, CO{sub 2} was the only product detected, but for MgO significant amounts of CO and C{sub 2}-hydrocarbons were formed. BMA needed a much lower temperature to achieve total conversion of other fuels, e.g. CO and hydrogen, compared to the temperature for total conversion of methane. This shows that BMA-like catalysts are interesting for combustion of fuel mixtures with high CO and H{sub 2} content, e.g. gas produced from gasification of biomass. 74 refs

  2. Catalytic activity trends of CO oxidation – A DFT study

    DEFF Research Database (Denmark)

    Jiang, Tao

    There are two goals of this thesis, the first one is to understand the reactivity of noble metal nanoparticles for CO oxidation reaction. The second goal is to gain understanding to the second derivative (Hessian matrix) of the potential energy surfaces (PES) of adsorption systems, especially its...... eigenmodes and eigenvalues, and improving algorithms for geometry optimization in electronic structure calculations. The catalytic activity of gold nanoparticles has received wide attention since the discovery of their activity on CO oxidation by Professor Haruta in 1987. By using density functional theory...... oxidation by molecular O2 occurs via a different reaction pathway, which instead involves a meta-stable intermediate CO-O2. However, although the two oxidizing agents used proceeded via different reaction pathways on different active sites, the apparent overall activation barriers obtained from both theory...

  3. Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature

    OpenAIRE

    Narsimhan, Karthik; Iyoki, Kenta; Dinh, Kimberly; Román-Leshkov, Yuriy

    2016-01-01

    The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C–H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483–498 K). Reaction kinetics studies show sustained catalytic acti...

  4. Catalytic oxidations by vanadium complexes

    OpenAIRE

    Ligtenbarg, A.G J; Hage, R.; Feringa, B. L.

    2003-01-01

    Vanadium haloperoxidases catalyse the oxidation of halides leading to halogenation of substrates or, in the absence of suitable substrates, to oxidation of hydrogen peroxide into singlet oxygen and water. Furthermore, V-haloperoxidases are capable to give enantioselective sulfoxidation under the appropriate conditions. The most interesting model compounds that have been synthesised and studied as bromination catalysts, and catalysts for, i.e. epoxidation, hydroxylation, sulfoxidation and alco...

  5. Catalytic Hydrogenation Reaction of Naringin-Chalcone. Study of the Electrochemical Reaction

    OpenAIRE

    B. A. López de Mishima; H. T. Mishima; A. N. Giannuzzo; M. A. Nazareno

    2000-01-01

    The electrocatalytic hydrogenation reaction of naringin derivated chalcone is studied. The reaction is carried out with different catalysts in order to compare with the classic catalytic hydrogenation.

  6. Heterogeneous Metal Catalysts for Oxidation Reactions

    Directory of Open Access Journals (Sweden)

    Md. Eaqub Ali

    2014-01-01

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

  7. Formaldehyde degradation by catalytic oxidation.

    OpenAIRE

    Shirey, W N; Hall, T. A.; Hanel, E; Sansone, E B

    1981-01-01

    Formaldehyde used for the disinfection of a laminar-flow biological safety cabinet was oxidatively degraded by using a catalyst. This technique reduced the formaldehyde concentration in the cabinet from about 5,000 to about 45 mg/m3 in 8 h. This technique should prove useful in other applications.

  8. Recent Advances on Electro-Oxidation of Ethanol on Pt- and Pd-Based Catalysts: From Reaction Mechanisms to Catalytic Materials

    Directory of Open Access Journals (Sweden)

    Ye Wang

    2015-09-01

    Full Text Available The ethanol oxidation reaction (EOR has drawn increasing interest in electrocatalysis and fuel cells by considering that ethanol as a biomass fuel has advantages of low toxicity, renewability, and a high theoretical energy density compared to methanol. Since EOR is a complex multiple-electron process involving various intermediates and products, the mechanistic investigation as well as the rational design of electrocatalysts are challenging yet essential for the desired complete oxidation to CO2. This mini review is aimed at presenting an overview of the advances in the study of reaction mechanisms and electrocatalytic materials for EOR over the past two decades with a focus on Pt- and Pd-based catalysts. We start with discussion on the mechanistic understanding of EOR on Pt and Pd surfaces using selected publications as examples. Consensuses from the mechanistic studies are that sufficient active surface sites to facilitate the cleavage of the C–C bond and the adsorption of water or its residue are critical for obtaining a higher electro-oxidation activity. We then show how this understanding has been applied to achieve improved performance on various Pt- and Pd-based catalysts through optimizing electronic and bifunctional effects, as well as by tuning their surface composition and structure. Finally we point out the remaining key problems in the development of anode electrocatalysts for EOR.

  9. Deep desulfurization of diesel fuels by catalytic oxidation

    Institute of Scientific and Technical Information of China (English)

    YU Guoxian; CHEN Hui; LU Shanxiang; ZHU Zhongnan

    2007-01-01

    Reaction feed was prepared by dissolving dibenzothiophene (DBT),which was selected as a model organosulfur compound in diesel fuels,in n-octane.The oxidant was a 30 wt-% aqueous solution of hydrogen peroxide.Catalytic performance of the activated carbons with saturation adsorption of DBT was investigated in the presence of formic acid.In addition,the effects of activated carbon dosage,formic acid concentration,initial concentration of hydrogen peroxide,initial concentration of DBT and reaction temperature on the oxidation of DBT were investigated.Experimental results indicated that performic acid and the hydroxyl radicals produced are coupled to oxidize DBT with a conversion ratio of 100%.Catalytic performance of the combination of activated carbon and formic acid is higher than that ofouly formic acid.The concentration of formic acid,activated carbon dosage,initial concentration of hydrogen peroxide and reaction temperature affect the oxidative removal of DBT.The higher the initial concentration of DBT in the n-octane solution,the more difficult the deep desulfurization by oxidation is.

  10. Catalytic Oxidized Reaction of Paraffin Wax Based on BP Neural Network%基于BP神经网络的石蜡催化氧化反应的研究

    Institute of Scientific and Technical Information of China (English)

    黄玮; 丛玉凤; 郭大鹏

    2012-01-01

    The oxidized wax was prepared by catalytic oxidized reaction of paraffin wax which used BP neural network to build mathematical model of acid value and saponification value influenced by the amount of reactive catalyst and accessory ingredient, airflow rate, reaction temperature and time, and utilized the model of neutral network to calculate the technology condition of preparing oxidized wax through catalyzing and oxidizing paraffin wax. Consequently, optimum technology conditions were gained in order to achieve the objective of reducing experimental number of times.%在石蜡催化氧化反应制备氧化蜡的研究中,利用BP神经网络建立反应催化剂用量、助剂用量、空气流量、反应温度和反应时间对酸值和皂化值影响的数学模型,并利用该神经网络模型对石蜡催化氧化制备氧化蜡的工艺条件进行预测,从而获得最优工艺条件,达到缩短实验次数的目的.

  11. One-pot synthesis of monodisperse palladium-copper nanocrystals supported on reduced graphene oxide nanosheets with improved catalytic activity and methanol tolerance for oxygen reduction reaction

    Science.gov (United States)

    Lv, Jing-Jing; Li, Shan-Shan; Wang, Ai-Jun; Mei, Li-Ping; Feng, Jiu-Ju; Chen, Jian-Rong; Chen, Zhaojiang

    2014-12-01

    Monodisperse bimetallic alloyed palladium-copper nanocrystals are uniformly supported on reduced graphene oxide nanosheets by a one-pot solvothermal strategy, with an average size of 6.81 nm. As a result, the as-prepared nanocomposites have the enlarged electrochemically active surface area (49.2 m2 g-1), and display the improved electrocatalytic performance and high methanol-tolerance ability for oxygen reduction reaction in alkaline media, compared with commercial Pd black and RGOs. Those RGOs-supporting Pd-Cu alloys would have potential applications in fuel cells.

  12. Side reactions in the selective catalytic reduction of NO with NH{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Madia, G.; Koebel, M.; Elsener, M.; Wokaun, A.

    2002-03-01

    The main and the side reactions of the SCR reaction with ammonia over TiO{sub 2}-WO{sub 3}-V{sub 2}O{sub 5} catalysts have been investigated using synthetic gas mixtures matching the composition of diesel exhaust. At high temperatures the selective catalytic oxidation of ammonia (SCO) and the formation of nitrous oxide compete with the SCR reaction. Water strongly inhibits the SCO of ammonia and the formation of nitrous oxide thus increasing the selectivity of the SCR reaction. However, water also inhibits SCR activity, most pronounced at low temperatures. (author)

  13. Catalytic aerobic oxidation of bio-renewable chemicals

    DEFF Research Database (Denmark)

    Gorbanev, Yury

    -free conditions. Moreover, a detailed study on the performance and stability of the ruthenium hydroxide catalysts on magnesium-containing supports under reaction conditions was conducted. The aerobic oxidation of HMF to form another value-added chemical, 2,5-diformylfuran (DFF), was also investigated......, EDS, XRF and other methods. Supported gold and ruthenium hydroxide catalyst systems were explored for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDA), a potential polymer building block for the plastic industry, or its dimethyl ester (FDMC). High product......Ox deposited on various metal oxides. Furthermore, this thesis presents the results of the catalytic aerobic oxidative degradation of higher alcohols over supported ruthenium hydroxide catalysts. A very efficient oxidative cleavage of vic-diols to form respective acids was also shown under examined conditions...

  14. Real time chemical imaging of a working catalytic membrane reactor during oxidative coupling of methane.

    Science.gov (United States)

    Vamvakeros, A; Jacques, S D M; Middelkoop, V; Di Michiel, M; Egan, C K; Ismagilov, I Z; Vaughan, G B M; Gallucci, F; van Sint Annaland, M; Shearing, P R; Cernik, R J; Beale, A M

    2015-08-18

    We report the results from an operando XRD-CT study of a working catalytic membrane reactor for the oxidative coupling of methane. These results reveal the importance of the evolving solid state chemistry during catalytic reaction, particularly the chemical interaction between the catalyst and the oxygen transport membrane.

  15. Catalytic and Gas-Solid Reactions Involving HCN over Limestone

    DEFF Research Database (Denmark)

    Jensen, Anker; Johnsson, Jan Erik; Dam-Johansen, Kim

    1997-01-01

    In coal-fired combustion systems solid calcium species may be present as ash components or limestone added to the combustion chamber. In this study heterogeneous reactions involving HCN over seven different limestones were investigated in a laboratory fixed-bed quartz reactor at 873-1,173 K....... Calcined limestone is an effective catalyst for oxidation of HCN. Under conditions with complete conversion of HCN at O-2 concentrations above about 5,000 ppmv the selectivity for formation of NO and N2O is 50-70% and below 5%, respectively. Nitric oxide can be reduced by HCN to N-2 in the absence of O-2...... and to N-2 and N2O in the presence of O-2. At low O-2 concentrations or low temperatures. HCN may react with CaO, forming calcium cyanamide, CaCN2. The selectivities for formation of NO and N2O from oxidation of CaCN2 is 20-25% for both species. The catalytic activity of limestone for oxidation of HCN...

  16. DNA-binding, catalytic oxidation, C—C coupling reactions and antibacterial activities of binuclear Ru(II thiosemicarbazone complexes: Synthesis and spectral characterization

    Directory of Open Access Journals (Sweden)

    Arumugam Manimaran

    2012-07-01

    Full Text Available New hexa-coordinated binuclear Ru(II thiosemicarbazone complexes of the type {[(B(EPh3(COClRu]2L} (where, E = P or As; B = PPh3 or AsPh3 or pyridine; L = mononucleating NS donor of N-substituted thiosemicarbazones have been synthesized and characterized by elemental analysis, FT-IR, UV–vis and 31P{1H} NMR cyclic voltammetric studies. The DNA-binding studies of Ru(II complexes with calf thymus DNA (CT-DNA were investigated by UV–vis, viscosity measurements, gel-electrophoresis and fluorescence spectroscopy. The new complexes have been used as catalysts in C—C coupling reaction and in the oxidation of alcohols to their corresponding carbonyl compounds by using NMO as co-oxidant and molecular oxygen (O2 atmosphere at ambient temperature. Further, the new binucleating thiosemicarbazone ligands and their Ru(II complexes were also screened for their antibacterial activity against Klebsiella pneumoniae, Shigella sp., Micrococcus luteus, Escherichia coli and Salmonella typhi. From this study, it was found out that the activity of the complexes almost reaches the effectiveness of the conventional bacteriocide.

  17. (Gold core) at (ceria shell) nanostructures for plasmon-enhanced catalytic reactions under visible light

    KAUST Repository

    Wang, Jianfang

    2014-08-26

    Driving catalytic reactions with sunlight is an excellent example of sustainable chemistry. A prerequisite of solar-driven catalytic reactions is the development of photocatalysts with high solar-harvesting efficiencies and catalytic activities. Herein, we describe a general approach for uniformly coating ceria on monometallic and bimetallic nanocrystals through heterogeneous nucleation and growth. The method allows for control of the shape, size, and type of the metal core as well as the thickness of the ceria shell. The plasmon shifts of the Au@CeO2 nanostructures resulting from the switching between Ce(IV) and Ce(III) are observed. The selective oxidation of benzyl alcohol to benzaldehyde, one of the fundamental reactions for organic synthesis, performed under both broad-band and monochromatic light, demonstrates the visible-light-driven catalytic activity and reveals the synergistic effect on the enhanced catalysis of the Au@CeO2 nanostructures. © 2014 American Chemical Society.

  18. Effect the conditions of the acid-thermal modification of clinoptilolite have on the catalytic properties of palladium-copper complexes anchored on it in the reaction of carbon monoxide oxidation

    Science.gov (United States)

    Rakitskaya, T. L.; Kiose, T. A.; Ennan, A. A.; Golubchik, K. O.; Oleksenko, L. P.; Gerasiova, V. G.

    2016-06-01

    The dependence of the physicochemical and structural-adsorption properties of natural and acid-thermal modified clinoptilolite, and of Pd(II)-Cu(II) catalysts based on them, on the duration of acid-thermal modification is investigated. The samples under study are described via XRD and thermal gravimetric (DTG and DTA) analysis, IR, DR UV-Vis, EPR spectroscopy, and water vapor adsorption. Values of both the specific surface area ( S sp) and pH of aqueous suspensions are determined. The resulting catalysts are tested in the reaction of low-temperature carbon monoxide oxidation with air oxygen. A conclusion is drawn about the nature of surface bimetallic Pd(II)-Cu(II) complexes. The greatest catalytic activity is shown by complexes based on clinoptilolite and modified with 3 M HNO3 for 0.5 and 1 h.

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

    Science.gov (United States)

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

    2004-06-01

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

  20. Biogas Catalytic Reforming Studies on Nickel-Based Solid Oxide Fuel Cell Anodes

    DEFF Research Database (Denmark)

    Johnson, Gregory B.; Hjalmarsson, Per; Norrman, Kion;

    2016-01-01

    of experiments were performed to study catalytic activity and effect of sulfur poisoning: (i) CH4 and CO2 dissociation; (ii) biogas (60% CH4 and 40% CO2) temperature-programmed reactions (TPRxn); and (iii) steady-state biogas reforming reactions followed by postmortem catalyst characterization by temperature......-programmed oxidation and time-of-flight secondary ion mass spectrometry. Results showed thatNi/ScYSZ/Pd-CGO was more active for catalytic dissociation of CH4 at 750°C and subsequent reactivity of deposited carbonaceous species. Sulfur deactivated most catalytic reactions except CO2 dissociation at 750°C. The presence...

  1. Reaction engineering calculation for ethylene catalytic oxidation over gear-shaped catalysts%外齿轮形颗粒催化剂上乙烯催化氧化的反应工程计算

    Institute of Scientific and Technical Information of China (English)

    周继鹏; 房鼎业; 李涛

    2016-01-01

    For the reaction of ethylene catalytic oxidation to ethylene oxide over a gear-shaped catalyst particle, a three-dimensional reaction-mass transfer-heat transfer model is developed to calculate effectiveness factor of the catalyst. Effective diffusivities and effective thermal conductivity are the function of temperature and concentration distribution in catalyst particle. The finite element method is employed to solve the set of highly nonlinear partial differential equations, and the values obtained agree well with those given by literatures. Geometric external surface area is a key parameter for the effectiveness factor. The effectiveness factor is 0.1804 for gear-shaped catalyst with geometric external surface area of 1862 m2·m−3, and 0.0993 for cylindrical catalyst with geometric external surface area of 924 m2·m−3. The quantitative calculation for reaction-transport phenomena in a single catalyst particle could be a guide for catalyst design and a basis for multi-scale simulation of coupling hydromechanics and catalytic reaction-transport phenomena.%针对乙烯氧化制环氧乙烷反应体系,对外齿轮异形催化剂建立三维反应-传质-传热模型。有效扩散系数和有效热导率均为待求解浓度场和温度场的函数,使得偏微分方程组模型为强非线性。采用有限元算法求解,并对模型有效性进行验证,定量研究了催化剂几何比外表面积和内扩散效率因子的关系。计算结果表明,几何比外表面积为1862 m2·m−3的外齿轮催化剂内扩散效率因子为0.1804,而几何比外表面积为924 m2·m−3的圆柱形催化剂内扩散效率因子为0.0993。对单个催化剂颗粒反应-传递现象的研究能定量指导催化剂设计,并为耦合反应器流体力学和催化剂反应传递现象多尺度模拟计算奠定基础。

  2. Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides. Progress report, August 1, 1991--January 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1992-02-03

    This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.

  3. Utilization of the Recycle Reactor in Determining Kinetics of Gas-Solid Catalytic Reactions.

    Science.gov (United States)

    Paspek, Stephen C.; And Others

    1980-01-01

    Describes a laboratory scale reactor that determines the kinetics of a gas-solid catalytic reaction. The external recycle reactor construction is detailed with accompanying diagrams. Experimental details, application of the reactor to CO oxidation kinetics, interphase gradients, and intraphase gradients are discussed. (CS)

  4. Catalytic Hydrogenation Reaction of Naringin-Chalcone. Study of the Electrochemical Reaction

    Directory of Open Access Journals (Sweden)

    B. A. López de Mishima

    2000-03-01

    Full Text Available The electrocatalytic hydrogenation reaction of naringin derivated chalcone is studied. The reaction is carried out with different catalysts in order to compare with the classic catalytic hydrogenation.

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

    Institute of Scientific and Technical Information of China (English)

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

    2004-01-01

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

  6. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: kinetics and biodegradability enhancement.

    Science.gov (United States)

    Suárez-Ojeda, María Eugenia; Kim, Jungkwon; Carrera, Julián; Metcalfe, Ian S; Font, Josep

    2007-06-18

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15 bar of oxygen partial pressure (P(O2)) and at 180, 200 and 220 degrees C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P(O2) were 140-160 degrees C and 2-9 bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160 degrees C and 2 bar of P(O2), which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD(RB)) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture. PMID:17363148

  7. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: Kinetics and biodegradability enhancement

    International Nuclear Information System (INIS)

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15bar of oxygen partial pressure (PO2) and at 180, 200 and 220deg. C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and PO2 were 140-160deg. C and 2-9bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160deg. C and 2 bar of PO2, which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (CODRB) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture

  8. Rapid and facile preparation of zinc ferrite (ZnFe2O4) oxide by microwave-solvothermal technique and its catalytic activity in heterogeneous photo-Fenton reaction

    International Nuclear Information System (INIS)

    In this work zinc ferrite (ZnFe2O4) oxide was rapidly and easily prepared by microwave-solvothermal route and its catalytic property in photo-Fenton reaction was evaluated. The effects of microwave heating time and power on the properties of produced particles were investigated. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM) and nitrogen adsorption–desorption isotherms were the techniques used for characterizing the solid products. The synthesized material was tested as a catalyst in the degradation of the textile dye molecule by the heterogeneous photo-Fenton process. Characterization results showed that the microwave heating time and power have significant influences on the formation of the phase spinel as well as on its physical properties. The reaction results showed that the ZnFe2O4 oxide has good photocatalytic activity, which can be attributed to high surface area and pore volume, and large pore size. The ZnFe2O4 oxide produced by the microwave irradiation exhibited promising photocatalytic activity for the removal of textile dye, reaching nearly 100% of decolorization at 40 min and 60% of mineralization at 240 min. Therefore, ZnFe2O4 particles rapidly prepared by the microwave route have the potential for use in treatment of textile wastewater by the heterogeneous photo-Fenton process. - Highlights: • ZnFe2O4 was synthesized by microwave-solvothermal method. • ZnFe2O4 was prepared by different microwave heating times and powers. • ZnFe2O4 was used as heterogeneous photo-Fenton catalyst. • Degradation of Procion red dye using heterogeneous photo-Fenton process. • ZnFe2O4 was highly efficient to degrade textile dye under visible light

  9. Rapid and facile preparation of zinc ferrite (ZnFe{sub 2}O{sub 4}) oxide by microwave-solvothermal technique and its catalytic activity in heterogeneous photo-Fenton reaction

    Energy Technology Data Exchange (ETDEWEB)

    Anchieta, Chayene G.; Severo, Eric C.; Rigo, Caroline; Mazutti, Marcio A. [Department of Chemical Engineering, Federal University of Santa Maria, 97105-900, Santa Maria (Brazil); Kuhn, Raquel C., E-mail: raquelckuhn@yahoo.com.br [Department of Chemical Engineering, Federal University of Santa Maria, 97105-900, Santa Maria (Brazil); Muller, Edson I.; Flores, Erico M.M. [Department of Chemistry, Federal University of Santa Maria, 97105-900, Santa Maria (Brazil); Moreira, Regina F.P.M. [Department of Chemical Engineering and Food Engineering, Federal University of Santa Catarina, 88040-970, Florianópolis (Brazil); Foletto, Edson L. [Department of Chemical Engineering, Federal University of Santa Maria, 97105-900, Santa Maria (Brazil)

    2015-06-15

    In this work zinc ferrite (ZnFe{sub 2}O{sub 4}) oxide was rapidly and easily prepared by microwave-solvothermal route and its catalytic property in photo-Fenton reaction was evaluated. The effects of microwave heating time and power on the properties of produced particles were investigated. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM) and nitrogen adsorption–desorption isotherms were the techniques used for characterizing the solid products. The synthesized material was tested as a catalyst in the degradation of the textile dye molecule by the heterogeneous photo-Fenton process. Characterization results showed that the microwave heating time and power have significant influences on the formation of the phase spinel as well as on its physical properties. The reaction results showed that the ZnFe{sub 2}O{sub 4} oxide has good photocatalytic activity, which can be attributed to high surface area and pore volume, and large pore size. The ZnFe{sub 2}O{sub 4} oxide produced by the microwave irradiation exhibited promising photocatalytic activity for the removal of textile dye, reaching nearly 100% of decolorization at 40 min and 60% of mineralization at 240 min. Therefore, ZnFe{sub 2}O{sub 4} particles rapidly prepared by the microwave route have the potential for use in treatment of textile wastewater by the heterogeneous photo-Fenton process. - Highlights: • ZnFe{sub 2}O{sub 4} was synthesized by microwave-solvothermal method. • ZnFe{sub 2}O{sub 4} was prepared by different microwave heating times and powers. • ZnFe{sub 2}O{sub 4} was used as heterogeneous photo-Fenton catalyst. • Degradation of Procion red dye using heterogeneous photo-Fenton process. • ZnFe{sub 2}O{sub 4} was highly efficient to degrade textile dye under visible light.

  10. Catalytic Conversion of Methanol by Oxidative Dehydrogenation

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    This study investigates the effects of addition of oxygen on the oxidative dehydrogenation (ODH) of methanol when a fluorotetrasilicic mica ion-exchanged with palladium (Pd2+-TSM) was used as the catalyst. The reaction proceeded at a very low temperature in the presence of oxygen, and HCOOCH3 was obtained at high selectivity. By calculating the equilibrium conversion, it has been shown that substantial ODH took place for HCOOCH3 production. Consequently, this reaction would make dehydrogenation the dominant reaction at equilibrium. Not all the H dissociated from CH3OH was converted to H2O by oxidation. It has been shown that the H2O was not produced from oxidative dehydrogenation by the direct reaction of CH3OH and O2 when an attempt was made to carry out oxidative dehydrogenation using an isotope oxygen trace method in the gas phase. Therefore, when CH3OH was converted to CO2 and dehydrogenated to HCOOCH3, the C-O bonds were not dissociated.

  11. Catalytic Friedel-Crafts reaction of aminocyclopropanes.

    Science.gov (United States)

    de Nanteuil, Florian; Loup, Joachim; Waser, Jérôme

    2013-07-19

    A Lewis acid catalyzed Friedel-Crafts reaction between donor-acceptor aminocyclopropanes and indoles and other electron-rich aromatic compounds is reported. Indole alkylation at the C3 position was generally obtained for a broad range of functional groups and substitution patterns. In the case of C3-substituted indoles, C2 alkylation was observed. The reaction gives a rapid access to gamma amino acid derivatives present in numerous bioactive molecules. PMID:23815365

  12. Titanium-Containing Mesoporous Materials: Synthesis and Application in Selective Catalytic Oxidation

    Institute of Scientific and Technical Information of China (English)

    Jie Li; Chunhui Zhou; Huali Xie; Zhonghua Ge; Liangcai Yuan; Xiaonian Li

    2006-01-01

    Titanium-containing mesoporous molecular sieves are of great significance in selective catalytic oxidation processes with bulky molecules. Recent researches and developments on the designing and synthesis of Ti-containing mesoporous materials have been reviewed. Various strategies for the preparation of Ti-containing mesoporous materials, such as direct synthesis and post-synthesis, are described. Modifications of Ti-containing mesoporous materials by surface-grafting and atom-planting are also discussed. All approaches aimed mainly at the improving of the stability, the hydrophobicity, and mostly the catalytic activity. Structural and mechanistic features of various synthetic systems are discussed. Ticontaining mesoporous materials in liquid phase catalytic oxidation of organic compounds with H2O2 as an oxidant is briefly summarized, showing their broad utilities for green synthesis of fine chemicals by catalytic oxidative reactions.

  13. High-pressure catalytic reactions over single-crystal metal surfaces

    Science.gov (United States)

    Rodriguez, JoséA.; Wayne Goodman, D.

    1991-11-01

    Studies dealing with high-pressure catalytic reactions over single-crystal surfaces are reviewed. The coupling of an apparatus for the measurement of reaction kinetics at elevated pressures with an ultrahigh vacuum system for surface analysis allows detailed study of structure sensitivity, the effects of promoters and inhibitors on catalytic activity, and, in certain cases, identification of reaction intermediates by post-reaction surface analysis. Examples are provided which demonstrate the relevance of single-crystal studies for modeling the behaviour of high-surface-area supported catalysts. Studies of CO methanation and CO oxidation over single-crystal surfaces provide convincing evidence that these reactions are structure insensitive. For structure-sensitive reactions (ammonia synthesis, alkane hydrogenolysis, alkane isomerization, water-gas shift reaction, etc.) model single-crystal studies allow correlations to be established between surface structure and catalytic activity. The effects of both electronegative (S and P) and electropositive (alkali metals) impurities upon the catalytic activity of metal single crystals for ammonia synthesis, CO methanation, alkane hydrogenolysis, ethylene epoxidation and water-gas shift are discussed. The roles of "ensemble" and "ligand" effects in bimetallic catalysts are examined in light of data obtained using surfaces prepared by vapor-depositing one metal onto a crystal face of a dissimilar metal.

  14. Homogeneous catalytic wet air oxidation for the treatment oftextile wastewaters

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    An extensive series of experiments was carried out in order to identify suitable catalysts to boost the reaction rate of wet air oxidation of real textile wastewaters at relatively mild temperature and pressure. Experimental results indicated that all catalysts tested in this investigation had shown an impressive increase in the initial COD and TOC removal rate as well as the COD and TOC removal levels in two hours reaction. Among all the catalysts tested, copper salts were more effective than the rest. Anions of the salt soluffonsalso played a role in the catalytic process with nitrate ions having better effect than sulfate ions. Hence copper nitrates were more effective than copper sulfates. It was also found that a mixture of salts with different metals performed better than either of the component single salt alone.

  15. Identifying systematic DFT errors in catalytic reactions

    DEFF Research Database (Denmark)

    Christensen, Rune; Hansen, Heine Anton; Vegge, Tejs

    2015-01-01

    Using CO2 reduction reactions as examples, we present a widely applicable method for identifying the main source of errors in density functional theory (DFT) calculations. The method has broad applications for error correction in DFT calculations in general, as it relies on the dependence...

  16. Coupling catalytic hydrolysis and oxidation for CS2 removal

    Institute of Scientific and Technical Information of China (English)

    WANG Li; WU Diyong; WANG Shudong; YUAN Quan

    2008-01-01

    CS2 removal was Obtained by coupling catalytic hyidation on bi-functional catalyst.On the hydrolysis active sites,CS2 is hydrolyzed to H2S,while on the oxidation active sites,H2S is oxidized to elemental S or sulfuric acid deposited on the porous support.The above process can be expressed as follows:CS2→H2O COS →H2O H2S→O2 S/SO2- 4.H2S oxidation eliminates its prohibition on CS2 hydrolysis so that the rate of coupling removal CS2 is 5 times higher than that of CS2 hydrolysis.The same active energy of hydrolysis and coupling reaction also indicates that H2S oxidation does not change the reaction mechanism of CS2 hydrolysis.Temperature has obvious effect on the process while the mole ratio of O2 concentration to CS2 concentration (O/S) does not,especially in excess of 2.5.The formation of sulfuric acid on the catalyst surface poisons hydrolysis active sites and causes the decrease of left OH-1 concentration on the catalysts surface.Lower temperature is suggested for this bi-functional catalyst owing to the low yield ratio of S/SO4 2-.

  17. Catalytic partial oxidation of pyrolysis oils

    Science.gov (United States)

    Rennard, David Carl

    2009-12-01

    This thesis explores the catalytic partial oxidation (CPO) of pyrolysis oils to syngas and chemicals. First, an exploration of model compounds and their chemistries under CPO conditions is considered. Then CPO experiments of raw pyrolysis oils are detailed. Finally, plans for future development in this field are discussed. In Chapter 2, organic acids such as propionic acid and lactic acid are oxidized to syngas over Pt catalysts. Equilibrium production of syngas can be achieved over Rh-Ce catalysts; alternatively mechanistic evidence is derived using Pt catalysts in a fuel rich mixture. These experiments show that organic acids, present in pyrolysis oils up to 25%, can undergo CPO to syngas or for the production of chemicals. As the fossil fuels industry also provides organic chemicals such as monomers for plastics, the possibility of deriving such species from pyrolysis oils allows for a greater application of the CPO of biomass. However, chemical production is highly dependent on the originating molecular species. As bio oil comprises up to 400 chemicals, it is essential to understand how difficult it would be to develop a pure product stream. Chapter 3 continues the experimentation from Chapter 2, exploring the CPO of another organic functionality: the ester group. These experiments demonstrate that equilibrium syngas production is possible for esters as well as acids in autothermal operation with contact times as low as tau = 10 ms over Rh-based catalysts. Conversion for these experiments and those with organic acids is >98%, demonstrating the high reactivity of oxygenated compounds on noble metal catalysts. Under CPO conditions, esters decompose in a predictable manner: over Pt and with high fuel to oxygen, non-equilibrium products show a similarity to those from related acids. A mechanism is proposed in which ethyl esters thermally decompose to ethylene and an acid, which decarbonylates homogeneously, driven by heat produced at the catalyst surface. Chapter 4

  18. [Lipases in catalytic reactions of organic chemistry].

    Science.gov (United States)

    Bezborodov, A M; Zagustina, N A

    2014-01-01

    Aspects of enzymatic catalysis in lipase-catalyzed reactions of organic synthesis are discussed in the review. The data on modern methods of protein engineering and enzyme modification allowing a broader range of used substrates are briefly summarized. The application of lipase in the preparation of pharmaceuticals and agrochemicals containing no inactive enantiomers and in the synthesis of secondary alcohol enantiomers and optically active amides is demonstrated. The subject of lipase involvement in the C-C bond formation in the Michael reaction is discussed. Data on the enzymatic synthesis of construction materials--polyesters, siloxanes, etc.--are presented. Examples demonstrating the application of lipase enzymatic catalysis in industry are given. PMID:25707112

  19. Kinetics of catalytic reactions-solutions manual

    CERN Document Server

    Vannice, M Albert

    2008-01-01

    Including countless exercises and worked examples, this advanced reference work and textbook will be extremely useful for the work of many industrial scientists. It teaches readers to design kinetic experiments involving heterogeneous catalysts, to characterize these catalysts, to acquire rate data, to find heat and mass transfer limitations in these data, to select reaction models, to derive rate expressions based on these models, and to assess the consistency of these rate equations.

  20. Characterization of catalytic supports based in mixed oxides for control reactions of NO and N{sub 2}O; Caracterizacion de soportes cataliticos basados en oxidos mixtos para reacciones de control de NO y N{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Garcia C, M.A.; Perez H, R.; Gomez C, A.; Diaz, G. [Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, 11801 Mexico D.F. (Mexico)

    1999-07-01

    The catalytic supports Al{sub 2}O{sub 3}, La{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-La{sub 2}O{sub 3} were prepared by the Precipitation and Coprecipitation techniques. The catalytic supports Al{sub 2}O{sub 3}, La{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-La{sub 2}O{sub 3} were characterized by several techniques to determine: texture (Bet), crystallinity (XRD), chemical composition (Sem)(Ftir) and it was evaluated their total acidity by reaction with 2-propanol. The investigation will be continued with the cobalt addition and this will be evaluated for its catalytic activity in control reactions of N O and N{sub 2}O. (Author)

  1. Graphene-based materials in catalytic wet peroxide oxidation

    OpenAIRE

    Gomes, Helder; Ribeiro, Rui; Pastrana-Martínez, Luisa; Figueiredo, José; Faria, Joaquim; Silva, Adrián

    2014-01-01

    In catalytic wet peroxide oxidation (CWPO),an advanced oxidation process, hydrogen peroxide (H2O2) is decomposed catalytically giving rise to hydroxyl radicals (HO•).These radicals, exhibiting high oxidizing potential, serve as effective and non selective species for the degradation of several organic pollutants in liquid phase. Since the report of Lücking et al. [1], carbon materials have been explored as catalysts for CWPO[2]. Recent reports address process intensification issues, br...

  2. Preparation of nitric humic acid by catalytic oxidation from Guizhou coal with catalysts

    Institute of Scientific and Technical Information of China (English)

    Yang Zhiyuan; Gong Liang; Ran Pan

    2012-01-01

    Nitric humic acid was prepared by catalytic oxidation between nitric acid and Guizhou coal,with added catalysts.We investigated catalytic oxidation processes and the factors that affect the reactions.The effects of different catalysts,including NiSO4 support on active carbon (AC-NiSO4),NiSO4 support on silicon dioxide (SiO2-NiSO4),composites of SO42-/Fe2O3,Zr-iron and vanadium-iron composite were studied.As well.we investigated nitric humic acid yields and the chemical structure of products by element analysis,FT-IR and E4/E6 (an absorbance ratio at wavelengths of 465 and 665 nm of humic acid alkaline extraction solutions).The results show that the catalytic oxidation reaction with added catalysts can increase humic acid yields by 18.7%,16.36%,12.94%,5.61% and 8.59%,respectively.The highest yield of humic acid,i.e.,36.0%,was obtained with AC-NiSO4 as the catalyst.The amounts of C and H decreased with the amount of nitrogen.The increase in the E4/E6 ratio in catalytic oxidation of (Guizhou) coal shows that small molecular weights and high yields of nitric humic acid can be obtained by catalytic oxidation reactions.

  3. Atmospheric Pressure Microwave Assisted Heterogeneous Catalytic Reactions

    Directory of Open Access Journals (Sweden)

    Ken Belmore

    2007-07-01

    Full Text Available The newly synthesized 5,10,15,20-tetra[3-(3-trifluoromethylphenoxy]porphyrin, TTFMPP, has been characterized using mass spectroscopy, 1H-, 13C- and 19F-NMR, MALDI-TOF mass spectrometry, UV-Vis and fluorescence spectrophotometry, andcyclic voltammetry. The NMR confirmed the structure of the compound and the massspectrum was in agreement with the proposed molecular formula. The UV-Vis absorptionspectrum of TTFMPP shows characteristic spectral patterns similar to those of tetraphenylporphryin, with a Soret band at 419 nm and four Q bands at 515, 550, 590, and 648 nm.Protonation of the porphyrin with TFA resulted in the expected red shift of the Soret band.Excitation at 419 nm gave an emission at 650 nm. The quantum yield of the porphyrin wasdetermined to be 0.08. Cyclic voltammetry was used to determine the oxidation andreduction potentials of the new porphyrin. Two quasi-reversible one-electron reductions at–1.00 and –1.32 V and a quasi-reversible oxidation at 1.20 V versus the silver/silverchloride reference electrode with tetrabutylammonium tetrafluoroborate as the supportingelectrolyte in methylene chloride were observed.

  4. Catalytic wet air oxidation for the treatment of emulsifying wastewater

    Institute of Scientific and Technical Information of China (English)

    ZHAO Jian-fu; CHEN Ling; LU Yi-cheng; TANG Wen-wei

    2005-01-01

    The wet air oxidation (WAO) and catalytic WAO (CWAO) of the high strength emulsifying wastewater containing nonionic surfactants have been investigated in terms of COD and TOC removal. The WAO and homogeneous CWAO processes were carried out at the temperature from 433 K to 513 K, with initial oxygen pressure 1.2 MPa. It was found that homogeneous catalyst copper(Cu ( NO3 )2 )had an fairly good catalytic activity for the WAO process, and the oxidation was catalyzed when the temperature was higher than 473 K.Moreover, several heterogeneous catalysts were proved to be effective for the WAO process. At the temperature 473 K, after 2 h reaction,WAO process could achieve about 75% COD removal and 66% TOC removal, while catalysts Cu/Al2O3 and Mn-Ce/Al2O3 elevated the COD removal up to 86%-89% and that of TOC up to 82%. However, complete elimination of COD and TOC was proved to be difficult even the best non-noble catalyst was used. Therefore, the effluent from WAO or CWAO process need to be further disposed. The bioassay proved that the effluent from WAO process was amenable to the biochemical method.

  5. Reaction Performance of MnO2/Graphene for Ozone Catalytic Oxidation of Toluene%二氧化锰/石墨烯臭氧催化氧化甲苯反应性能

    Institute of Scientific and Technical Information of China (English)

    姚振华; 胡茂从

    2015-01-01

    采用一步水热合成法,在180℃,12 h条件下制备了30%二氧化锰/石墨烯( MnO2/G)复合材料。实验结果表明:MnO2均匀且较为牢固地锚定于石墨烯表面,同时MnO2的沉积阻止了多层石墨烯的复合,从而使得复合物具有较大的比表面积。相同条件下, MnO2/石墨烯相较于单纯MnO2或石墨烯具有很好的臭氧催化氧化甲苯性能,这可以归结于MnO2和石墨烯间的协同催化作用。%30%MnO2/graphene composite was synthesized at 180 ℃ for 12 h under hydrothermal condition. MnO2 nanoparticles were uniformly distributed throughout the surface of graphene nanosheets. In turn, the aggregation of graphene sheets can be partly prevented by the intercalation of MnO2 particles within the graphene layers, which resulted in high surface area on MnO2/graphene composite. Under same reaction condition, MnO2/graphene composite showed better reaction performance than pure MnO2 or graphene in ozone catalytic oxidation of toluene which was attributed to the synergetic effect of graphene and MnO2.

  6. Selective catalytic oxidations of alkylaromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, R.W. [Celanese GmbH, Oberhausen (Germany); Roehrscheid, F. [Hoechst AG, Frankfurt am Main (Germany). Zentralforschung und Technologie

    1998-12-31

    Focused to the guidelines of `Sustainable Development` `Responsible Care` and `Customer Satisfaction`, modern production processes are critically assessed on their balance between their ecological benefits and their economical parameters as well as their value to the community. Also in the area of fine chemicals, it is obvious that more and more processes are devolved which save feedstock, reduce emissions and minimize the potential for safety hazards: Less additive but more integrated protection of the environment yielding ecologically highly valuable processes. The described production of aromatic carboxylic acids is an ideal example for such a modern process. Nowadays the synthesis of derivatives of benzoic acid utilizes air as Ideal oxidant and acetic acid as environmental unquestionable solvent. The major byproduct of the oxidation reaction is water in some cases, dependend on the substrate also carbon dioxide. (orig.)

  7. Structure and catalytic reactivity of Rh oxides

    DEFF Research Database (Denmark)

    Gustafson, J.; Westerström, R.; Resta, A.;

    2009-01-01

    as well as on Rh nanoparticles. The detailed structure of this film was previously determined using UHV based techniques and density functional theory. In the present paper, we also examine the structure of the bulk Rh2O3 corundum oxide using surface X-ray diffraction. Being armed with this...... structural information, we have explored the CO oxidation reaction over Rh(1 1 1), Rh(1 0 0) and Pt25Rh75(1 0 0) at realistic pressures using in situ surface X-ray diffraction and online mass spectrometry. In all three cases we find that an increase of the CO2 production coincides with the formation of the...

  8. Single-species reactions on a random catalytic chain

    Energy Technology Data Exchange (ETDEWEB)

    Oshanin, G [Laboratoire de Physique Theorique des Liquides, Universite Paris 6, 4 Place Jussieu, 75252 Paris (France); Burlatsky, S F [United Technologies Research Center, United Technologies Corporation, 411 Silver Lane, 129-21 East Hartford, CT (United States)

    2002-11-29

    We present an exact solution for a catalytically activated annihilation A+A {yields} 0 reaction taking place on a one-dimensional chain in which some segments (placed at random, with mean concentration p) possess special, catalytic properties. An annihilation reaction takes place as soon as any two A particles land from the reservoir onto two vacant sites at the extremities of the catalytic segment, or when any A particle lands onto a vacant site on a catalytic segment while the site at the other extremity of this segment is already occupied by another A particle. We find that the disorder-average pressure P{sup (quen)} per site of such a chain is given by P{sup (quen)} P{sup (Lan)} + {beta}{sup -1}F, where P{sup (Lan)}={beta}{sup -1} ln(1+z) is the Langmuir adsorption pressure, (z being the activity and {beta}{sup -1} the temperature), while {beta}{sup -1}F is the reaction-induced contribution, which can be expressed, under appropriate change of notation, as the Lyapunov exponent for the product of 2x2 random matrices, obtained exactly by Derrida and Hilhorst (1983 J. Phys. A: Math. Gen. 16 2641). Explicit asymptotic formulae for the particle mean density and the compressibility are also presented. (letter to the editor)

  9. Catalytic oxidation of CO on Ir(100)

    Energy Technology Data Exchange (ETDEWEB)

    Erikat, I.A. [Department of Physics, Jerash Private University (Jordan); Hamad, B.A.; Khalifeh, J.M. [Department of Physics, University of Jordan, Amman-11942 (Jordan)

    2011-06-15

    Density functional theory (DFT) calculations are performed to investigate the CO oxidation on Ir(100) surface at different CO coverages, 0.125, 0.25, and 0.5 monolayers (ML). The reaction pathway and transition state (TS) are determined using constrained minimization and nudged elastic band (NEB) methods. We found that the CO molecule is significantly more mobile toward O atoms, which causes a weakening of the O-metal bond. The increase of CO coverage leads to a decrease in the activation energy of the reaction and an increase of O{sub a}-CO distance where O coverage is kept at 0.25 ML. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Catalytic Potential of Nano-Magnesium Oxide on Degradation of Humic Acids From Aquatic Solutions

    Directory of Open Access Journals (Sweden)

    Ghorban Asgari

    2014-12-01

    Full Text Available Catalytic ozonation is a new and promising process used to remove the contaminants from drinking water and wastewater. This study aimed to evaluate the catalytic potential of nano-magnesium oxide (nano-MgO for the removal of humic acids (HA from water. Mg (NO32 solution was used to prepare MgO powder by the calcination method. In a semi-batch reactor, the catalytic ozonation was carried out. The effects of the various operating parameters, including pH, reaction time, T-butyl alcohol (TBA and phosphate on HA degradation were evaluated. Experimental results indicated that degradation of HA was increased as the pH solution and reaction time were increased. Maximum HA degradation was obtained at pH = 10 and the reaction time of 10 minutes in the catalytic process. The calculated catalytic potential of nano-MgO on ozonation of HA was 60%. Moreover, catalytic ozonation process was not affected by TBA and the main reaction on HA degradation HA have effect take place on MgO surface. According to the results of this study, the developed MgO catalyst is the active and proficient catalyst in HA degradation using the catalytic ozonation process.

  11. Studies of Cyclohexane Catalytic Oxidation Processes over Titanium Silicate-1 Zeolite

    Institute of Scientific and Technical Information of China (English)

    Cheng Shibiao; Wu Wei; Sun Bin; Min Enze

    2003-01-01

    The catalytic oxidation processes for cyclohexane/H2O2/acetone system over the TS-1 zeolite was studied. Study results have revealed that the cyclohexane conversion was 27% after the reaction proceeded at 100C for 2 hours at a cyclohexane/H2O2 molar ratio of 0.8. The cyclohexanol/cyclohexanone molar ratio was 1.3along with a certain amount of organic acids and esters, the formation of which was closely associated with the oxidation of reaction solvent and deep oxidation of cyclohexanone and cyclohexanol contained in the reaction products. With respect to the catalytic oxidation of cyclohexane/H2O2 system the selection of appropriate solvent was critically important.

  12. Selective catalytic oxidation of H2S over iron oxide supported on alumina-intercalated Laponite clay catalysts

    International Nuclear Information System (INIS)

    Graphical abstract: The catalytic reaction and deactivation mechanisms for H2S selective oxidation over Fe/Al-Lap catalysts are shown in the illustration. The catalytic reaction follows Mars–van Krevelen mechanism. Moreover, the interaction between iron oxide and alumina, the strong acidity of the catalysts and the well dispersion of iron oxide improve the catalytic performance efficiently. Meanwhile, the catalyst deactivation is mainly due to the formation of Fe2(SO4)3 and elemental sulfur deposits on the surface. -- Highlights: • Fe/Al-Lap catalysts with mesoporous structure were synthesized. • Iron oxide mainly exists in form of isolate Fe3+ in an oxidic environment. •Fe/Al-Lap catalysts show high catalytic activities at low temperature. •The high catalytic activities are ascribed to the interaction between iron oxide and alumina. •The formed Fe2(SO4)3 and elemental sulfur deposits on surface cause catalyst deactivation. -- Abstract: A series of iron oxide supported on alumina-intercalated clay catalysts (named Fe/Al-Lap catalysts) with mesoporous structure and high specific surface area were prepared. The structural and chemical properties were studied by nitrogen sorption isotherms, X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (UV–vis DRS), X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FTIR), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature-programmed desorption (NH3-TPD) techniques. It was realized that iron oxide mainly existed in the form of isolated Fe3+ in an oxidic environment. Fe/Al-Lap catalysts showed high catalytic activities in the temperature range of 120–200 °C without the presence of excessive O2. This can be attributed to the interaction between iron oxide and alumina, which improve the redox property of Fe3+ efficiently. In addition, the strong acidity of catalysts and good dispersion of iron oxide were also beneficial to oxidation reaction. Among them, 7% Fe

  13. CO catalytic oxidation on iron-embedded monolayer MoS{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Dongwei, E-mail: dwmachina@126.com [School of Physics, Anyang Normal University, Anyang, Henan 455000 (China); Tang, Yanan [Department of Physics and Electronic Science, Zhengzhou Normal University, Zhengzhou, Henan 450044 (China); Yang, Gui; Zeng, Jun [School of Physics, Anyang Normal University, Anyang, Henan 455000 (China); He, Chaozheng [Physics and Electronic Engineering College, Nanyang Normal University, Nanyang 473061 (China); Lu, Zhansheng [College of Physics and Electronic Engineering, Henan Normal University, Xinxiang, Henan 453007 (China)

    2015-02-15

    Highlights: • CO catalytic oxidation on the Fe-embedded monolayer MoS{sub 2} has been studied. • Fe atom can be strongly constrained at the S vacancy of monolayer MoS{sub 2}. • Fe-embedded monolayer MoS{sub 2} shows high catalytic activity toward CO oxidation. - Abstract: Based on first-principles calculations, the CO catalytic oxidation on the Fe-embedded monolayer MoS{sub 2} (Fe-MoS{sub 2}) was investigated. It is found that Fe atom can be strongly constrained at the S vacancy of monolayer MoS{sub 2} with a high diffusion barrier. The CO oxidation reaction proceeds via a two-step mechanism with the highest energy barrier of 0.51 eV, which is started by the Langmuir–Hinshelwood reaction and ended by the Eley–Rideal reaction. The high catalytic activity of the Fe-MoS{sub 2} system may be attributed to the charge transfer and the orbital hybridization between the adsorbates and the Fe atom. This study proposes that embedding transition-metals is a promising way for making the basal plane of monolayer MoS{sub 2} catalytically active.

  14. Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

    KAUST Repository

    Hong, Jongsup

    2013-10-01

    The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

  15. Effects of Oxygen Transfer Limitation and Kinetic Control on Biomimetic Catalytic Oxidation of Toluene

    Institute of Scientific and Technical Information of China (English)

    罗伟平; 刘大为; 孙俊; 邓伟; 盛文兵; 刘强; 郭灿城

    2014-01-01

    Under oxygen transfer limitation and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin was studied. An improved technique of measuring dissolved oxygen levels for gas-liquid reaction at the elevated temperature and pressure was used to take the sequential data in the oxidation of toluene catalyzed by metalloporphyrin. By this technique the corresponding control step of toluene oxidation could be obtained by varying reaction conditions. When the partial pressure of oxygen in the feed is lower than or equal to 0.070 MPa at 463 K, the oxidation of toluene would be controlled by oxygen transfer, otherwise the reaction would be controlled by kinetics. The effects of both oxygen transfer and kinetic control on the toluene conversion and the selectivity of benzaldehyde and benzyl alcohol in biomimetic catalytic oxidation of toluene were systematically investigated. Three conclusions have been made from the experimental results. Firstly, under the oxygen transfer limitation the toluene conversion is lower than that under kinetic control at the same oxidation conditions. Secondly, under the oxygen transfer limitation the total selectivity of benzaldehyde and benzyl alcohol is lower than that under kinetic control with the same conversion of toluene. Finally, under the kinetics control the oxidation rate of toluene is zero-order with respect to oxygen. The experimental results are identical with the biomimetic catalytic mechanism of toluene oxidation over metalloporphyrins.

  16. Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature.

    Science.gov (United States)

    Narsimhan, Karthik; Iyoki, Kenta; Dinh, Kimberly; Román-Leshkov, Yuriy

    2016-06-22

    The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C-H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483-498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions. PMID:27413787

  17. Stereodivergent catalytic doubly diastereoselective nitroaldol reactions using heterobimetallic complexes.

    Science.gov (United States)

    Sohtome, Yoshihiro; Kato, Yuko; Handa, Shinya; Aoyama, Naohiro; Nagawa, Keita; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2008-06-01

    Stereodivergent construction of three contiguous stereocenters in catalytic doubly diastereoselective nitroaldol reactions of alpha-chiral aldehydes with nitroacetaldehyde dimethyl acetal using two types of heterobimetallic catalysts is described. A La-Li-BINOL (LLB) catalyst afforded anti,syn-nitroaldol products in >20:1-14:1 selectivity, and a Pd/La/Schiff base catalyst afforded complimentary syn,syn-nitroaldol products in 10:1-5:1 selectivity. PMID:18465868

  18. Synthesis of (+)-Discodermolide by Catalytic Stereoselective Borylation Reactions**

    OpenAIRE

    Yu, Zhiyong; Ely, Robert J.; Morken, James P.

    2014-01-01

    The marine natural product (+)-discodermolide was first isolated in 1990 and, to this day, remains a compelling synthesis target. Not only does the compound possess fascinating biological activity, but it also presents an opportunity to test current methods for chemical synthesis and provides a forum for the inspiration of new reaction development. In this manuscript, we present a synthesis of discodermolide that employs a previously undisclosed stereoselective catalytic diene hydroboration a...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-07-31

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

  20. Structure and reactivity of surface oxides on Pt(110) during catalytic CO oxidation

    OpenAIRE

    Ackermann, M. D.; Pedersen, T. M.; Hendriksen, B.L.M.; ROBACH, O.; Bobaru, S. C.; Quiros, C.; Kim, H.; Hammer, B; Ferrer Fàbregas, Salvador; Frenke, J. W. M.

    2005-01-01

    We present the first structure determination by surface x-ray diffraction during the restructuring of a model catalyst under reaction conditions, i.e., at high pressure and high temperature, and correlate the restructuring with a change in catalytic activity. We have analyzed the Pt(110) surface during CO oxidation at pressures up to 0.5 bar and temperatures up to 625 K. Depending on the O2/CO pressure ratio, we find three well-defined structures: namely, (i) the bulk-terminated Pt(110) surfa...

  1. Highly Chemical and Regio-selective Catalytic Oxidation with a Novel Manganese Catalyst

    Institute of Scientific and Technical Information of China (English)

    刘斌; 陈怡; 余成志; 沈征武

    2003-01-01

    The chemical selectivity of a novel active manganese compound [Mn2IVμ-O)3(TMTACN)2] (PF6)2 (1) in catalytic oxidation reactions depended on the structure of substrates and 1 was able to catalyze the oxidation of toluene into benzaldehyde and/or benzoic acid under very mild conditions. The following results were obtained: (1) The selectivity of the oxidation depended on the electronic density of double bonds. Reactivity was absent when strong electron-witherawing groups were conjugated with double bonds. (2) Allylic oxidation reactions mostly take place when double bond is present inside a ring system, whilst epoxiclarion reactions occur when the alkene moiety is part of linear chain. (3) In ring systems, the methylene group was more likely to be oxidized than the methyl group on ailylic position. As expected, the C--H bonds at the bridgeheads were unreactive.The secondary hydroxyl groups are more easily to be oxidized than the primary hydroxyl groups.

  2. Catalytic and regioselective oxidation of carbohydrates to synthesize keto-sugars under mild conditions.

    Science.gov (United States)

    Muramatsu, Wataru

    2014-09-19

    A new catalytic and regioselective approach for the synthesis of keto-sugars is described. An organotin catalyst, Oc2SnCl2, in the presence of trimethylphenylammonium tribromide ([TMPhA](+)Br3(-)) accelerates the regioselective oxidation at the "axial"-OH group of 1,2-diol moieties in galactopyranosides. The reaction conditions can also be used for the regioselective oxidation of various carbohydrates.

  3. Lacunary Keggin Polyoxotungstate as Reaction-controlled Phasetransfer Catalyst for Catalytic Epoxidation of Olefins

    Institute of Scientific and Technical Information of China (English)

    LI,Ming-Qiang(李明强); JIAN,Xi-Gao(蹇锡高); YANG,Yong-Qiang(杨永强)

    2004-01-01

    A new reaction-controlled phase-transfer catalyst system, lacunary Keggin polyoxotungstate [C7H7N(CH3)3]9PW9O34 has been synthesized and used for catalytic epoxidation of olefins with H2O2 as the oxidant.Infrared spectra were used to analyze the behavior of the phase transfer of catalyst. In this system, the catalyst not only can act as homogeneous catalyst but also as heterogeneous catalyst to be easily filtered and reused. The epoxidation reaction is clean and exhibits high conversion and selectivity as well as excellent catalyst stability.

  4. Effect of reaction time on the characteristics of catalytically grown boron nitride nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Mohamed, Norani Muti, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: pervaiz-pas@yahoo.com, E-mail: shuaib-penang@yahoo.com, E-mail: zainabh@petronas.com.my; Ahmad, Pervaiz, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: pervaiz-pas@yahoo.com, E-mail: shuaib-penang@yahoo.com, E-mail: zainabh@petronas.com.my; Saheed, Mohamed Shuaib Mohamed, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: pervaiz-pas@yahoo.com, E-mail: shuaib-penang@yahoo.com, E-mail: zainabh@petronas.com.my; Burhanudin, Zainal Arif, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: pervaiz-pas@yahoo.com, E-mail: shuaib-penang@yahoo.com, E-mail: zainabh@petronas.com.my [Center of Innovative Nanostructures and Nanodevices (COINN), Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750, Tronoh, Perak (Malaysia)

    2014-10-24

    The paper reports on the growth of boron nitride nanotube (BNNTs) on Si substrate by catalytic chemical vapor deposition technique and the effect of reaction time and temperature on the size and purity were investigated. Scanning electron microscopy image revealed the bamboo-like BNNTs of multiwalled type with interlayer spacing of 0.34 nm. EDX analysis described the presence of a small percentage of Mg in the sample, indicating the combination of base-tip growth model for the sample synthesized at 1200°C. The reaction time has an effect of extending the length of the BNNTs until the catalyst is oxidized or covered by growth precursor.

  5. Electrochemical promotion of catalytic reactions with Pt/C (or Pt/Ru/C)//PBI catalysts

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bjerrum, Niels; Bandur, Viktor;

    2007-01-01

    The paper is an overview of the results of the investigation on electrochemical promotion of three catalytic reactions: methane oxidation with oxygen, NO reduction with hydrogen at 135 degrees C and Fischer-Tropsch synthesis (FTS) at 170 degrees C in the [CH4/O-2(or NO/H-2 or CO/H-2)/Ar//Pt(or Pt...... by the electrochemical pumping of H+ from the catalyst, i.e. at positive polarization. FTS demonstrated the highest methane production rate (11% of CO conversion) at zero fuel cell voltage.......The paper is an overview of the results of the investigation on electrochemical promotion of three catalytic reactions: methane oxidation with oxygen, NO reduction with hydrogen at 135 degrees C and Fischer-Tropsch synthesis (FTS) at 170 degrees C in the [CH4/O-2(or NO/H-2 or CO/H-2)/Ar//Pt(or Pt....../Ru)//PBI(H3PO4)/H-2, Ar] fuel cell. It has been shown that the partial methane oxidation to C2H2 and the C-2 selectivity were electrochemically promoted by the negative catalyst polarization. This was also the case in NO reduction with hydrogen for low NO and H-2 partial pressures. In both cases the catalytic...

  6. Heterogeneous selective oxidation of formaldehyde over oxide catalysts. 1. Catalytic properties of H3PMo12O40 and K3PMoO12O40

    International Nuclear Information System (INIS)

    Catalytic properties of H3PMo12O40 and K3PMo12O40, dried at 120 deg C and calcinated at 420 deg C, were investigated in the reaction of heterogenous oxidation of formaldehyde in temperature range 120-180 deg C. It is shown that catalytic properties are determined by heat treatment conditions. Formic acid is the main product of formaldehyde oxidation on dried samples. Samples calcinated at 42 deg C are inactive in reaction of formaldehyde oxidation. It is shown that hydrated forms of H3PMo12O40 and K3PMo12O40 are effective in this reaction. (author)

  7. Catalytic abatement of nitrous oxide from nitric and production

    NARCIS (Netherlands)

    Oonk, J.

    1998-01-01

    Nitric acid production is identified as a main source of nitrous oxide. Options for emission reduction however are not available. TNO and Hydro Agri studied the technological and economic feasibility of catalytic decomposition of nitrous oxide in nitric acid tail-gases. Although in literature promis

  8. Catalytic oxidative cracking of hexane as a route to olefins

    NARCIS (Netherlands)

    Boyadjian, Cassia; Lefferts, Leon; Seshan, K.

    2010-01-01

    Catalytic oxidative cracking of naphtha is conceptually an alternative process to steam cracking. The performance of sol–gel synthesized Li/MgO in oxidative cracking of hexane as a model compound of naphtha, has been studied and compared to that of conventionally prepared catalyst. At a temperature

  9. Synthesis and Catalytic Asymmetric Reaction of Chiral Pyridine Prolinol Derivatives

    Institute of Scientific and Technical Information of China (English)

    CHEN Xiao; ZHANG Yong-Xin; DU Da-Ming; HUA Wen-Ting

    2003-01-01

    @@ The enantioselective reduction of prochiral ketones with borane in the presence of a chiral ligand leading to enantiomerically pure secondary alcohols has received considerable attention in recent years. [1] Enantiomerically pure secondary alcohols are important intermediates for the synthesis of various other organic compounds such as halides, esters, ethers, ketones and amines. To the best of our knowledge, the use of pyridine prolinol derivatives in the reduction of ketones has not been reported so far. Thus, it should be of interest to investigate the catalytic a bility of such ligands. We have an ongoing project in the synthesis and application of chiral pyridine derivatives in chiral molecular recognition[2] and we want to evaluate the effect resulting from the introduction of a pyridinyl moiety onto the catalysts. We expect that the cooperation of pyridine unit and chiral prolinol unit in new ligands may result in unique properties for catalytic reaction.

  10. The chemical and catalytic properties of nanocrystalline metal oxides prepared through modified sol-gel synthesis

    Science.gov (United States)

    Carnes, Corrie Leigh

    The goal of this research was to synthesize, characterize and study the chemical properties of nanocrystalline metal oxides. Nanocrystalline (NC) ZnO, CuO, NiO, Al2O3, and the binary Al2O 3/MgO and ZnO/CuO were prepared through modified sol gel methods. These NC metal oxides were studied in comparison to the commercial (CM) metal oxides. The samples were characterized by XRD, TGA, FTIR, BET, and TEM. The NC samples were all accompanied by a significant increase in surface area and decrease in crystallite size. Several chemical reactions were studied to compare the NC samples to the CM samples. One of the reactions involved a high temperature reaction between carbon tetrachloride and the oxide to form carbon dioxide and the corresponding metal chloride. A similar high temperature reaction was conducted between the metal oxide and hydrogen sulfide to form water and the corresponding metal sulfide. A room temperature gas phase adsorption was studied where SO2 was adsorbed onto the oxide. A liquid phase adsorption conducted at room temperature was the destructive adsorption of paraoxon (a toxic insecticide). In all reactions the NC samples exhibited greater activity, destroying or adsorbing a larger amount of the toxins compared to the CM samples. To better study surface area effects catalytic reactions were also studied. The catalysis of methanol was studied over the nanocrystalline ZnO, CuO, NiO, and ZnO/CuO samples in comparison to their commercial counterparts. In most cases the NC samples proved to be more active catalysts, having higher percent conversions and turnover numbers. A second catalytic reaction was also studied, this reaction was investigated to look at the support effects. The catalysis of cyclopropane to propane was studied over Pt and Co catalysts. These catalysts were supported onto NC and CM alumina by impregnation. By observing differences in the catalytic behavior, support effects have become apparent.

  11. Preparation of Pt-Ru hydrophobic catalysts and catalytic activities for liquid phase catalytic exchange reaction

    International Nuclear Information System (INIS)

    Pt/C and Pt-Ru/C catalysts with different ratios of Pt to Ru were synthesized, using ethylene glycol as both the dispersant and reducing agent at 1-2 MPa by microwave-assisted method. The catalysts were characterized by XRD, TEM and XPS. The mean particle sizes of the Pt/C and Pt-Ru/C catalysts were 1.9-2.0 nm. Pt and Ru existed as Pt(0), Pt(II), Pt(IV), Ru(0) and Ru(IV) for Pt-Ru/C catalysts, respectively. The face-centered cubic structure of the active mental particles would be changed upon the addition of Ru gradually. Then polytetrafluoroethylene and carbon-supported Pt and Pt-Ru catalysts were supported on foamed nickel to obtain hydrophobic catalysts. The catalytic activity was increased for liquid phase catalytic exchange (LPCE) when uniform Pt based hydrophobic catalysts was mixed into appropriate Ru. Hydrogen isotope exchange reaction occurs between hydration layer(H2O)nH+(ads)(n≥2) and D atoms due to intact water molecules being on Pt surface for LPCE. Water molecules have a tendency to dissociate to OH(ads) and H(ads) on metal Ru surface, and there is the other reaction path for Pt-Ru binary catalysts, which is probably the main reason of the increase of the catalytic activity of the hydrophobic Pt-Ru catalyst. (authors)

  12. Graphene-Semiconductor Catalytic Nanodiodes for Quantitative Detection of Hot Electrons Induced by a Chemical Reaction.

    Science.gov (United States)

    Lee, Hyosun; Nedrygailov, Ievgen I; Lee, Young Keun; Lee, Changhwan; Choi, Hongkyw; Choi, Jin Sik; Choi, Choon-Gi; Park, Jeong Young

    2016-03-01

    Direct detection of hot electrons generated by exothermic surface reactions on nanocatalysts is an effective strategy to obtain insight into electronic excitation during chemical reactions. For this purpose, we fabricated a novel catalytic nanodiode based on a Schottky junction between a single layer of graphene and an n-type TiO2 layer that enables the detection of hot electron flows produced by hydrogen oxidation on Pt nanoparticles. By making a comparative analysis of data obtained from measuring the hot electron current (chemicurrent) and turnover frequency, we demonstrate that graphene's unique electronic structure and extraordinary material properties, including its atomically thin nature and ballistic electron transport, allow improved conductivity at the interface between the catalytic Pt nanoparticles and the support. Thereby, graphene-based nanodiodes offer an effective and facile way to approach the study of chemical energy conversion mechanisms in composite catalysts with carbon-based supports. PMID:26910271

  13. Modifying the catalytic and adsorption properties of metals and oxides

    Science.gov (United States)

    Yagodovskii, V. D.

    2015-11-01

    A new approach to interpreting the effect of promoters (inhibitors) of nonmetals and metals added to a host metal (catalyst) is considered. Theoretical calculations are based on a model of an actual two-dimensional electron gas and adsorbate particles. An equation is derived for the isotherm of induced adsorption on metals and semiconductors with respect to small fillings of θ ~ 0.1-0.15. The applicability of this equation is verified experimentally for metals (Ag, Pd, Cu, Fe, and Ni), graphitized ash, and semiconductor oxides Ta2O5, ZnO, and Ni. The applicability of the theoretical model of promotion is verified by the hydrogenation reaction of CO on ultradispersed nickel powder. The use of plasmachemical surface treatments of metals and oxides, accompanied by an increase in activity and variation in selectivity, are investigated based on the dehydrocyclization reactions of n-hexane and the dehydrogenation and dehydration of alcohols. It is established that such treatments for metals (Pt, Cu, Ni, and Co) raise their activity due to the growth of the number of active centers upon an increase in the activation energy. Applying XPES and XRD methods to metallic catalysts, it is shown that the rise in activity is associated with a change in their surface states (variation in the structural characteristics of metal particles and localization of certain forms of carbon in catalytically active centers). It is shown that plasmachemical treatments also alter their surface composition, surface activity, and raise their activity when used with complex phosphate oxides of the NASICON type. It is shown by the example of conversion of butanol-2 that abrupt variations in selectivity (prevalence of dehydration over dehydrogenation and vice versa) occur, depending on the type of plasma. It is concluded that plasmachemical treatments of metals and ZnO and NiO alter the isosteric heats and entropies of adsorption of isopropanol.

  14. [Current research situation of H2S selective catalytic oxidation technologies and catalysts].

    Science.gov (United States)

    Hao, Zheng-ping; Dou, Guang-yu; Zhang, Xin; Qu, Si-qiu

    2012-08-01

    This review summarizes and discusses different selective catalytic oxidation technologies and various catalysts for removing H2S, the undesirable byproduct of the fluid catalytic cracking (FCC) processing. Currently the selective oxidation technologies used include Superclaus, Euroclaus, Clinsulf-Do, BSR/Hi-Activity, Selectox and Modop techniques, which have various characteristics and application areas. Catalysts for H2S selective oxidation mainly contain the following systems: carbon, supported SiC, zeolite, oxide, and pillared clay. Former studies focused on carbon and oxide systems. The research interest on zeolite system decreased in recent years, while SiC is regarded as a typical support with great potential for this reaction and continues to be attractive. Pillared clay system is at the preliminary research stage, and is still far from practical application.

  15. Removal of nitrogen compounds from gasification gas by selective catalytic or non-catalytic oxidation; Typpiyhdisteiden poisto kaasutuskaasusta selektiivisellae katalyyttisellae ja ei-katalyyttisellae hapetuksella

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J.; Koljonen, T. [VTT Energy, Espoo (Finland)

    1996-12-01

    In gasification reactive nitrogenous compounds are formed from fuel nitrogen, which may form nitrogen oxides in gas combustion. In fluidized bed gasification the most important nitrogenous compound is ammonia (NH{sub 3}). If ammonia could be decomposed to N{sub 2} already before combustion, the emissions if nitrogen oxides could be reduced significantly. One way of increasing the decomposition rate of NH{sub 3} could be the addition of suitable reactants to the gas, which would react with NH{sub 3} and produce N{sub 2}. The aim of this research is to create basic information, which can be used to develop a new method for removal of nitrogen compounds from gasification gas. The reactions of nitrogen compounds and added reactants are studied in reductive atmosphere in order to find conditions, in which nitrogen compounds can be oxidized selectively to N{sub 2}. The project consists of following subtasks: (1) Selective non-catalytic oxidation (SNCO): Reactions of nitrogen compounds and oxidizers in the gas phase, (2) Selective catalytic oxidation (SCO): Reactions of nitrogen compounds and oxidizers on catalytically active surfaces, (3) Kinetic modelling of experimental results in co-operation with the Combustion Chemistry Research Group of Aabo Akademi University. The most important finding has been that NH{sub 3} can be made to react selectively with the oxidizers even in the presence of large amounts of CO and H{sub 2}. Aluminium oxides were found to be the most effective materials promoting selectivity. (author)

  16. Lignin Valorization using Heterogenous Catalytic Oxidation

    DEFF Research Database (Denmark)

    Melián Rodríguez, Mayra; Shunmugavel, Saravanamurugan; Kegnæs, Søren;

    is complex so different model compounds are often used to study lignin valorization. These model compounds contain the linkages present in lignin, simplifying catalytic analysis and present analytical challenges related to the study of the complicated lignin polymer and the plethora of products that could...

  17. Catalytic partial oxidation of methane to synthesis gas over ZRO2-based defective oxides

    NARCIS (Netherlands)

    Zhu, Jianjun

    2005-01-01

    the work presented in this thesis provides both fundamental scientific knowledge as well as a new technical dual-bed concept for synthesis gas production via catalytic partial oxidation of methane over defective ZrO2-based oxides.

  18. Recent developments in research on catalytic reaction networks

    Directory of Open Access Journals (Sweden)

    Roberto Serra

    2013-09-01

    Full Text Available Over the last years, analyses performed on a stochastic model of catalytic reaction networks have provided some indications about the reasons why wet-lab experiments hardly ever comply with the phase transition typically predicted by theoretical models with regard to the emergence of collectively self-replicating sets of molecule (also defined as autocatalytic sets, ACSs, a phenomenon that is often observed in nature and that is supposed to have played a major role in the emergence of the primitive forms of life. The model at issue has allowed to reveal that the emerging ACSs are characterized by a general dynamical fragility, which might explain the difficulty to observe them in lab experiments. In this work, the main results of the various analyses are reviewed, with particular regard to the factors able to affect the generic properties of catalytic reactions network, for what concerns, not only the probability of ACSs to be observed, but also the overall activity of the system, in terms of production of new species, reactions and matter.

  19. Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ju, Hua [School of Urban Rail Transportation, Soochow University, Suzhou 215006 (China); Li, Zhihu [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China); Xu, Yanhui, E-mail: xuyanhui@suda.edu.cn [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China)

    2015-04-15

    Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.

  20. Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction

    International Nuclear Information System (INIS)

    Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm−2 for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm−2 (the real surface area), and the reaction rate constant has an order of magnitude of 10−7–10−6 cm s−1. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER

  1. Catalytic X-H insertion reactions based on carbenoids.

    Science.gov (United States)

    Gillingham, Dennis; Fei, Na

    2013-06-21

    Catalysed X-H insertion reactions into diazo compounds (where X is any heteroatom) are a powerful yet underutilized class of transformations. The following review will explore the historical development of X-H insertion and give an up-to-date account of the metal catalysts most often employed, including an assessment of their strengths and weaknesses. Despite decades of development, recent work on enantioselective variants, as well as applying catalytic X-H insertion towards problems in chemical biology indicate that this field has ample room for innovation. PMID:23407887

  2. Synthesis of (+)-discodermolide by catalytic stereoselective borylation reactions.

    Science.gov (United States)

    Yu, Zhiyong; Ely, Robert J; Morken, James P

    2014-09-01

    The marine natural product (+)-discodermolide was first isolated in 1990 and, to this day, remains a compelling synthesis target. Not only does the compound possess fascinating biological activity, but it also presents an opportunity to test current methods for chemical synthesis and provides an inspiration for new reaction development. A new synthesis of discodermolide employs a previously undisclosed stereoselective catalytic diene hydroboration and also establishes a strategy for the alkylation of chiral enolates. Furthermore, this synthesis of discodermolide provides the first examples of the asymmetric 1,4-diboration of dienes and borylative diene-aldehyde couplings in complex-molecule synthesis.

  3. Synthesis of (+)-Discodermolide by Catalytic Stereoselective Borylation Reactions**

    Science.gov (United States)

    Yu, Zhiyong; Ely, Robert J.

    2014-01-01

    The marine natural product (+)-discodermolide was first isolated in 1990 and, to this day, remains a compelling synthesis target. Not only does the compound possess fascinating biological activity, but it also presents an opportunity to test current methods for chemical synthesis and provides a forum for the inspiration of new reaction development. In this manuscript, we present a synthesis of discodermolide that employs a previously undisclosed stereoselective catalytic diene hydroboration and also establishes a strategy for chiral enolate alkylation. In addition, this synthesis of discodermolide provides the first examples of diene 1,4-diboration and borylative diene-aldehyde couplings in complex molecule synthesis. PMID:25045037

  4. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    ZHANG; XuMu

    2001-01-01

    Chiral Quest's Toolbox Approach: During the last several decades, chemists have made major progress in discovering man-made catalysts to perform challenging asymmetric transformations. However, there is no universal chiral ligand or catalyst for solving problems in enantioselective transformations. The focus of Chiral Quest's research is to develop a useful chiral toolbox for strategically important asymmetric catalytic reactions by inventing a diverse set of novel chiral ligands and combining them with transition metals as effective enantioselective catalysts. The toolbox approach addresses significant problems in organic stereochemistry and has resulted in practical methods for the synthesis of chiral pharmaceuticals and agrochemicals  ……

  5. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Chiral Quest's Toolbox Approach: During the last several decades, chemists have made major progress in discovering man-made catalysts to perform challenging asymmetric transformations. However, there is no universal chiral ligand or catalyst for solving problems in enantioselective transformations. The focus of Chiral Quest's research is to develop a useful chiral toolbox for strategically important asymmetric catalytic reactions by inventing a diverse set of novel chiral ligands and combining them with transition metals as effective enantioselective catalysts. The toolbox approach addresses significant problems in organic stereochemistry and has resulted in practical methods for the synthesis of chiral pharmaceuticals and agrochemicals

  6. Catalytic wet Air Oxidation of o-Chlorophenol in Wastewater

    Institute of Scientific and Technical Information of China (English)

    徐新华; 汪大翬

    2003-01-01

    Catalytic wet air oxidation (CWAO) was investigated in laboratory-scale experiments for the treatment of o-chlorophenol in wastewater. Experimental results showed that wet air oxidation (WAO) process in the absence of catalyst was also effective for o-chlorophenol in wastewater treatment. Up to 80% of the initial CODCr was removed by wet air oxidation at 270℃ with twice amount of the required stoichiometric oxygen supply. At temperature of 150℃, the removal rate of CODCr was only 30%. Fe2(SO4)3, CuSO4, Cu(NO3)2 and MnSO4 exhibited high catalytic activity. Higher removal rate of CODCr was obtained by CWAO. More than 96% of the initial CODCr was removed at 270℃ and 84.6%-93.6% of the initial CODCr was removed at 150℃. Mixed catalysts had better catalytic activity for the degradation of o-chlorophenol in wastewater.

  7. Studies on Nitrogen Oxides Removal Using Plasma Assisted Catalytic Reactor

    Institute of Scientific and Technical Information of China (English)

    V. Ravi; Young Sun Mok; B. S. Rajanikanth; Ho-Chul Kang

    2003-01-01

    An electric discharge plasma reactor combined with a catalytic reactor was studied for removing nitrogen oxides. To understand the combined process thoroughly, discharge plasma and catalytic process were separately studied first, and then the two processes were combined for the study. The plasma reactor was able to oxidize NO to NO2 well although the oxidation rate decreased with temperature. The plasma reactor alone did not reduce the NOx (NO+NO2)level effectively, but the increase in the ratio of NO2 to NO as a result of plasma discharge led to the enhancement of NOx removal efficiency even at lower temperatures over the catalyst surface (V2O5-WOa/TiO2). At a gas temperature of 100℃, the NOx removal efficiency obtained using the combined plasma catalytic process was 88% for an energy input of 36 eV/molecule or 30 J/1.

  8. SPONTANEOUS CATALYTIC WET AIR OXIDATION DURING PRE-TREATMENT OF HIGH-LEVEL RADIOACTIVE WASTE SLUDGE

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D.; Herman, C.; Pareizs, J.; Bannochie, C.; Best, D.; Bibler, N.; Fellinger, T.

    2009-10-01

    Savannah River Remediation, LLC (SRR) operates the Defense Waste Processing Facility for the U.S. Department of Energy at the Savannah River Site. This facility immobilizes high-level radioactive waste through vitrification following chemical pretreatment. Catalytic destruction of formate and oxalate ions to carbon dioxide has been observed during qualification testing of non-radioactive analog systems. Carbon dioxide production greatly exceeded hydrogen production, indicating the occurrence of a process other than the catalytic decomposition of formic acid. Statistical modeling was used to relate the new reaction chemistry to partial catalytic wet air oxidation of both formate and oxalate ions driven by the low concentrations of palladium, rhodium, and/or ruthenium in the waste. Variations in process conditions led to increases or decreases in the total oxidative destruction, as well as partially shifting the preferred species undergoing destruction from oxalate ion to formate ion.

  9. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, October 1--December 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Heinemann, H.; Somorjai, G.A.; Perry, D.L.

    1992-12-01

    Work on catalytic steam gasification with chars and coals will be extended from atmospheric to elevated pressures using the newly built pressure unit. The novel finding that coking of petroleum in the presence of small amounts of caustic greatly improves the gasification rates and characteristics of the coke will be extended to chars; in the oxidative coupling of methane over ternary catalysts, emphasis will be placed on low temperature coupling and on the oxidative production of syngas from methane at low temperature. Experimental work will continue on the synthesis of the mixed catalyst, and they will be characterized by a number of techniques, including elemental analyses, x-ray diffraction, and surface area determination.

  10. CO oxidation over ruthenium: identification of the catalytically active phases at near-atmospheric pressures

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Feng; Goodman, Wayne D.

    2012-05-21

    CO oxidation was carried out over Ru(0001) and RuO2(110) thin film grown on Ru(0001) at various O2/CO ratios near atmospheric pressures. Reaction kinetics, coupled with in situ polarization modulation infrared reflection absorption spectroscopy (PM-IRAS) and post-reaction Auger electron spectroscopy (AES) measurements were used to identify the catalytically relevant phases at different reaction conditions. Under stoichiometric and reducing conditions at all reaction temperatures, as well as net-oxidizing reaction conditions below {approx}475 K, a reduced metallic phase with chemisorbed oxygen is the thermodynamically stable and catalytically active phase. On this surface CO oxidation occurs at surface defect sites, for example step edges. Only at net-oxidizing reaction conditions and above {approx}475 K is the RuO2 thin film grown on metallic Ru stable and active. However, RuO2 is not active itself without the existence of the metal substrate, suggesting the importance of a strong metal-substrate interaction (SMSI).

  11. Roles of catalytic oxidation in control of vehicle exhaust emissions

    International Nuclear Information System (INIS)

    Catalytic oxidation was initially associated with the early development of catalysis and it subsequently became a part of many industrial processes, so it is not surprising it was used to remove hydrocarbons and CO when it became necessary to control these emissions from cars. Later NOx was reduced in a process involving reduction over a Pt/Rh catalyst followed by air injection in front of a Pt-based oxidation catalyst. If over-reduction of NO to NH3 took place, or if H2S was produced, it was important these undesirable species were converted to NOx and SOx in the catalytic oxidation stage. When exhaust gas composition could be kept stoichiometric hydrocarbons, CO and NOx were simultaneously converted over a single Pt/Rh three-way catalyst (TWC). With modern TWCs car tailpipe emissions can be exceptionally low. NO is not catalytically dissociated to O2 and N2 in the presence of O2, it can only be reduced to N2. Its control from lean-burn gasoline engines involves catalytic oxidation to NO2 and thence nitrate that is stored and periodically reduced to N2 by exhaust gas enrichment. This method is being modified for diesel engines. These engines produce soot, and filtration is being introduced to remove it. The exhaust temperature of heavy-duty diesels is sufficient (250-400oC) for NO to be catalytically oxidised to NO2 over an upstream platinum catalyst that smoothly oxidises soot in the filter. The exhaust gas temperature of passenger car diesels is too low for this to take place all of the time, so trapped soot is periodically burnt in O2 above 550oC. Catalytic oxidation of higher than normal amounts of hydrocarbon and CO over an upstream catalyst is used to give sufficient temperature for soot combustion with O2 to take place. (author)

  12. Reaction Current Phenomenon in Bifunctional Catalytic Metal-Semiconductor Nanostructures

    Science.gov (United States)

    Hashemian, Mohammad Amin

    Energy transfer processes accompany every elementary step of catalytic chemical processes on material surface including molecular adsorption and dissociation on atoms, interactions between intermediates, and desorption of reaction products from the catalyst surface. Therefore, detailed understanding of these processes on the molecular level is of great fundamental and practical interest in energy-related applications of nanomaterials. Two main mechanisms of energy transfer from adsorbed particles to a surface are known: (i) adiabatic via excitation of quantized lattice vibrations (phonons) and (ii) non-adiabatic via electronic excitations (electron/hole pairs). Electronic excitations play a key role in nanocatalysis, and it was recently shown that they can be efficiently detected and studied using Schottky-type catalytic nanostructures in the form of measureable electrical currents (chemicurrents) in an external electrical circuit. These nanostructures typically contain an electrically continuous nanocathode layers made of a catalytic metal deposited on a semiconductor substrate. The goal of this research is to study the direct observations of hot electron currents (chemicurrents) in catalytic Schottky structures, using a continuous mesh-like Pt nanofilm grown onto a mesoporous TiO2 substrate. Such devices showed qualitatively different and more diverse signal properties, compared to the earlier devices using smooth substrates, which could only be explained on the basis of bifunctionality. In particular, it was necessary to suggest that different stages of the reaction are occurring on both phases of the catalytic structure. Analysis of the signal behavior also led to discovery of a formerly unknown (very slow) mode of the oxyhydrogen reaction on the Pt/TiO2(por) system occurring at room temperature. This slow mode was producing surprisingly large stationary chemicurrents in the range 10--50 microA/cm2. Results of the chemicurrent measurements for the bifunctional

  13. Heterogeneous selective oxidation of formaldehyde over oxide catalysts. 2. Catalytic properties of V-Ti-oxide catalysts

    International Nuclear Information System (INIS)

    Catalytic properties of V-Ti-O-system and individual oxides V2O5 and TiO2 are investigated in reaction of formaldehyde oxidation within temperature range 120-160 deg C. Formic acid is the main product of formaldehyde oxidation on V2O5 and V-TiO-samples containing more than 5 mass% of V2O5, CO, CO2 and methyl formate form in small amounts. Selectivity with respect to formic acid for samples with 10-75 % V2O5-9025 % TiO2 composition in the conversion range 10-75 % at temperature 120 deg C is constant and comprises 98-93 %. V2O5 has high selectivity but low activity. (author)

  14. Catalytic wet air oxidation of 2-chlorophenol over sewage sludge-derived carbon-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Tu, Yuting [Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON), CNRS – Université Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France); School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Xiong, Ya; Tian, Shuanghong [School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, Guangzhou 510275 (China); Kong, Lingjun [School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Descorme, Claude, E-mail: claude.descorme@ircelyon.univ-lyon1.fr [Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON), CNRS – Université Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France)

    2014-07-15

    Highlights: • A sewage sludge derived carbon-supported iron oxide catalyst (FeSC) was prepared. • FeSC exhibited high catalytic activity in the wet air oxidation of 2-chlorophenol. • A strong correlation was observed between the 2-CP conversion, the iron leaching and the pH. • Using an acetate buffer, the iron leaching was suppressed while keeping some catalytic activity. • A simplified reaction pathway was proposed for the CWAO of 2-CP over the FeSC catalyst. - Abstract: A sewage sludge derived carbon-supported iron oxide catalyst (FeSC) was prepared and used in the Catalytic Wet Air Oxidation (CWAO) of 2-chlorophenol (2-CP). The catalysts were characterized in terms of elemental composition, surface area, pH{sub PZC}, XRD and SEM. The performances of the FeSC catalyst in the CWAO of 2-CP was assessed in a batch reactor operated at 120 °C under 0.9 MPa oxygen partial pressure. Complete decomposition of 2-CP was achieved within 5 h and 90% Total Organic Carbon (TOC) was removed after 24 h of reaction. Quite a straight correlation was observed between the 2-CP conversion, the amount of iron leached in solution and the pH of the reaction mixture at a given reaction time, indicating a strong predominance of the homogeneous catalysis contribution. The iron leaching could be efficiently prevented when the pH of the solution was maintained at values higher than 4.5, while the catalytic activity was only slightly reduced. Upon four successive batch CWAO experiments, using the same FeSC catalyst recovered by filtration after pH adjustment, only a very minor catalyst deactivation was observed. Finally, based on all the identified intermediates, a simplified reaction pathway was proposed for the CWAO of 2-CP over the FeSC catalyst.

  15. Surface and catalytic properties of doped tin oxide nanoparticles

    Science.gov (United States)

    Wang, Chien-Tsung; Lai, De-Lun; Chen, Miao-Ting

    2010-10-01

    Mixed oxides composed of Zn-Sn, Ti-Sn and V-Sn were prepared by a co-precipitation method and evaluated as catalysts for methanol oxidation in an ambient fixed-bed reactor. Surface analysis by X-ray photoelectron spectroscopy (XPS) revealed an electronic interaction between dopant and Sn atoms in the oxide structure and showed the formation of surface states associated with the dopants. Oxygen vacancies were present on the Zn-doped oxide, and the oxidation of methanol to carbon oxides was favored. The Ti-doped oxide exhibited a favorable selectivity to dimethyl ether, related to the oxygen anions near Ti centers. Vanadium dopants not only dramatically increased the catalytic activity but also promoted the partial oxidation of methanol to formaldehyde. Results demonstrate that the bridging dopant-O-Sn bond acts as active sites and influences product distribution.

  16. Catalytic oxidation of cyclohexane to cyclohexanone and cyclohexanol by tert-butyl hydroperoxide over Pt/oxide catalysts

    Indian Academy of Sciences (India)

    I Rekkab-Hammoumraoui; A Choukchou-Braham; L Pirault-Roy; C Kappenstein

    2011-08-01

    Heterogeneous oxidation of cyclohexane with tertiobutyl hydroperoxide was carried out on Pt/oxide (Al2O3, TiO2 and ZrO2) catalysts in the presence of different solvents (acetic acid and acetonitrile). The catalysts were prepared using Pt(NH3)2(NO2)2 as a precursor and characterized by chemical analysis using the ICP–AES method, XRD, TEM, FTIR and BET surface area determination. The oxidation reaction was carried out at 70°C under atmospheric pressure. The results showed the catalytic performance of Pt/Al2O3 as being very high in terms of turnover frequency.

  17. Monodisperse metal nanoparticle catalysts on silica mesoporous supports: synthesis, characterizations, and catalytic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Somorjai, G.A.

    2009-09-14

    The design of high performance catalyst achieving near 100% product selectivity at maximum activity is one of the most important goals in the modern catalytic science research. To this end, the preparation of model catalysts whose catalytic performances can be predicted in a systematic and rational manner is of significant importance, which thereby allows understanding of the molecular ingredients affecting the catalytic performances. We have designed novel 3-dimensional (3D) high surface area model catalysts by the integration of colloidal metal nanoparticles and mesoporous silica supports. Monodisperse colloidal metal NPs with controllable size and shape were synthesized using dendrimers, polymers, or surfactants as the surface stabilizers. The size of Pt, and Rh nanoparticles can be varied from sub 1 nm to 15 nm, while the shape of Pt can be controlled to cube, cuboctahedron, and octahedron. The 3D model catalysts were generated by the incorporation of metal nanoparticles into the pores of mesoporous silica supports via two methods: capillary inclusion (CI) and nanoparticle encapsulation (NE). The former method relies on the sonication-induced inclusion of metal nanoparticles into the pores of mesoporous silica, whereas the latter is performed by the encapsulation of metal nanoparticles during the hydrothermal synthesis of mesoporous silica. The 3D model catalysts were comprehensively characterized by a variety of physical and chemical methods. These catalysts were found to show structure sensitivity in hydrocarbon conversion reactions. The Pt NPs supported on mesoporous SBA-15 silica (Pt/SBA-15) displayed significant particle size sensitivity in ethane hydrogenolysis over the size range of 1-7 nm. The Pt/SBA-15 catalysts also exhibited particle size dependent product selectivity in cyclohexene hydrogenation, crotonaldehyde hydrogenation, and pyrrole hydrogenation. The Rh loaded SBA-15 silica catalyst showed structure sensitivity in CO oxidation reaction. In

  18. Trends in the Catalytic CO Oxidation Activity of Nanoparticles

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Falsig, Hanne; Larsen, Britt Hvolbæk;

    2008-01-01

    Going for gold: Density functional calculations show how gold nanoparticles are more active catalysts for CO oxidation than other metal nanoparticles. The high catalytic activity of nanosized gold clusters at low temperature is found to be related to the ability of low-coordinate metal atoms...

  19. Tunable catalytic properties of bi-functional mixed oxides in ethanol conversion to high value compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ramasamy, Karthikeyan K.; Gray, Michel J.; Job, Heather M.; Smith, Colin D.; Wang, Yong

    2016-04-10

    tA highly versatile ethanol conversion process to selectively generate high value compounds is pre-sented here. By changing the reaction temperature, ethanol can be selectively converted to >C2alcohols/oxygenates or phenolic compounds over hydrotalcite derived bi-functional MgO–Al2O3cata-lyst via complex cascade mechanism. Reaction temperature plays a role in whether aldol condensationor the acetone formation is the path taken in changing the product composition. This article containsthe catalytic activity comparison between the mono-functional and physical mixture counterpart to thehydrotalcite derived mixed oxides and the detailed discussion on the reaction mechanisms.

  20. Catalytic oxidation for treatment of ECLSS and PMMS waste streams. [Process Material Management Systems

    Science.gov (United States)

    Akse, James R.; Thompson, John; Scott, Bryan; Jolly, Clifford; Carter, Donald L.

    1992-01-01

    Catalytic oxidation was added to the baseline multifiltration technology for use on the Space Station Freedom in order to convert low-molecular weight organic waste components such as alcohols, aldehydes, ketones, amides, and thiocarbamides to CO2 at low temperature (121 C), thereby reducing the total organic carbon (TOC) to below 500 ppb. The rate of reaction for the catalytic oxidation of aqueous organics to CO2 and water depends primarily upon the catalyst, temperature, and concentration of reactants. This paper describes a kinetic study conducted to determine the impact of each of these parameters upon the reaction rate. The results indicate that a classic kinetic model, the Langmuir-Hinshelwood rate equation for heterogeneous catalysis, can accurately represent the functional dependencies of this rate.

  1. Novel monolithic electrochemically promoted catalytic reactor for environmentally important reactions

    Energy Technology Data Exchange (ETDEWEB)

    Balomenou, S.; Tsiplakides, D.; Katsaounis, A.; Vayenas, C.G. [Department of Chemical Engineering, University of Patras, Caratheodory 1 St., GR-26504 Patras (Greece); Thiemann-Handler, S.; Cramer, B. [Robert Bosch GmbH Stuttgart, FV/FLC, PF 10 60 50, 70 049 Stuttgart (Germany); Foti, G.; Comninellis, Ch. [Institute of Chemical Sciences and Engineering, Swiss Federal Institute of Technology, CH-1015 Lausanne (Switzerland)

    2004-09-28

    A novel dismantlable monolithic-type electrochemically promoted catalytic reactor and 'smart' sensor-catalytic reactor unit has been constructed and tested for hydrocarbon oxidation and NO reduction by C{sub 2}H{sub 4} in presence of O{sub 2}. In this novel reactor, thin (=20-40nm) porous catalyst films made of two different materials are sputter-deposited on opposing surfaces of thin (0.25mm) parallel solid electrolyte plates supported in the grooves of a ceramic monolithic holder and serve as sensor or electropromoted catalyst elements. Using Rh/YSZ/Pt-type catalyst elements, the 22-plate reactor operated with apparent Faradaic efficiency exceeding 25 achieving near complete fuel and NO conversion at 300C in presence of up to 1.1% O{sub 2} in the feed at gas flow rates exceeding 1.3l/min. The metal catalyst dispersion was of the order of at least 15%. The novel reactor design requires only two external electrical connections and permits easy practical utilization of the electrochemical promotion of catalysis.

  2. Polarographic catalytic wave of hydrogen--Parallel catalytic hydrogen wave of bovine serum albumin in thepresence of oxidants

    Institute of Scientific and Technical Information of China (English)

    GUO; Wei(过玮); LIU; Limin(刘利民); LIN; Hong(林洪); SONG; Junfeng(宋俊峰)

    2002-01-01

    A polarographic catalytic hydrogen wave of bovine serum albumin (BSA) at about -1.80 V (vs. SCE) in NH4Cl-NH3@H2O buffer is further catalyzed by such oxidants as iodate, persulfate and hydrogen peroxide, producing a kinetic wave. Studies show that the kinetic wave is a parallel catalytic wave of hydrogen, which resulted from that hydrogen ion is electrochemically reduced and chemically regenerated through oxidation of its reduction product, atomic hydrogen, by oxidants mentioned above. It is a new type of poralographic catalytic wave of protein, which is suggested to be named as a parallel catalytic hydrogen wave.

  3. The catalytic oxidation of biomass to new materials focusing on starch, cellulose and lignin

    OpenAIRE

    Collinson, S. R.; Thielemans, W.

    2010-01-01

    Biomass is a renewable class of materials of growing interest amongst researchers aiming to achieve global sustainability. This review focuses on the homogeneous catalysis of the oxidation of biomass, in particular starch, cellulose and lignin. Often such catalytic reactions lead to depolymerisation of the material as happens in Nature with for example brown rot fungi. This depolymerisation can be desirable or not, and control in industrial applications is thus important to obtain the desired...

  4. Catalytic water oxidation by mononuclear Ru complexes with an anionic ancillary ligand.

    Science.gov (United States)

    Tong, Lianpeng; Inge, A Ken; Duan, Lele; Wang, Lei; Zou, Xiaodong; Sun, Licheng

    2013-03-01

    Mononuclear Ru-based water oxidation catalysts containing anionic ancillary ligands have shown promising catalytic efficiency and intriguing properties. However, their insolubility in water restricts a detailed mechanism investigation. In order to overcome this disadvantage, complexes [Ru(II)(bpc)(bpy)OH2](+) (1(+), bpc = 2,2'-bipyridine-6-carboxylate, bpy = 2,2'-bipyridine) and [Ru(II)(bpc)(pic)3](+) (2(+), pic = 4-picoline) were prepared and fully characterized, which features an anionic tridentate ligand and has enough solubility for spectroscopic study in water. Using Ce(IV) as an electron acceptor, both complexes are able to catalyze O2-evolving reaction with an impressive rate constant. On the basis of the electrochemical and kinetic studies, a water nucleophilic attack pathway was proposed as the dominant catalytic cycle of the catalytic water oxidation by 1(+), within which several intermediates were detected by MS. Meanwhile, an auxiliary pathway that is related to the concentration of Ce(IV) was also revealed. The effect of anionic ligand regarding catalytic water oxidation was discussed explicitly in comparison with previously reported mononuclear Ru catalysts carrying neutral tridentate ligands, for example, 2,2':6',2″-terpyridine (tpy). When 2(+) was oxidized to the trivalent state, one of its picoline ligands dissociated from the Ru center. The rate constant of picoline dissociation was evaluated from time-resolved UV-vis spectra.

  5. The superior catalytic CO oxidation capacity of a Cr-phthalocyanine porous sheet

    Science.gov (United States)

    Li, Yawei; Sun, Qiang

    2014-02-01

    Two-dimensional organometallic sheets containing regularly and separately distributed transition atoms (TMs) have received tremendous attentions due to their flexibility in synthesis, well-defined geometry and the promising applications in hydrogen storage, electronic circuits, quantum Hall effect, and spintronics. Here for the first time we present a study on the superior catalytic CO oxidation capacity of a Cr-phthalocyanine porous sheet proceeding first via Langmuir-Hinshelwood (LH) mechanism and then via Eley-Rideal (ER) mechanism. Compared to the noble metal based catalysts or graphene supported catalysts, our studied system has following unique features: without poisoning effect and clustering problem, having comparable reaction energy barrier for low-temperature oxidation, and low cost for large-scale catalytic CO oxidation in industry.

  6. Simultaneous removal of methylene blue and copper(II) ions by photoelectron catalytic oxidation using stannic oxide modified iron(III) oxide composite electrodes

    International Nuclear Information System (INIS)

    Highlights: • Photoelectron catalytic oxidation was used for methylene blue and Cu2+ removal. • SnO2/Fe2O3 was prepared and characterized for use as photoanodes and photocathodes. • Optimal reaction conditions were determined for methylene blue and Cu2+ removal. • Methylene blue removal followed the Langmuir–Freundlich–Hinshelwood kinetic model. • Cu2+ removal followed the first-order rate model. - Abstract: Stannic oxide modified Fe(III) oxide composite electrodes (SnO2/Fe2O3) were synthesized for simultaneously removing methylene blue (MB) and Cu(II) from wastewater using photoelectron catalytic oxidation (PEO). The SnO2/Fe2O3 electrodes were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and photoelectrochemical techniques. The removal of MB and Cu(II) by PEO using the SnO2/Fe2O3 composite electrodes was studied in terms of reaction time, electric current density, and pH of the electrolyte. The kinetics of the reactions were investigated using batch assays. The optimal reaction time, pH, and electric current density of the PEO process were determined to be 30 min, 6.0, and 10 mA/cm2, respectively. The removal rates of MB from wastewater treated by PEO and electron catalytic oxidation process were 84.87% and 70.64%, respectively, while the recovery rates of Cu(II) were 91.75% and 96.78%, respectively. The results suggest that PEO is an effective method for the simultaneous removal of MB and Cu(II) from wastewater, and the PEO process exhibits a much higher removal rate for MB and Cu(II) compared to the electron catalytic oxidation process. Furthermore, the removal of MB was found to follow the Langmuir–Freundlich–Hinshelwood kinetic model, whereas the removal of Cu(II) fitted well to the first-order reaction model

  7. Simulation of a fuel reforming system based on catalytic partial oxidation

    Science.gov (United States)

    Hohn, Keith L.; DuBois, Terry

    Catalytic partial oxidation (CPO) has potential for producing hydrogen that can be fed to a fuel cell for portable power generation. In order to be used for this purpose, catalytic partial oxidation must be combined with other processes, such as water-gas shift and preferential oxidation, to produce hydrogen with minimal carbon monoxide. This paper evaluates the use of catalytic partial oxidation in an integrated system for conversion of a military logistic fuel, JP-8, to high-purity hydrogen. A fuel processing system using CPO as the first processing step is simulated to understand the trade-offs involved in using CPO. The effects of water flow rate, CPO reactor temperature, carbon to oxygen ratio in the CPO reactor, temperature of preferential oxidation, oxygen to carbon ratio in the preferential oxidation reactor, and temperature for the water-gas shift reaction are evaluated. The possibility of recycling water from the fuel cell for use in fuel processing is evaluated. Finally, heat integration options are explored. A process efficiency, defined as the ratio of the lower heating value of hydrogen to that of JP-8, of around 53% is possible with a carbon to oxygen ratio of 0.7. Higher efficiencies are possible (up to 71%) when higher C/O ratios are used, provided that olefin production can be minimized in the CPO reactor.

  8. Catalytic effects of trace ruthenium on oxidation of dimethyl yellow with bromate and its application

    Institute of Scientific and Technical Information of China (English)

    ZHOU Zhi-rong; WANG Qun; ZHANG Shu-yuan

    2008-01-01

    A spectrophotometric method for the determination of ruthenium(Ⅲ) is described, based on its catalytic effect on the oxidation reaction of dimethyl yellow (DMY) with potassium bromate in an acid solution medium and in the presence of an OP emulsifier (p-iso-octyl phenoxy polyethoxy ethanol) at 100 ℃. This reaction was followed spectrophotometrically by measuring the decrease in the absorbance at 530 nm of the catalytic reaction of DMY. The calibration curve for the recommended method was linear in the concentration range over 0.0-1.0 μg/Land the detection limit of the method for Ru(Ⅲ) was 0.01 μg/L. The method is highly sensitive, selective and very stable and has been successfully applied for the determination of trace amounts of ruthenium in some ores and metallurgy products with the relative standard deviations (RSD) over 1.6%-2.8% and a recovery over 98.7%-104.0%.

  9. Application of Catalytic Wet Air Oxidation to Treatment of Landfill Leachate on Co/Bi Catalyst

    Institute of Scientific and Technical Information of China (English)

    LI Hai-sheng; LIU Liang; ZHANG Rong; DONG De-ming; LIU Hong-liang; LI Yu

    2004-01-01

    Catalytic wet air oxidation(CWAO) was employed to reduce the organic compounds in landfill leachate and the effects of temperature, oxygen pressure, catalyst dosage, and concentration of the organic compounds on the TOC and CODCr removal rates were studied. The degradation kinetics of landfill leachate was also investigated and an exponential experiential model consisting of four influential factors was established to describe the reduction of the organic compounds in the landfill leachate. Meanwhile, the GC-MS technique was used to detect the components of the organic intermediates for the inference of the decomposition mechanisms of the organic compounds in landfill leachate. The results reveal that the reaction temperature and the catalyst dosage are the most important factors affecting the degradation reaction of the organic compounds and that the principal intermediates confirmed by GC-MS are organic acids at a percentage of more than 88% with no aldehydes or alcohols detected. The decomposition mechanisms of the organic compounds in landfill leachate were inferred based on the GC-MS information as follows: the activated gas phase O2 captured the hydrogen of the organic pollutants to produce free radicals, which then initiated the catalytic reaction. So most of the organic compounds were oxidized into CO2 and H2O ultimately. In general, catalytic wet air oxidation over catalyst Co3O4/Bi2O3 was a very promising technique for the treatment of landfill leachate.

  10. Effect of hydrogen combustion reaction on the dehydrogenation of ethane in a fixed-bed catalytic membrane reactor

    Institute of Scientific and Technical Information of China (English)

    Masoud Hasany; Mohammad Malakootikhah; Vahid Rahmanian; Soheila Yaghmaei

    2015-01-01

    A two-dimensional non-isothermal mathematical model has been developed for the ethane dehydrogenation reaction in a fixed-bed catalytic membrane reactor. Since ethane dehydrogenation is an equilibrium reaction, removal of produced hydrogen by the membrane shifts the thermodynamic equilibrium to ethylene production. For further displacement of the dehydrogenation reaction, oxidative dehydrogenation method has been used. Since ethane dehydrogenation is an endothermic reaction, the energy produced by the oxidative dehydrogena-tion method is consumed by the dehydrogenation reaction. The results show that the oxidative dehydrogenation method generated a substantial improvement in the reactor performance in terms of high conversions and significant energy saving. It was also established that the sweep gas velocity in the shell side of the reactor is one of the most important factors in the effectiveness of the reactor.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-05-15

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

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

    Science.gov (United States)

    Collado, Sergio; Laca, Adriana; Díaz, Mario

    2010-05-15

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

  13. Catalytic performance of heteroatom-modified carbon nanotubes in advanced oxidation processes

    Institute of Scientific and Technical Information of China (English)

    João Restivo; Raquel P. Rocha; Adrián M. T. Silva; José J. M. Órfão; Manuel F. R. Pereira; José L. Figueiredo

    2014-01-01

    Multi-walled carbon nanotubes (CNTs) were submitted to chemical and thermal treatments in or-der to incorporate different heteroatoms on the surface. O-, S-and N-containing groups were suc-cessfully introduced onto the CNTs without significant changes of the textural properties. The cata-lytic activity of these heteroatom-modified CNTs was studied in two liquid phase oxidation pro-cesses:catalytic ozonation and catalytic wet air oxidation (CWAO), using oxalic acid and phenol as model compounds. In both cases, the presence of strongly acidic O-containing groups was found to decrease the catalytic activity of the CNTs. On the other hand, the introduction of S species (mainly sulfonic acids) enhanced the removal rate of the model compounds, particularly in the CWAO of phenol. Additional experiments were performed with a radical scavenger and sodium persulfate, in order to clarify the reaction mechanism. Nitrogen functionalities improve the catalytic performance of the original CNTs, regardless of the process or of the pollutant.

  14. How surface reparation prevents catalytic oxidation of carbon monoxide on atomic gold at defective magnesium oxide surfaces.

    Science.gov (United States)

    Töpfer, Kai; Tremblay, Jean Christophe

    2016-07-21

    In this contribution, we study using first principles the co-adsorption and catalytic behaviors of CO and O2 on a single gold atom deposited at defective magnesium oxide surfaces. Using cluster models and point charge embedding within a density functional theory framework, we simulate the CO oxidation reaction for Au1 on differently charged oxygen vacancies of MgO(001) to rationalize its experimentally observed lack of catalytic activity. Our results show that: (1) co-adsorption is weakly supported at F(0) and F(2+) defects but not at F(1+) sites, (2) electron redistribution from the F(0) vacancy via the Au1 cluster to the adsorbed molecular oxygen weakens the O2 bond, as required for a sustainable catalytic cycle, (3) a metastable carbonate intermediate can form on defects of the F(0) type, (4) only a small activation barrier exists for the highly favorable dissociation of CO2 from F(0), and (5) the moderate adsorption energy of the gold atom on the F(0) defect cannot prevent insertion of molecular oxygen inside the defect. Due to the lack of protection of the color centers, the surface becomes invariably repaired by the surrounding oxygen and the catalytic cycle is irreversibly broken in the first oxidation step. PMID:27345190

  15. Molecular studies of model surfaces of metals from single crystals to nanoparticles under catalytic reaction conditions. Evolution from prenatal and postmortem studies of catalysts.

    Science.gov (United States)

    Somorjai, Gabor A; Aliaga, Cesar

    2010-11-01

    Molecular level studies of metal crystal and nanoparticle surfaces under catalytic reaction conditions at ambient pressures during turnover were made possible by the use of instruments developed at the University of California at Berkeley. Sum frequency generation vibrational spectroscopy (SFGVS), owing to its surface specificity and sensitivity, is able to identify the vibrational features of adsorbed monolayers of molecules. We identified reaction intermediates, different from reactants and products, under reaction conditions and for multipath reactions on metal single crystals and nanoparticles of varying size and shape. The high-pressure scanning tunneling microscope (HP-STM) revealed the dynamics of a catalytically active metallic surface by detecting the mobility of the adsorbed species during catalytic turnover. It also demonstrated the reversible and adsorbate-driven surface restructuring of platinum when exposed to molecules such as CO and ethylene. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) detected the reversible changes of surface composition in rhodium-palladium, platinum-palladium, and other bimetallic nanoparticles as the reactant atmosphere changed from oxidizing to reducing. It was found that metal nanoparticles of less than 2 nm in size are present in higher oxidation states, which alters and enhances their catalytic activity. The catalytic nanodiode (CND) confirmed that a catalytic reaction-induced current flow exists at oxide-metal interfaces, which correlates well with the reaction turnover.

  16. Selective catalytic oxidation of NO over iron and manganese oxides supported on mesoporous silica

    Institute of Scientific and Technical Information of China (English)

    Junfeng Zhang; Yan Huang; Xia Chen

    2008-01-01

    The selective catalytic oxidation (SCO)of NO was studied on a catalyst consisting of iron-manganese oxide supported on mesoporous silica (MPS) with different Mn/Fe ratios.Effects of the amount of manganese and iron,oxygen,and calcination temperature on NO conversion were also investigated.It was found that the Mn-Fe/MPS catalyst with a Mn/Fe molar ratio of l showed the highest activity at the calcination temperature of 400℃.The results showed that over this catalyst,NO conversion reached 70%under the condition of 280℃ and a space velocity of 5000 h-1.SO2 and H2O had no adverse impact on the reaction activity when the SCO reaction temperature was above 240℃.In addition,the SCO activity was suppressed gradually in the presence of SO2 and H2O below 240℃.and such an effect was reversible after heating treatment.

  17. Catalytic control of diesel engine particulate emission: studies on model reactions over a EURO Pt-1 (Pt/SiO2) catalyst

    OpenAIRE

    Xue, E.; Seshan, K.; Ommen, van, B.; Ross, J.R.H.

    1993-01-01

    The catalytic oxidation of nitric oxide to nitrogen dioxide in the presence of sulphur dioxide over a standard Pt/SiO2 catalyst (EuroPt-1) was studied. The gas-phase reactions between nitric oxide, sulphur dioxide and oxygen were found to be insignificant under the experimental conditions concerned. The Pt/SiO2 catalyst was observed to be very active in catalyzing the reactions both of NO + O2 to NO2 and of SO2 + O2 to SO3. In the presence of sulphur dioxide, the catalytic activity for nitric...

  18. Visualizing the mobility of silver during catalytic soot oxidation

    DEFF Research Database (Denmark)

    Gardini, Diego; Christensen, Jakob M.; Damsgaard, Christian Danvad;

    2016-01-01

    The catalytic activity and mobility of silver nanoparticles used as catalysts in temperature programmed oxidation of soot:silver (1:5 wt:wt) mixtures have been investigated by means of flow reactor experiments and in situ environmental transmission electron microscopy (ETEM). The carbon oxidation...... temperature was significantly lower compared to uncatalyzed soot oxidation with soot and silver loosely stirred together (loose contact) and lowered further with the two components crushed together (tight contact). The in situ TEM investigations revealed that the silver particles exhibited significant...... mobility during the soot oxidation, and this mobility, which increases the soot/catalyst contact, is expected to be an important factor for the lower oxidation temperature. In the intimate tight contact mixture the initial dispersion of the silver particles is greater,,and the onset of mobility occurs...

  19. Partial catalytic oxidation of CH{sub 4} to synthesis gas for power generation - Final report

    Energy Technology Data Exchange (ETDEWEB)

    Mantzaras, I.; Schneider, A.

    2006-03-15

    The partial oxidation of methane to synthesis gas over rhodium catalysts has been investigated experimentally and numerically in the pressure range of 4 to 10 bar. The methane/oxidizer feed has been diluted with large amounts of H{sub 2}O and CO{sub 2} (up to 70% vol.) in order to simulate new power generation cycles with large exhaust gas recycle. Experiments were carried out in an optically accessible channel-flow reactor that facilitated laser-based in situ measurements, and also in a subscale gas-turbine catalytic reactor. Full-elliptic steady and transient two-dimensional numerical codes were used, which included elementary hetero-/homogeneous chemical reaction schemes. The following are the key conclusions: a) Heterogeneous (catalytic) and homogeneous (gas-phase) schemes have been validated for the partial catalytic oxidation of methane with large exhaust gas recycle. b) The impact of added H{sub 2}O and CO{sub 2} has been elucidated. The added H{sub 2}O increased the methane conversion and hydrogen selectivity, while it decreased the CO selectivity. The chemical impact of CO{sub 2} (dry reforming) was minimal. c) The numerical model reproduced the measured catalytic ignition times. It was further shown that the chemical impact of H{sub 2}O and CO{sub 2} on the catalytic ignition delay times was minimal. d) The noble metal dispersion increased with different support materials, in the order Rh/{alpha}-Al{sub 2}O{sub 3}, Rh/ZrO{sub 2}, and Rh/Ce-ZrO{sub 2}. An evident relationship was established between the noble metal dispersion and the catalytic behavior. (authors)

  20. A new process for preparing dialdehyde by catalytic oxidation of cyclic olefins with aqueous hydrogen peroxide

    Institute of Scientific and Technical Information of China (English)

    YU, Hong-Kun; PANG, Zhen; HUANG, Zu-En; CAI, Rui-Fang

    2000-01-01

    A novel peroxo-nioboplosphate was synthesized for the first time and used as a catalyst in the oxidation reaction of cyclic olefins with aqueous hydrogen peroxide to prepare dialdehydes. The catalyst was characterized by elemental analysis,thermographic analyses, IR, UV/vis, 31P NMR and XPS ~ as [ π-C5H5N(CH2)i3CH3 ]2 [Nb406 (O2)2 (PO4)2] ·6H20 (PTNP). It showed high selectivity to glutaraldehyde in the catalytic oxidation of cyclopentene with aqueous hydrogen peroxide in ethanol.

  1. Facile synthesis and excellent catalytic activity of gold nanoparticles on graphene oxide

    Institute of Scientific and Technical Information of China (English)

    Yong Qiang He; Na Na Zhang; Yu Liu; Jian Ping Gao; Mao Cong Yi; Qiao Juan Gong; Hai Xia Qiu

    2012-01-01

    For the first time,Au nanoparticles on graphene oxide (GO-AuNPs) were successfully fabricated without applying any additional reductants,just by the redox reaction between AuCl4-1 and GO.Their structure was characterized by transmission electron microscopy and X-ray powder diffraction.The results show that flower-like AuNPs were successfully dispersed on GO surface.Importantly,they showed a high catalytic activity for the Suzuki-Miyaura coupling reaction in an aqueous medium.

  2. Catalytic Partial Oxidation of Biomass/Oil Mixture

    OpenAIRE

    Veselý, V; Hanika, J. (Jiří); Tukač, V.; LEDERER, J.; Kovač, D.

    2013-01-01

    Investigation was focussed to application of waste POX (partial oxidation), e.g., meal rape in form of suspension in high boiling hydrocarbons from crude oil distillation. There is an opportunity for utilization of biomass waste resulted from fuels bio-components production. A decrease of oxygen and water steam demand in feed for POX process was observed in this variant. Catalytic effect of iron nanoparticles or nickel nitrate as catalysts in improvement of the pilot plant biomass/oil partial...

  3. Catalytic oxidation of pulping effluent by activated carbon-supported heterogeneous catalysts.

    Science.gov (United States)

    Yadav, Bholu Ram; Garg, Anurag

    2016-01-01

    The present study deals with the non-catalytic and catalytic wet oxidation (CWO) for the removal of persistent organic compounds from the pulping effluent. Two activated carbon-supported heterogeneous catalysts (Cu/Ce/AC and Cu/Mn/AC) were used for CWO after characterization by the following techniques: temperature-programmed reduction, Fourier transform infrared spectroscopy and thermo-gravimetric analysis. The oxidation reaction was performed in a batch high-pressure reactor (capacity = 0.7  L) at moderate oxidation conditions (temperature = 190°C and oxygen pressure = 0.9 MPa). With Cu/Ce/AC catalyst, the maximum chemical oxygen demand (COD), total organic carbon (TOC) and lignin removals of 79%, 77% and 88% were achieved compared to only 50% removal during the non-catalytic process. The 5-day biochemical oxygen demand (BOD5) to COD ratio (a measure for biodegradability) of the pulping effluent was improved to 0.52 from an initial value of 0.16. The mass balance calculations for solid recovered after CWO reaction showed 8% and 10% deduction in catalyst mass primarily attributed to the loss of carbon and metal leaching. After the CWO process, carbon deposition was also observed on the recovered catalyst which was responsible for around 3-4% TOC reduction. PMID:26508075

  4. Magnetic bimetallic nanoparticles supported reduced graphene oxide nanocomposite: Fabrication, characterization and catalytic capability

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lei; Wu, Tao; Xu, Xiaoyang; Xia, Fengling; Na, Heya [School of Science, Tianjin University, Tianjin 300072 (China); Liu, Yu, E-mail: liuyuls@163.com [School of Science, Tianjin University, Tianjin 300072 (China); Qiu, Haixia [School of Science, Tianjin University, Tianjin 300072 (China); Wang, Wei [School of Chemical Engineering, Tianjin University, Tianjin 300072 (China); Gao, Jianping, E-mail: jianpinggao2012@126.com [School of Science, Tianjin University, Tianjin 300072 (China)

    2015-04-15

    Highlights: • Ni and Ag nanoparticles loaded on RGO (Ni–Ag@RGO) were fabricated in a one-pot reaction. • The Ni–Ag@RGO were excellent catalysts for the reduction of 4-nitrophenol. • The Ni–Ag@RGO showed superior catalytic activity for photodegradation of methyl orange. • The Ni–Ag@RGO exhibit good reusability in a magnetic field. - Abstract: A facile method for preparing Ni–Ag bimetallic nanoparticles supported on reduced graphene oxide (Ni–Ag@RGO hybrid) has been established. Hydrazine hydrate was used as the reducing agent to reduce the graphene oxide, Ni{sup 2+} and Ag{sup +} to form Ni–Ag@RGO hybrid. The prepared hybrid was further characterized by X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy, and transmission electron microscopy. Interestingly, the prepared material shown good magnetic properties, which were determined by vibrating sample magnetometer. In addition, the Ni–Ag@RGO hybrid exhibited excellent catalytic activity for the reduction of 4-nitrophenol and the photodegradation of methyl orange. The catalytic process was monitored by determining the change in the concentration of the reactants with time using ultraviolet–visible absorption spectroscopy. After completion of the reaction, the catalyst can be separated from the reaction system simply under a magnet field and shows good recyclability.

  5. Anchoring and promotion effects of metal oxides on silica supported catalytic gold nanoparticles.

    Science.gov (United States)

    Luo, Jingjie; Ersen, Ovidiu; Chu, Wei; Dintzer, Thierry; Petit, Pierre; Petit, Corinne

    2016-11-15

    The understanding of the interactions between the different components of supported metal doped gold catalysts is of crucial importance for selecting and designing efficient gold catalysts for reactions such as CO oxidation. To progress in this direction, a unique supported nano gold catalyst Au/SS was prepared, and three doped samples (Au/SS@M) were elaborated. The samples before and after test were characterized by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). It is found that the doping metal species prefer to be located on the surface of gold nanoparticles and that a small amount of additional reductive metal leads to more efficient reaction. During the catalytic test, the nano-structure of the metal species transforms depending on its chemical nature. This study allows one to identify and address the contribution of each metal on the CO reaction in regard to oxidative species of gold, silica and dopants. Metal doping leads to different exposure of interface sites between Au and metal oxide, which is one of the key factors for the change of the catalytic activity. The metal oxides help the activation of oxygen by two actions: mobility inside the metal bulk and transfer of water species onto of gold nanoparticles.

  6. Influence of Rare Earth Doping on the Structural and Catalytic Properties of Nanostructured Tin Oxide

    Directory of Open Access Journals (Sweden)

    Maciel Adeilton

    2008-01-01

    Full Text Available AbstractNanoparticles of tin oxide, doped with Ce and Y, were prepared using the polymeric precursor method. The structural variations of the tin oxide nanoparticles were characterized by means of nitrogen physisorption, carbon dioxide chemisorption, X-ray diffraction, and X-ray photoelectron spectroscopy. The synthesized samples, undoped and doped with the rare earths, were used to promote the ethanol steam reforming reaction. The SnO2-based nanoparticles were shown to be active catalysts for the ethanol steam reforming. The surface properties, such as surface area, basicity/base strength distribution, and catalytic activity/selectivity, were influenced by the rare earth doping of SnO2and also by the annealing temperatures. Doping led to chemical and micro-structural variations at the surface of the SnO2particles. Changes in the catalytic properties of the samples, such as selectivity toward ethylene, may be ascribed to different dopings and annealing temperatures.

  7. Modelling of catalytic oxidation of NH3 and reduction of NO on limestone during sulphur capture

    DEFF Research Database (Denmark)

    Kiil, Søren; Bhatia, Suresh K.; Dam-Johansen, Kim

    1996-01-01

    A theoretical study of the complex transient system of simultaneous sulphur capture and catalytic reactions of N-containing compounds taking place on a single limestone particle is conducted. The numerical technique developed previously by the authors (Kiil et al. 1994) based on collocation...... on moving finite elements is used to solve the model equations. To our knowledge, this is the first serious attempt to model such transient systems in detail. The particle is divided into moving zones, described by the reaction between limestone and SO2, and each zone is assigned a certain catalytic...... activity with respect to each species involved. An existing particle model, the Grain-Micrograin Model, which simulates sulphur capture on limestone under oxidizing conditions is considered in the modelling. Simulation results in good qualitative agreement with experimental data are obtained here...

  8. Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions.

    Science.gov (United States)

    Collins, Gillian; Holmes, Justin D

    2016-07-01

    Recent developments in tailoring the structural and chemical properties of colloidal metal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal synthesis has also allowed tailor-made NPs to serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic and electrocatalytic applications. The engineering of future heterogenous catalysts is also moving beyond size, shape and composition considerations. Advancements in understanding structure-property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behavior of catalytic NPs. Exploiting plasmonic properties and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to the future design of catalytic NPs. PMID:26823380

  9. Supercritical carbon dioxide as an innovative reaction medium for selective oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Loeker, F.; Leitner, W. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    1998-12-31

    Although the catalytic efficiency of all catalytic oxidation processes studied in scCO{sub 2} up to now is far from being satisfactory, the principle possibility to carry out such reactions in this medium is clearly evident. Future research in our group will be directed towards the development of homogeneous and heterogeneous catalysts that are adopted to the special requirements of both the oxidation process and the supercritical reaction medium. Preliminary results from these studies regarding the epoxidation of olefins with molecular oxygen as oxidant will be presented on the conference poster. (orig.)

  10. Synthesis of propylene carbonate from urea and propylene glycol over zinc oxide: A homogeneous reaction

    Directory of Open Access Journals (Sweden)

    Dengfeng Wang

    2014-11-01

    Full Text Available In this work, several metal oxides and zinc salts were used to catalyze propylene carbonate (PC synthesis from urea and propylene glycol (PG. According to the results of catalytic test and characterization, the catalytic pattern of ZnO was different from that of other metal oxides such as CaO, MgO and La2O3, but similar to that of zinc salts. In fact, the leaching of Zn species took place during reaction for ZnO. And ZnO was found to be the precursor of homogenous catalyst for reaction of urea and PG. Thus, the relationship between the amount of dissolved zinc species and the catalytic performance of employed ZnO was revealed. In addition, a possible reaction mechanism over ZnO was discussed based on the catalytic runs and the characterization of XRD, FTIR, and element analysis.

  11. A green surfactant-assisted synthesis of hierarchical TS-1 zeolites with excellent catalytic properties for oxidative desulfurization.

    Science.gov (United States)

    Du, Shuting; Li, Fen; Sun, Qiming; Wang, Ning; Jia, Mingjun; Yu, Jihong

    2016-02-25

    Hierarchical TS-1 zeolites with uniform intracrystalline mesopores have been successfully synthesized through the hydrothermal method by using the green and cheap surfactant Triton X-100 as the mesoporous template. The resultant materials exhibit remarkably enhanced catalytic activity in oxidative desulfurization reactions compared to the conventional TS-1 zeolite. PMID:26881277

  12. Oxidation of Borneol to Camphor Using Oxone and Catalytic Sodium Chloride: A Green Experiment for the Undergraduate Organic Chemistry Laboratory

    Science.gov (United States)

    Lang, Patrick T.; Harned, Andrew M.; Wissinger, Jane E.

    2011-01-01

    A new green oxidation procedure was developed for the undergraduate organic teaching laboratories using Oxone and a catalytic quantity of sodium chloride for the conversion of borneol to camphor. This simple 1 h, room temperature reaction afforded high quality and yield of product, was environmentally friendly, and produced negligible quantities…

  13. Catalytic oxidation of volatile organic compounds (VOCs) - A review

    Science.gov (United States)

    Kamal, Muhammad Shahzad; Razzak, Shaikh A.; Hossain, Mohammad M.

    2016-09-01

    Emission of volatile organic compounds (VOCs) is one of the major contributors to air pollution. The main sources of VOCs are petroleum refineries, fuel combustions, chemical industries, decomposition in the biosphere and biomass, pharmaceutical plants, automobile industries, textile manufacturers, solvents processes, cleaning products, printing presses, insulating materials, office supplies, printers etc. The most common VOCs are halogenated compounds, aldehydes, alcohols, ketones, aromatic compounds, and ethers. High concentrations of these VOCs can cause irritations, nausea, dizziness, and headaches. Some VOCs are also carcinogenic for both humans and animals. Therefore, it is crucial to minimize the emission of VOCs. Among the available technologies, the catalytic oxidation of VOCs is the most popular because of its versatility of handling a range of organic emissions under mild operating conditions. Due to that fact, there are numerous research initiatives focused on developing advanced technologies for the catalytic destruction of VOCs. This review discusses recent developments in catalytic systems for the destruction of VOCs. Review also describes various VOCs and their sources of emission, mechanisms of catalytic destruction, the causes of catalyst deactivation, and catalyst regeneration methods.

  14. Developing soft X-ray spectroscopy for in situ characterization of nanocatalysts in catalytic reactions

    International Nuclear Information System (INIS)

    Understanding the mechanisms of catalytic and reactions calls for in situ/operando spectroscopic characterization. Here we report the developments of in situ reaction cells at the Advanced Light Source for soft X-ray spectroscopic studies of nanoparticle catalysts during the catalytic reactions. The operation of these various cells and their capabilities are illustrated with examples from the studies of Co-based nanocatalysts

  15. Skeletal Isomerization and Inter-molecular Hydrogen Transfer Reactions in Catalytic Cracking

    Institute of Scientific and Technical Information of China (English)

    Gao Yongcan; Zhang Jiushun; Xie Chaogang; Long Jun

    2002-01-01

    Bimolecular hydrogen transfer and skeletal isomerization are the important secondary reac tions among catalytic cracking reactions, which affect product yield distribution and product quality.Catalyst properties and operating parameters have great impact on bimolecular hydrogen transfer and skeletal isomerization reactions. Bimolecular hydrogen transfer activity and skeletal isomerization activity of USY-containing catalysts are higher than that of ZSM-5-containing catalyst. Coke deposition on the active sites of catalyst may suppress bimolecular hydrogen transfer activity and skeletal isomerization activity of catalyst in different degrees. Short reaction time causes a decrease of hydrogen trans fer reaction, but an increase of skeletal isomerization reaction compared to cracking reaction in catalytic cracking process.

  16. Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption - Catalytic wet air oxidation on activated carbons

    Energy Technology Data Exchange (ETDEWEB)

    Quesada-Penate, I. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Julcour-Lebigue, C., E-mail: carine.julcour@ensiacet.fr [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Jauregui-Haza, U.J. [Instituto Superior de Tecnologias y Ciencias Aplicadas, Ave. Salvador Allende y Luaces, Habana (Cuba); Wilhelm, A.M.; Delmas, H. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France)

    2012-06-30

    Highlights: Black-Right-Pointing-Pointer Three activated carbons (AC) compared as adsorbents and oxidation catalysts. Black-Right-Pointing-Pointer Similar evolution for catalytic and adsorptive properties of AC over reuses. Black-Right-Pointing-Pointer Acidic and mesoporous AC to be preferred, despite lower initial efficiency. Black-Right-Pointing-Pointer Oxidative degradation of paracetamol improves biodegradability. Black-Right-Pointing-Pointer Convenient hybrid adsorption-regenerative oxidation process for continuous treatment. - Abstract: The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties.

  17. Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

    Science.gov (United States)

    Abraham, Martin; Fisher, John W.

    1995-01-01

    The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst, prepared at The University of Tulsa, at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

  18. Sulfur recovery from low H{sub 2}S content acid gas using catalytic partial oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Clark, P.D.; Dowling, N.I.; Huang, M.

    2010-01-15

    The poster presentation discussed a new strategy for recovering sulfur from low hydrogen-sulphide-content acid gas using catalytic partial oxidation. In a new technology for dealing with BTX-contaminated lean acid gas, a catalytic reactor replaces the burner-furnace stage to achieve BTX conversion greater than 95 percent and control the hydrogen sulfide/sulfur dioxide ratio. The product gas is then sent to the Claus catalytic converters. The best catalysts for this process are alumina-supported Co-Mo and y-alumina. This process was compared with SELECTOX, another process that deals with poor acid gas with BTX conversion better than 95 percent. Catalytic oxidation can deal with a higher BTX feed content than SELECTOX, but the running temperature is higher. Both processes produce acceptable sulfur quality. To improve this process, the quality of the sulfur produced and the lifetime of the catalyst need to be increased, and an economic way to increase the heat to reach the running temperature needs to be found. The partial oxidation (POX) of CH{sub 4} solves both of these problems. The catalytic POX of acid gas is combined with the POX of fuel gas in the pre-heating zone. This process has the advantage that the burner-furnace stage of the Claus process can be replaced by a stream containing H{sub 2}S/SO{sub 2}=2; the reaction is performed at its adiabatic temperature requiring only a small amount of fuel gas; the presence of H{sub 2} and CO produced by the POX of fuel gas improves the quality of sulfur; the catalyst remains active for about 30 hours; and the process can tolerate high BTX content. 6 tabs., 2 figs.

  19. Uranium oxidation: characterization of oxides formed by reaction with water

    International Nuclear Information System (INIS)

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

  20. Synthesis and characterization of Cr-MSU-1 and its catalytic application for oxidation of styrene

    Science.gov (United States)

    Liu, Hong; Wang, Zhigang; Hu, Hongjiu; Liang, Yuguang; Wang, Mengyang

    2009-07-01

    Chromium-containing mesoporous silica material Cr-MSU-1 was synthesized using lauryl alcohol-polyoxyethylene (23) ether as templating agent under the neutral pH condition by two-step method. The sample was characterized by XRD, TEM, FT-IR, UV-Vis, ESR, ICP-AES and N 2 adsorption. Its catalytic performance for oxidation of styrene was studied. Effects of the solvent used, the styrene/H 2O 2 mole ratio and the reaction temperature and time on the oxidation of styrene over the Cr-MSU-1 catalyst were examined. The results indicate that Cr ions have been successfully incorporated into the framework of MSU-1 and the Cr-MSU-1 material has a uniform worm-like holes mesoporous structure. After Cr-MSU-1 is calcined, most of Cr 3+ is oxidized to Cr 5+ and Cr 6+ in tetrahedral coordination and no extra-framework Cr 2O 3 is formed. The Cr-MSU-1 catalyst is highly active for the selective oxidation of styrene and the main reaction products over Cr-MSU-1 are benzaldehyde and phenylacetaldehyde. Its catalytic performance remains stable within five repeated runs and no leaching is noticed for this chromium-based catalyst.

  1. Heterogeneous catalytic oxidation of As(III) on nonferrous metal oxides in the presence of H2O2.

    Science.gov (United States)

    Kim, Dong-hyo; Bokare, Alok D; Koo, Min suk; Choi, Wonyong

    2015-03-17

    The oxidation of As(III) (arsenite) to As(V) (arsenate), a critical pretreatment process for total arsenic removal, is easily achieved using chemical oxidation methods. Hydrogen peroxide (H2O2) is widely used as an environmentally benign oxidant but its practical use for the arsenite oxidation is limited by the strong pH dependence and slow oxidation kinetics. This study demonstrated that H2O2-induced oxidation of As(III) can be markedly enhanced in the presence of nonferrous metal oxides (e.g., WO3, TiO2, ZrO2) as a heterogeneous catalyst working over a wide pH range in ambient reaction conditions. In particular, TiO2 is an ideal catalyst because it is not only active and stable but also easily available and inexpensive. Although the photocatalytic oxidation of As(III) on TiO2 was intensively studied, the thermal catalytic activities of TiO2 and other nonferrous metal oxides for the arsenic oxidation have been little investigated. The heterogeneous oxidation rate increased with increasing the TiO2 surface area and [H2O2] and weakly depended on pH whereas the homogeneous oxidation by H2O2 alone was favored only at alkaline condition. The oxidation rate in the TiO2/H2O2 system was not reduced at all in the absence of dioxygen. It was not retarded at all by OH radical scavengers but markedly inhibited by hydroperoxyl radical scavengers. It is proposed that the surface complexation of H2O2 on TiO2 induces the generation of the surface hydroperoxyl radical through an inner-sphere electron transfer, which subsequently reacts with As(III). The catalytic activity of TiO2 was maintained without showing any sign of deactivation. The heterogeneous catalytic oxidation is proposed as a viable method for the preoxidation treatment of As(III)-contaminated water under ambient conditions. PMID:25695481

  2. Molybdatophosphoric acid as an efficient catalyst for the catalytic and chemoselective oxidation of sulfides to sulfoxides using urea hydrogen peroxide as a commercially available oxidant

    Directory of Open Access Journals (Sweden)

    ALIREZA HASANINEJAD

    2010-03-01

    Full Text Available An efficient procedure for the chemoselective oxidation of alkyl (aryl sulfides to the corresponding sulfoxides using urea hydrogen peroxide (UHP in the presence of a catalytic amount of molybdatophosphoric acid at room temperature is described. The advantages of described method are: generality, high yield and chemoselectivity, short reaction time, low cost and compliment with green chemistry protocols.

  3. Structure and Catalytic Behavior of CuO-ZrO-CeO2 Mixed Oxides

    Institute of Scientific and Technical Information of China (English)

    王恩过; 陈诵英

    2002-01-01

    The effect of doping CuO on the structure and properties of zirconia-ceria mixed oxide was studied. The results show that addition of CuO decreases the reduction temperature of ceria, and stabilizes the cubic structure of mixed oxides, and enhances catalytic activity of CuO-ZrO-CeO2 mixed oxides for CO oxidation. Increasing ceria content in the mixed oxides can enhance the catalytic activity, but some impurities such as sulfate make catalytic activity falling. There is little effect of calcination temperature on catalytic activities, implying that these catalysts are effective with good thermal stability.

  4. Highly n-Type Titanium Oxide as an Electronically Active Support for Platinum in the Catalytic Oxidation of Carbon Monoxide

    KAUST Repository

    Baker, L. Robert

    2011-08-18

    The role of the oxide-metal interface in determining the activity and selectivity of chemical reactions catalyzed by metal particles on an oxide support is an important topic in science and industry. A proposed mechanism for this strong metal-support interaction is electronic activation of surface adsorbates by charge carriers. Motivated by the goal of using electronic activation to drive nonthermal chemistry, we investigated the ability of the oxide support to mediate charge transfer. We report an approximately 2-fold increase in the turnover rate of catalytic carbon monoxide oxidation on platinum nanoparticles supported on stoichiometric titanium dioxide (TiO2) when the TiO2 is made highly n-type by fluorine (F) doping. However, for nonstoichiometric titanium oxide (TiOX<2) the effect of F on the turnover rate is negligible. Studies of the titanium oxide electronic structure show that the energy of free electrons in the oxide determines the rate of reaction. These results suggest that highly n-type TiO2 electronically activates adsorbed oxygen (O) by electron spillover to form an active O- intermediate. © 2011 American Chemical Society.

  5. Flame Synthesis of Composite Oxides for Catalytic Applications

    DEFF Research Database (Denmark)

    Jensen, Joakim Reimer

    2002-01-01

    The scope of this work is to investigate flame synthesis of oxides and oxide composites for catalytic applications. Vaporized acetylcetonate precursors are combusted in a flame leading to the formation of metal oxides with high specific surface areas. The employed flame setup is a premixed flat...... the flame temperature, the high temperature residence time and the precursor concentration. The Cu/ZnO/Al2O3 methanol catalyst is used as a model system for the preparation of catalytic materials. The flame synthesized catalyst exhibits a high and reproducible activity for methanol formation from synthesis...... gas (CO/CO2/H2) and an excellent thermal stability. Addition of alumina as a structural promoter is necessary in order to obtain a high activity for methanol formation. The binary systems, i.e., CuO/ZnO, ZnO/Al2O3 and CuO/Al2O3 are investigated as a prelude to the preparation of the ternary catalyst...

  6. Catalytic reactor for promoting a chemical reaction on a fluid passing therethrough

    Science.gov (United States)

    Roychoudhury, Subir (Inventor); Pfefferle, William C. (Inventor)

    2001-01-01

    A catalytic reactor with an auxiliary heating structure for raising the temperature of a fluid passing therethrough whereby the catalytic reaction is promoted. The invention is a apparatus employing multiple electrical heating elements electrically isolated from one another by insulators that are an integral part of the flow path. The invention provides step heating of a fluid as the fluid passes through the reactor.

  7. SpaciMS: spatial and temporal operando resolution of reactions within catalytic monoliths

    Energy Technology Data Exchange (ETDEWEB)

    Sa, Jacinto [Queen' s University, Belfast; Fernandes, Daniel [University of Aveiro, Portugal; Aiouache, Farid [Queen' s University, Belfast; Goguet, Alexandre [Queen' s University, Belfast; Hardacdre, Christopher [Queen' s University, Belfast; Lundie, David [Hiden Analytical Ltd; Naeem, Wasif [Queen' s University, Belfast; Partridge Jr, William P [ORNL; Stere, Cristina [Queen' s University, Belfast

    2010-01-01

    Monolithic catalysts are widely used as structured catalysts, especially in the abatement of pollutants. Probing what happens inside these monoliths during operation is, therefore, vital for modelling and prediction of the catalyst behavior. SpaciMS is a spatially resolved capillary-inlet mass spectroscopy system allowing for the generation of spatially resolved maps of the reactions within monoliths. In this study SpaciMS results combined with 3D CFD modelling demonstrate that SpaciMS is a highly sensitive and minimally invasive technique that can provide reaction maps as well as catalytic temporal behavior. Herein we illustrate this by examining kinetic oscillations during a CO oxidation reaction over a Pt/Rh on alumina catalyst supported on a cordierite monolith. These oscillations were only observed within the monolith by SpaciMS between 30 and 90% CO conversion. Equivalent experiments performed in a plug-flow reactor using this catalyst in a crushed form over a similar range of reaction conditions did not display any oscillations demonstrating the importance of intra monolith analysis. This work demonstrates that the SpaciMS offers an accurate and comprehensive picture of structured catalysts under operation.

  8. Reactions of oxidation of plutonium metal

    International Nuclear Information System (INIS)

    The investigation into preparation of the powdery plutonium oxides under the reaction of metal plutonium with moist (5 % H2O) air and moist (5 % H2O) argon was carried out. The kinetic dependences in the 250 - 400 Deg C range are demonstrated. The vicissitude of the oxidation is shown, the activation energy is calculated for every stage. The mechanism of the metal plutonium oxidation is proposed. The obtained plutonium oxides were shown to have a high reaction ability at 300 - 400 Deg C in the moist air and moist argon media, and to be feasible for the further chemical treatment - dissolving in nitric acid, fluorination and chlorination

  9. The plausible role of carbonate in photo-catalytic water oxidation processes.

    Science.gov (United States)

    Kornweitz, Haya; Meyerstein, Dan

    2016-04-28

    DFT calculations point out that the photo-oxidation of water on GaN is energetically considerably facilitated by adsorbed carbonate. As the redox potential of the couple CO3(˙-)/CO3(2-) is considerably lower than that of the couple OH˙/OH(-) but still enables the oxidation of water it is suggested that carbonate should be considered as a catalyst/co-catalyst in a variety of catalytic/photo-catalytic/electro-catalytic oxidation processes.

  10. Synthesis of propylene carbonate from urea and propylene glycol over zinc oxide: A homogeneous reaction

    OpenAIRE

    Dengfeng Wang; Xuelan Zhang; Tingting Cheng; Jing Wu; Qijun Xue

    2014-01-01

    In this work, several metal oxides and zinc salts were used to catalyze propylene carbonate (PC) synthesis from urea and propylene glycol (PG). According to the results of catalytic test and characterization, the catalytic pattern of ZnO was different from that of other metal oxides such as CaO, MgO and La2O3, but similar to that of zinc salts. In fact, the leaching of Zn species took place during reaction for ZnO. And ZnO was found to be the precursor of homogenous catalyst for reaction of u...

  11. Catalytic properties of Cu/Co/Zn/Zr oxides prepared by various methods

    Institute of Scientific and Technical Information of China (English)

    Limin Shi; Wei Chu; Siyu Deng; Huiyuan Xu

    2008-01-01

    The new Cu-Co based (Cu/Co/Zn/Zr) catalysts for higher-alcohol synthesis were prepared using coprecipitation method, plasma enhanced method and reverse coprecipitation method under ultrasound irradiation. The catalysts were investi-gated by the means of BET, SEM, XRD, H2-TPR and XPS. Catalytic properties of the catalysts prepared by various methods were examined using CO hydrogenation reaction. It was found that plasma enhanced method and reverse coprecipitation method under ultrasound irradiation were both effective in enhancing the catalytic properties of Cu/Co/Zn/Zr mixed oxides. The small particle size, high dispersion of active components, the improvement of specific surface area and surface contents of active phases could account for the excellent performance of the experimental Cu/Co/Zn/Zr catalysts.

  12. Influence of Supports on Catalytic Performance and Carbon Deposition of Palladium Catalyst for Methane Partial Oxidation

    Institute of Scientific and Technical Information of China (English)

    Shi Fangli; Shen Meiqing; Fei Yanan; Wang Jun; Weng Duan

    2007-01-01

    The catalytic performance of methane partial oxidation was investigated on Pd/CeO2-ZrO2 and Pd/α-Al2O3 catalysts. The catalysts were characterized by XRD, Raman spectra, and TG-DTA techniques. The results show that CeO2-ZrO2 support is more advantageous for the catalytic activity and stability of catalysts compared to α-Al2O3. TG-DTA and Raman spectra results indicated that carbon deposited on the catalysts was in the form of graphite, which is the main reason for the deactivation of catalysts after a 24-hour reaction. Moreover, CeO2-ZrO2 had positive effect on inhibiting carbon deposition.

  13. Communication: Towards catalytic nitric oxide reduction via oligomerization on boron doped graphene

    Science.gov (United States)

    Cantatore, Valentina; Panas, Itai

    2016-04-01

    We use density functional theory to describe a novel way for metal free catalytic reduction of nitric oxide NO utilizing boron doped graphene. The present study is based on the observation that boron doped graphene and O—N=N—O- act as Lewis acid-base pair allowing the graphene surface to act as a catalyst. The process implies electron assisted N=N bond formation prior to N—O dissociation. Two N2 + O2 product channels, one of which favoring N2O formation, are envisaged as outcome of the catalytic process. Besides, we show also that the N2 + O2 formation pathways are contrasted by a side reaction that brings to N3O3- formation and decomposition into N2O + NO2-.

  14. Green synthesis of silver nanoparticles, decorated on graphene oxide nanosheets and their catalytic activity

    Science.gov (United States)

    Sreekanth, T. V. M.; Jung, Min-Ji; Eom, In-Yong

    2016-01-01

    In this study, we develop an inexpensive and green route for the synthesis of silver nanoparticles (AgNPs) using Picrasma quassioides bark aqueous extract as reducing and capping agent and also eco-friendly decorate graphene oxide (GO) nanosheets with AgNPs (GO-AgNPs). Green synthesized AgNPs and GO-AgNPs composites were characterized by UV-Visible spectroscopy, SEM-EDX, and TEM-SAED techniques. The resulting GO-AgNPs contained about 41.35% of Ag and the AgNPs size ranges 17.5-66.5 nm, and GO-AgNPs size ranges 10-49.5 nm. Moreover, the GO-AgNPs exhibited excellent catalytic activity towards the methylene blue (MB) in the presence of sodium borohydride (NaBH4) at room temperature. This catalytic reaction completed within 15 min.

  15. A general catalytic reaction sequence to access alkaloid-inspired indole polycycles.

    Science.gov (United States)

    Danda, Adithi; Kumar, Kamal; Waldmann, Herbert

    2015-05-01

    A catalytic two-step reaction sequence was developed to access a range of complex heterocyclic frameworks based on biorelevant indole/oxindole scaffolds. The reaction sequence includes catalytic Pictet-Spengler cyclization followed by Au(I) catalyzed intramolecular hydroamination of acetylenes. A related cascade polycyclization of a designed β-carboline embodying a 1,5-enyne group yields the analogues of the alkaloid harmicine. PMID:25846800

  16. Acid Separation, Catalytic Oxidation and Coagulation for ATC Waste Liquid Treatment

    Institute of Scientific and Technical Information of China (English)

    DING Xiaoling; JIA Chunning

    2005-01-01

    It is difficult to treat 2-amino-thiazoline-4-carboxylic acid (ATC) waste liquid effectively at present for its characteristics of high chemical oxygen demand (COD), high salinity and low biodegradability. In order to solve this problem, this paper presents several kinds of physical-chemical treatment unit techniques, including acid separation, catalytic oxidation and coagulation. First of all, acid separation was adopted to precipitate relevant organics at isoelectric point. When the temperature and pH value of acid separation were controlled at about 5 ℃ and 2.2 respectively, the COD removal rate could reach 27.6%. Secondly, oxidation was used to break chemical constitution of refractory organics. The optimal reaction parameters of catalytic oxidation should be 20 ℃, pH adjusted to 5.0 and [Fe2+] 300 mg/L. Then with 5% H 2O 2 added and after one-hour reaction, the COD removal rate could achieve about 52%. Finally, coagulation was adopted to remove a portion of refractory organics, and 15% polymeric molysite flocculant was the best for the coagulation, and the COD removal rate could reach about 15%. Therefore, the proposed feasible process of physical-chemical pretreatment for ATC waste liquid could have about 70% COD removed in total.

  17. Oscillations, period doublings, and chaos in CO oxidation and catalytic mufflers.

    Science.gov (United States)

    Marek, Milos; Schejbal, Matyás; Kocí, Petr; Nevoral, Vladislav; Kubícek, Milan; Hadac, Otto; Schreiber, Igor

    2006-09-01

    Early experimental observations of chaotic behavior arising via the period-doubling route for the CO catalytic oxidation both on Pt(110) and Ptgamma-Al(2)O(3) porous catalyst were reported more than 15 years ago. Recently, a detailed kinetic reaction scheme including over 20 reaction steps was proposed for the catalytic CO oxidation, NO(x) reduction, and hydrocarbon oxidation taking place in a three-way catalyst (TWC) converter, the most common reactor for detoxification of automobile exhaust gases. This reactor is typically operated with periodic variation of inlet oxygen concentration. For an unforced lumped model, we report results of the stoichiometric network analysis of a CO reaction subnetwork determining feedback loops, which cause the oscillations within certain regions of parameters in bifurcation diagrams constructed by numerical continuation techniques. For a forced system, numerical simulations of the CO oxidation reveal the existence of a period-doubling route to chaos. The dependence of the rotation number on the amplitude and period of forcing shows a typical bifurcation structure of Arnold tongues ordered according to Farey sequences, and positive Lyapunov exponents for sufficiently large forcing amplitudes indicate the presence of chaotic dynamics. Multiple periodic and aperiodic time courses of outlet concentrations were also found in simulations using the lumped model with the full TWC kinetics. Numerical solutions of the distributed model in two geometric coordinates with the CO oxidation subnetwork consisting of several tens of nonlinear partial differential equations show oscillations of the outlet reactor concentrations and, in the presence of forcing, multiple periodic and aperiodic oscillations. Spatiotemporal concentration patterns illustrate the complexity of processes within the reactor. PMID:17014241

  18. Catalytic ozonation of sulfosalicylic acid over manganese oxide supported on mesoporous ceria.

    Science.gov (United States)

    Xing, Shengtao; Lu, Xiaoyang; Liu, Jia; Zhu, Lin; Ma, Zichuan; Wu, Yinsu

    2016-02-01

    Manganese oxide supported on mesoporous ceria was prepared and used as catalyst for catalytic ozonation of sulfosalicylic acid (SA). Characterization results indicated that the manganese oxide was mostly incorporated into the pores of ceria. The synthesized catalyst exhibited high activity and stability for the mineralization of SA in aqueous solution by ozone, and more than 95% of total organic carbon was removed in 30 min under various conditions. Mechanism studies indicated that SA was mainly degraded by ozone molecules, and hydroxyl radical reaction played an important role for the degradation of its ozonation products (small molecular organic acids). The manganese oxide in the pores of CeO2 improved the adsorption of small molecular organic acids and the generation of hydroxyl radicals from ozone decomposition, resulting in high TOC removal efficiency.

  19. Metallo-deuteroporphyrin as a biomimetic catalyst for the catalytic oxidation of lignin to aromatics.

    Science.gov (United States)

    Zhu, Chenjie; Ding, Weiwei; Shen, Tao; Tang, Chenglun; Sun, Chenguo; Xu, Shichao; Chen, Yong; Wu, Jinglan; Ying, Hanjie

    2015-05-22

    A series of metallo-deuteroporphyrins derived from hemin were prepared as models of the cytochrome P450 enzyme. With the aid of the highly active Co(II) deuteroporphyrin complex, the catalytic oxidation system was applied for the oxidation of several lignin model compounds, and high yields of monomeric products were obtained under mild reaction conditions. It was found that the modified cobalt deuteroporphyrin that has no substituents at the meso sites but does have the disulfide linkage in the propionate side chains at the β sites exhibited much higher activity and stability than the synthetic tetraphenylporphyrin. The changes in the propionate side chains can divert the reactivity of cobalt deuteroporphyrins from the typical CC bond cleavage to CO bond cleavage. Furthermore, this novel oxidative system can convert enzymolysis lignin into depolymerized products including a significant portion of well-defined aromatic monomers.

  20. Electro-catalytic effect of manganese oxide on oxygen reduction at teflonbonded carbon electrode

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Oxygen reduction(OR)on Teflon-bonded carbon electrodes with manganese oxide as catalyst in 6 mol/L KOH solution was investigated using AC impedance spectroscopy combined with other techniques. For OR at this electrode, the Tafel slope is-0.084V/dec and the apparent exchange current density is (1.02-3.0)×10-7 A/cm2. In the presence of manganese oxide on carbon electrode,the couple Mn3+/Mn4+ reacts with the O2 adsorbed on carbon sites forming O2- radicals and acceletes the dismutation of O2-, which contributes to the catalytic effect of manganese oxide for OR reaction.

  1. Removal of formaldehyde over MnxCe1-xO2 catalysts: Thermal catalytic oxidation versus ozone catalytic oxidation

    Institute of Scientific and Technical Information of China (English)

    Jia Wei Li; Kuan Lun Pan; Sheng Jen Yu; Shaw Yi Yan; Moo Been Chang

    2014-01-01

    MnxCe1-xO2 (x:0.3-0.9) prepared by Pechini method was used as a catalyst for the thermal catalytic oxidation of formaldehyde (HCHO).At x =0.3 and 0.5,most of the manganese was incorporated in the fluorite structure of CeO2 to form a solid solution.The catalytic activity was best at x =0.5,at which the temperature of 100% removal rate is the lowest (270℃).The temperature for 100% removal of HCHO oxidation is reduced by approximately 40℃ by loading 5 wt.% CuOx into Mn0.5Ce0.5O2.With ozone catalytic oxidation,HCHO (61 ppm) in gas stream was completely oxidized by adding 506 ppm O3 over Mn0.5Ce0.5O2 catalyst with a GHSV (gas hourly space velocity) of 10,000 hr-1 at 25℃.The effect of the molar ratio of O3 to HCHO was also investigated.As O3/HCHO ratio was increased from 3 to 8,the removal efficiency of HCHO was increased from 83.3% to 100%.With O3/HCHO ratio of 8,the mineralization efficiency of HCHO to CO2 was 86.1%.At 25℃,the p-type oxide semiconductor (Mn0.5Ce0.5O2) exhibited an excellent ozone decomposition efficiency of 99.2%,which significantly exceeded that of n-type oxide semiconductors such as TiO2,which had a low ozone decomposition efficiency (9.81%).At a GHSV of 10,000 hr-1,[O3]/[HCHO] =3 and temperature of 25℃,a high HCHO removal efficiency (≥81.2%) was maintained throughout the durability test of 80 hr,indicating the long-term stability of the catalyst for HCHO removal.

  2. In situ generation of electron acceptor for photoelectrochemical biosensing via hemin-mediated catalytic reaction.

    Science.gov (United States)

    Zang, Yang; Lei, Jianping; Zhang, Lei; Ju, Huangxian

    2014-12-16

    A novel photoelectrochemical sensing strategy is designed for DNA detection on the basis of in situ generation of an electron acceptor via the catalytic reaction of hemin toward H2O2. The photoelectrochemical platform was established by sequential assembly of near-infrared CdTe quantum dots, capture DNA, and a hemin-labeled DNA probe to form a triple-helix molecular beacon (THMB) structure on an indium tin oxide electrode. According to the highly catalytic capacity of hemin toward H2O2, a photoelectrochemical mechanism was then proposed, in which the electron acceptor of O2 was in situ-generated on the electrode surface, leading to the enhancement of the photocurrent response. The utilization of CdTe QDs can extend the absorption edge to the near-infrared band, resulting in an increase in the light-to-electricity efficiency. After introducing target DNA, the THMB structure is disassembled and releases hemin and, thus, quenches the photocurrent. Under optimized conditions, this biosensor shows high sensitivity with a linear range from 1 to 1000 pM and detection limit of 0.8 pM. Moreover, it exhibits good performance of excellent selectivity, high stability, and acceptable fabrication reproducibility. This present strategy opens an alternative avenue for photoelectrochemical signal transduction and expands the applications of hemin-based materials in photoelectrochemical biosensing and clinical diagnosis. PMID:25393151

  3. Kinetic and catalytic performance of a BI-porous composite material in catalytic cracking and isomerisation reactions

    KAUST Repository

    Al-Khattaf, S.

    2012-01-10

    Catalytic behaviour of pure zeolite ZSM-5 and a bi-porous composite material (BCM) were investigated in transformation of m-xylene, while zeolite HY and the bi-porous composite were used in the cracking of 1,3,5-triisopropylbenzene (TIPB). The micro/mesoporous material was used to understand the effect of the presence of mesopores on these reactions. Various characterisation techniques, that is, XRD, SEM, TGA, FT-IR and nitrogen sorption measurements were applied for complete characterisation of the catalysts. Catalytic tests using CREC riser simulator showed that the micro/mesoporous composite catalyst exhibited higher catalytic activity as compared with the conventional microporous ZSM-5 and HY zeolite for transformation of m-xylene and for the catalytic cracking of TIPB, respectively. The outstanding catalytic reactivity of m-xylene and TIPB molecules were mainly attributed to the easier access of active sites provided by the mesopores. Apparent activation energies for the disappearance of m-xylene and TIPB over all catalysts were found to decrease in the order: EBCM>EZSM-5 and EBCM>EHY, respectively. © 2012 Canadian Society for Chemical Engineering.

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

    Directory of Open Access Journals (Sweden)

    Seiki eWada

    2013-06-01

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

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

    Science.gov (United States)

    Wada, Seiki; Oka, Kazuki; Watanabe, Kentaro; Izumi, Yasuo

    2013-06-01

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

  6. Precipitation of antimony from the solution of sodium thioantimonite by air oxidation in the presence of catalytic agents

    Institute of Scientific and Technical Information of China (English)

    杨天足; 赖琼琳; 唐建军; 楚广

    2002-01-01

    The behavior of antimony oxidation in the solution of sodium thioantimonite was studied in the presence of catalytic agents. The catalytic effects of the respective addition of cupric sulfate, sodium tartrate, potassium permanganate, phenol, 1,2-dihydroxybenzene and their combination on the oxidation of sodium thioantimonite were investigated. A pilot test was carried out. The results show that the respective use of sodium tartrate, cupric sulfate, potassium permanganate, phenol and 1,2-dihydroxybenzene have little catalytic effect on the oxidation of sodium thioantimonite. However there exists obvious catalytic oxidation by the combination of 0.25 g/L 1,2-dihydroxybenzene, 0.5 g/L potassium permanganate and 1.0 g/L phenol. Moreover, high blast intensity, the increase of temperature and NaOH concentration favor the oxidation of antimony. The oxidation process of antimony has such advantages as quick reaction and low operation costs. The results of the pilot test are consistent with those of laboratory experiments.

  7. Catalytic ignition of light hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    K. L. Hohn; C.-C. Huang; C. Cao

    2009-01-01

    Catalytic ignition refers to phenomenon where sufficient energy is released from a catalytic reaction to maintain further reaction without additional extemai heating. This phenomenon is important in the development of catalytic combustion and catalytic partial oxidation processes, both of which have received extensive attention in recent years. In addition, catalytic ignition studies provide experimental data which can be used to test theoretical hydrocarbon oxidation models. For these reasons, catalytic ignition has been frequently studied. This review summarizes the experimental methods used to study catalytic ignition of light hydrocarbons and describes the experimental and theoretical results obtained related to catalytic ignition. The role of catalyst metal, fuel and fuel concentration, and catalyst state in catalytic ignition are examined, and some conclusions are drawn on the mechanism of catalytic ignition.

  8. Accelerated Catalytic Fenton Reaction with Traces of Iron: An Fe-Pd-Multicatalysis Approach.

    Science.gov (United States)

    Georgi, Anett; Velasco Polo, Miriam; Crincoli, Klara; Mackenzie, Katrin; Kopinke, Frank-Dieter

    2016-06-01

    An accelerated catalytic Fenton (ACF) reaction was developed based upon a multicatalysis approach, facilitating efficient contaminant oxidation at trace levels of dissolved iron. Beside the Fe(II)/H2O2 catalyst/oxidant pair for production of OH-radicals, the ACF system contains Pd/H2 as catalyst/reductant pair for fast reduction of Fe(III) back to Fe(II) which accelerates the Fenton cycle and leads to faster contaminant degradation. By this means, the concentration of the dissolved iron catalyst can be reduced to trace levels (1 mg L(-1)) below common discharge limits, thus eliminating the need for iron sludge removal, which is one of the major drawbacks of conventional Fenton processes. ACF provides fast degradation of the model contaminant methyl tert-butyl ether (MTBE, C0 = 0.17 mM) with a half-life of 11 min with 1 mg L(-1) dissolved iron, 500 mg L(-1) H2O2, 5 mg L(-1) Pd (as suspended Pd/Al2O3 catalyst) and 0.1 MPa H2, pH 3. The effects of pH, H2 partial pressure and H2O2 concentration on MTBE degradation rates were studied. Results on kinetic deuterium isotope effect and quenching studies are in conformity with OH-radicals as main oxidant. The heterogeneous Pd/Al2O3 catalyst was reused within six cycles without significant loss in activity. PMID:27167833

  9. A PROCESS FOR THE CATALYTIC OXIDATION OF HYDROCARBONS

    DEFF Research Database (Denmark)

    1999-01-01

    A process for producing an alcohol from a gaseous hydrocarbon, e.g. a lower alkane such as methane, via oxidative reaction of the hydrocarbon in a concentrated sulfuric acid medium in the presence of a catalyst employs an added catalyst comprising a substance selected from iodine, iodine compounds...

  10. Catalytic oxidation of calcium sulfite in solution/aqueous slurry

    Institute of Scientific and Technical Information of China (English)

    WU Xiao-qin; WU Zhong-biao; WANG Da-hui

    2004-01-01

    Forced oxidation of calcium sulfite aqueous slurry is a key step for the calcium-based flue gas desulfurization(FGD) residue. Experiments were conducted in a semi-batch system and a continuous flow system on lab scales. The main reactor in semi-batch system is a 1000 ml volume flask. It has five necks for continuous feeding of gas and a batch of calcium sulfite solution/aqueous slurry. In continuous flow system, the main part is a jacketed Pyrex glass reactor in which gas and solution/aqueous slurry are fed continuously. Calcium sulfite oxidation is a series of complex free-radical reactions. According to experimental results and literature data, the reactions are influenced significantly by manganese as catalyst. At low concentration of manganese and calcium sulfite, the reaction rate is dependent on 1.5 order of sulfite concentration, 0.5 order of manganese concentration, and zero order of oxygen concentration in which the oxidation is controlled by chemical kinetics. With concentrations of calcium sulfite and manganese increasing, the reactions are independent gradually on the constituents in solution but are impacted by oxygen concentration. Manganese can accelerate the free-radical reactions, and then enhances the mass transfer of oxygen from gas to liquid. The critical concentration of calcium sulfite is 0.007 mol/L, manganese is 10-4 mol/L, and oxygen is of 0.2-0.4 atm.

  11. Catalytic performance of Fe-ZSM-5 catalysts for selective catalytic reduction of nitric oxide by ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Long, R.Q.; Yang, R.T.

    1999-12-10

    A series of Fe-exchanged molecular sieves were studied as catalysts for the selective catalytic reduction (SCR) of NO with ammonia. It was found that Fe-ZSM-5 and Fe-mordenite catalysts were highly active for the SCR reaction. Nearly 100% NO conversions were obtained at 400--500 C under conditions with a high space velocity (GHSV = 4.6 x 10{sup 5} 1/h). However, Fe-Y and Fe-MCM-41 with larger pore sizes showed lower activities for this reaction. F or Fe-ZSM-5 catalysts, the SCR activity decreased with increasing Si/Al ratio in the zeolites. As the Fe-exchange level in the Fe-ZSM-5 catalysts was increased from 58 to 252%, NO conversion increased at lower temperatures (e.g., 300 C), but decreased at high temperatures (e.g., 600 C). Compared with the commercial vanadia catalyst, based on the first-order rate constants, the Fe-ZSM-5 catalyst was five times more active at 400 C and seven times more active at 450 C. It also functioned in a broader temperature window, produced only N{sub 2} (rather than N{sub 2}O) and H{sub 2}O, and showed a substantially lower activity for oxidation of SO{sub 2} to SO{sub 3}.

  12. Catalytic Chan–Lam coupling using a ‘tube-in-tube’ reactor to deliver molecular oxygen as an oxidant

    Science.gov (United States)

    Mallia, Carl J; Burton, Paul M; Smith, Alexander M R; Walter, Gary C

    2016-01-01

    Summary A flow system to perform Chan–Lam coupling reactions of various amines and arylboronic acids has been realised employing molecular oxygen as an oxidant for the re-oxidation of the copper catalyst enabling a catalytic process. A tube-in-tube gas reactor has been used to simplify the delivery of the oxygen accelerating the optimisation phase and allowing easy access to elevated pressures. A small exemplification library of heteroaromatic products has been prepared and the process has been shown to be robust over extended reaction times. PMID:27559412

  13. Catalytic Behavior of CO Oxidization over Pd/ZrO2 - CeO2 Catalyst

    Institute of Scientific and Technical Information of China (English)

    Wang Enguo; Mei Fang

    2004-01-01

    The effects of Pd loading, cerium content, the special surface area of the support and calcination temperature on the catalytic properties of Pd-loaded zirconia-ceria mixed oxide were studied.The results show that loading Pd and increasing cerium content in the mixed oxides can enhance the catalytic activity.There is a little effect of calcination temperature on catalytic activities, implying that these catalysts are effective with good thermal stability.

  14. Catalytic properties and biomedical applications of cerium oxide nanoparticles

    KAUST Repository

    Walkey, Carl D.

    2014-11-10

    Cerium oxide nanoparticles (nanoceria) have shown promise as catalytic antioxidants in the test tube, cell culture models and animal models of disease. However given the reactivity that is well established at the surface of these nanoparticles, the biological utilization of nanoceria as a therapeutic still poses many challenges. Moreover the form that these particles take in a biological environment, such as the changes that can occur due to a protein corona, are not well established. This review aims to summarize the existing literature on biological use of nanoceria, and to raise questions about what further study is needed to apply this interesting catalytic material to biomedical applications. These questions include: 1) How does preparation, exposure dose, route and experimental model influence the reported effects of nanoceria in animal studies? 2) What are the considerations to develop nanoceria as a therapeutic agent in regards to these parameters? 3) What biological targets of reactive oxygen species (ROS) and reactive nitrogen species (RNS) are relevant to this targeting, and how do these properties also influence the safety of these nanomaterials?

  15. Catalytic graphitization of carbon/carbon composites by lanthanum oxide

    Institute of Scientific and Technical Information of China (English)

    ZHANG Can; LU Guimin; SUN Ze; YU Jianguo

    2012-01-01

    Graphitized carbon/carbon composites were prepared by the process of catalytic graphitization with the rare-earth catalyst,lanthanum oxide (La2O3),in order to increase the degree of graphitization and reduce the electrical resistivity.The modified coal tar pitch and coal-based needle coke were used as carbon source,and a small amount of La2O3 was added to catalyze the graphitization of the disordered carbon materials.The effects of La2O3 catalyst on the graphitization degree and microstructure oftbe carbon/carbon composites were investigated by X-ray diffraction,scanning electron microscopy,and Raman spectroscopy.The results showed that La2O3 promoted the formation of more perfect and larger crystallites,and improved the electrical/mechanical properties of carbon/carbon composites.Carbon/carbon composites with a lower electrical resistivity (7.0 μΩ·m) could be prepared when adding 5 wt.% La2O3 powder with heating treatment at 2800 ℃.The catalytic effect of La2O3 for the graphitization of carbon/carbon composites was analyzed.

  16. Theoretical study of the catalytic CO oxidation by Pt catalyst supported on Ge-doped grapheme.

    Science.gov (United States)

    Tang, Yanan; Yang, Zongxian; Dai, Xianqi; Lu, Zhansheng; Zhang, Yanxing; Fu, Zhaoming

    2014-09-01

    The geometry, electronic structure and catalytic properties of the anchored Pt atom on the Ge-doped graphene (Pt/Ge-graphene) substrates are investigated using the first-principles computations. It is found that Ge atoms can form strong covalent bonds with the carbon atoms at the vacancy site on the defective graphene. The Ge-graphene as substrate can effectively anchored Pt atoms and form supported Pt catalyst, which exhibits good catalytic activity for CO oxidation with a two-step route, starting with the Langmuir-Hinshelwood (LH) reaction followed by the Eley-Rideal (ER) reaction. The Ge dopant in graphene plays a vital role in enhancing the substrate-adsorbate interaction through facilitating the charge redistribution at their interfaces. The Ge-graphene can be used as the reactive support to control the stability and activity of the Pt catalysts. This work provides valuable guidance on fabricating carbon-based catalysts for CO oxidation, and validates the reactivity of single-atom catalyst for designing atomic-scale catalysts.

  17. Oscillatory Behavior during the Catalytic Partial Oxidation of Methane: Following Dynamic Structural Changes of Palladium Using the QEXAFS Technique

    OpenAIRE

    Stoetzel, Jan; Frahm, Ronald; Kimmerle, Bertram; Nachtegaal, Maarten; Grunwaldt, Jan-Dierk

    2012-01-01

    Pd/Al2O3 catalysts oscillate between ignition and extinction of the catalytic partial oxidation of methane when they are exposed to a 2:1 reaction mixture of methane and oxygen. The oscillations of the catalytic performance and the structure of Pd/Al2O3 catalysts in a fixed-bed reactor were investigated using spatially and time-resolved in situ quick scanning X-ray absorption spectroscopy with online mass spectrometry. The dynamic methane conversion oscillated between an inactive state, where...

  18. Catalytic hydrogen peroxide decomposition on La1-xSrxCo03-d perovskite oxides

    NARCIS (Netherlands)

    Dam, Van-Ahn. T.; Olthuis, W.; Bergveld, P.; Berg, van den A.

    2005-01-01

    Lanthanide perovskite oxides are mentioned as material for hydrogen peroxide sensor because they can catalytically decompose hydrogen peroxide in an aqueous medium. The catalytic properties of these perovskite oxides to hydrogen peroxide are suggested due to their oxygen vacancies influenced by the

  19. Catalytic conversion reactions in nanoporous systems with concentration-dependent selectivity: Statistical mechanical modeling

    Science.gov (United States)

    García, Andrés; Wang, Jing; Windus, Theresa L.; Sadow, Aaron D.; Evans, James W.

    2016-05-01

    Statistical mechanical modeling is developed to describe a catalytic conversion reaction A →Bc or Bt with concentration-dependent selectivity of the products, Bc or Bt, where reaction occurs inside catalytic particles traversed by narrow linear nanopores. The associated restricted diffusive transport, which in the extreme case is described by single-file diffusion, naturally induces strong concentration gradients. Furthermore, by comparing kinetic Monte Carlo simulation results with analytic treatments, selectivity is shown to be impacted by strong spatial correlations induced by restricted diffusivity in the presence of reaction and also by a subtle clustering of reactants, A .

  20. Mercury Oxidation via Catalytic Barrier Filters Phase II

    Energy Technology Data Exchange (ETDEWEB)

    Wayne Seames; Michael Mann; Darrin Muggli; Jason Hrdlicka; Carol Horabik

    2007-09-30

    In 2004, the Department of Energy National Energy Technology Laboratory awarded the University of North Dakota a Phase II University Coal Research grant to explore the feasibility of using barrier filters coated with a catalyst to oxidize elemental mercury in coal combustion flue gas streams. Oxidized mercury is substantially easier to remove than elemental mercury. If successful, this technique has the potential to substantially reduce mercury control costs for those installations that already utilize baghouse barrier filters for particulate removal. Completed in 2004, Phase I of this project successfully met its objectives of screening and assessing the possible feasibility of using catalyst coated barrier filters for the oxidation of vapor phase elemental mercury in coal combustion generated flue gas streams. Completed in September 2007, Phase II of this project successfully met its three objectives. First, an effective coating method for a catalytic barrier filter was found. Second, the effects of a simulated flue gas on the catalysts in a bench-scale reactor were determined. Finally, the performance of the best catalyst was assessed using real flue gas generated by a 19 kW research combustor firing each of three separate coal types.

  1. Methylene Blue Inhibits Caspases by Oxidation of the Catalytic Cysteine.

    Science.gov (United States)

    Pakavathkumar, Prateep; Sharma, Gyanesh; Kaushal, Vikas; Foveau, Bénédicte; LeBlanc, Andrea C

    2015-09-24

    Methylene blue, currently in phase 3 clinical trials against Alzheimer Disease, disaggregates the Tau protein of neurofibrillary tangles by oxidizing specific cysteine residues. Here, we investigated if methylene blue can inhibit caspases via the oxidation of their active site cysteine. Methylene blue, and derivatives, azure A and azure B competitively inhibited recombinant Caspase-6 (Casp6), and inhibited Casp6 activity in transfected human colon carcinoma cells and in serum-deprived primary human neuron cultures. Methylene blue also inhibited recombinant Casp1 and Casp3. Furthermore, methylene blue inhibited Casp3 activity in an acute mouse model of liver toxicity. Mass spectrometry confirmed methylene blue and azure B oxidation of the catalytic Cys163 cysteine of Casp6. Together, these results show a novel inhibitory mechanism of caspases via sulfenation of the active site cysteine. These results indicate that methylene blue or its derivatives could (1) have an additional effect against Alzheimer Disease by inhibiting brain caspase activity, (2) be used as a drug to prevent caspase activation in other conditions, and (3) predispose chronically treated individuals to cancer via the inhibition of caspases.

  2. Methylene Blue Inhibits Caspases by Oxidation of the Catalytic Cysteine.

    Science.gov (United States)

    Pakavathkumar, Prateep; Sharma, Gyanesh; Kaushal, Vikas; Foveau, Bénédicte; LeBlanc, Andrea C

    2015-01-01

    Methylene blue, currently in phase 3 clinical trials against Alzheimer Disease, disaggregates the Tau protein of neurofibrillary tangles by oxidizing specific cysteine residues. Here, we investigated if methylene blue can inhibit caspases via the oxidation of their active site cysteine. Methylene blue, and derivatives, azure A and azure B competitively inhibited recombinant Caspase-6 (Casp6), and inhibited Casp6 activity in transfected human colon carcinoma cells and in serum-deprived primary human neuron cultures. Methylene blue also inhibited recombinant Casp1 and Casp3. Furthermore, methylene blue inhibited Casp3 activity in an acute mouse model of liver toxicity. Mass spectrometry confirmed methylene blue and azure B oxidation of the catalytic Cys163 cysteine of Casp6. Together, these results show a novel inhibitory mechanism of caspases via sulfenation of the active site cysteine. These results indicate that methylene blue or its derivatives could (1) have an additional effect against Alzheimer Disease by inhibiting brain caspase activity, (2) be used as a drug to prevent caspase activation in other conditions, and (3) predispose chronically treated individuals to cancer via the inhibition of caspases. PMID:26400108

  3. Dynamics of ultrathin V-oxide layers on Rh(111) in catalytic oxidation of ammonia and CO.

    Science.gov (United States)

    von Boehn, B; Preiss, A; Imbihl, R

    2016-07-20

    Catalytic oxidation of ammonia and CO has been studied in the 10(-4) mbar range using a catalyst prepared by depositing ultra-thin vanadium oxide layers on Rh(111) (θV ≈ 0.2 MLE). Using photoemission electron microscopy (PEEM) as a spatially resolving method, we observe that upon heating in an atmosphere of NH3 and O2 the spatial homogeneity of the VOx layer is removed at 800 K and a pattern consisting of macroscopic stripes develops; at elevated temperatures this pattern transforms into a pattern of circular VOx islands. Under reaction conditions the neighboring VOx islands become attracted by each other and coalesce. Similar processes of pattern formation and island coalescence are observed in catalytic CO oxidation. Reoxidation of the reduced VOx catalyst proceeds via surface diffusion of oxygen adsorbed onto Rh(111). A pattern consisting of macroscopic circular VOx islands can also be obtained by heating a Rh(111)/VOx catalyst in pure O2. PMID:27380822

  4. Periodic and random perturbation of catalytic oxidation of CO

    Institute of Scientific and Technical Information of China (English)

    杨灵法; 侯中怀; 辛厚文

    1999-01-01

    When a controllable input is modulated by noise and signal, the response of a nonlinear system may exhibit a synchronized effect, which is referred to as stochastic resonance(SR). With the help of noise, the detection of weak signal may become possible and its signal-to-noise ratio can be increased. A model to describe catalytic oxidation of CO on single crystal was adopted, and its stability was studied by linear analysis method. Through computer simulation, the responses under periodic and random perturbation were analyzed. Stochastic resonance behavior was found in a narrow bistable region, or near the oscillatory region. The results shows more characteristics than those of 1-dimensional system does.

  5. On the catalytic gas phase oxidation of butadiene to furan

    Energy Technology Data Exchange (ETDEWEB)

    Kubias, B.; Rodemerck, U. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany); Ritschl, F.; Meisel, M. [Humboldt-Universitaet, Berlin (Germany). Inst. fuer Chemie

    1998-12-31

    Applying the thermochemical selectivity criterion of Hadnett et al. It is shown that the selectivity of the furan formation is not limited by a too low strength of the C-H bonds in furan when compared with the C-H bond dissociation energy in the educt molecule butadiene. In the oxidation of butadiene on a CsH{sub 2}PMo{sub 12}O{sub 40} catalyst a maximum yield of 22 mol% furan has been obtained. To improve this comparatively low furan yield oxidation activity of the catalyst must be lowered to prevent the consecutive reaction to maleic anhydride. (orig.)

  6. Characterization of microstructure and catalytic of cerium oxide obtained by colloidal solution

    International Nuclear Information System (INIS)

    This study investigated to obtain particles of cerium oxide, for use as catalysts for the combustion of methane using the technique of through polymeric colloidal solution. Obtaining the colloidal system is based on hydrolysis of salts such as cerium acetylacetonate, cerium nitrate in the presence of additives such as polyvinylbutyral (PVB), polyvinylpyrrolidone (PVP) and polyvinyl acetate (PVA), at concentrations of 5, 10 and 15% in aqueous or alcoholic medium. These solutions containing ions of interest were subjected to a heat treatment at 650° C for 30 minutes, with heating rate of 2 ° C/ min. After heat treatment, the fibers were characterized according to their morphology, surface area, crystallinity, weight loss and catalytic activity. Samples obtained from cerium acetylacetonate were more reactive than the cerium nitrate to the combustion of methane, as showed greater conversions and higher temperatures reached during the process, which is of utmost importance since the combustion catalytic methane is used for generating thermal energy. After the reaction with methane, the samples underwent significant change in surface area, probably due to the intensity of combustion reactions of the nitrate and the generation of heat involved in this reaction, which gave rise to coarse particles. During the combustion process using the obtained from particles of cerium acetylacetonate, there was the release of large quantities of nitrogen compared to the results of assays with the particles obtained with cerium nitrate. (author)

  7. Synthesis of 7,7'-Disubstituted BINAP and Their Application in Asymmetric Catalytic Reaction

    Institute of Scientific and Technical Information of China (English)

    Yuan Wei-Cheng; Liu Hua; Mi Ai-Qiao; Gong Liu-Zhu; Jiang Yao-Zhong

    2004-01-01

    The design of new chiral ligands plays a very important role in the development of transition metal catalyzed asymmetric synthesis. Many chiral diphosphine ligands have been prepared and applied in asymmetric catalytic reactions with excellent enantioselectivities. Among the chiral diphosphine ligands reported, BINAP was found to have been the widest application in the transition metal catalyzed reaction. Recently we have developed a novel oxovanadium (Ⅳ)complex catalyst for the oxidative coupling of naphthol with high enantioselectivity.[1] And then a series of optically pure 7,7'-disubstituted BINOLs were successfully synthesized by using the catalyst,[2] on the basis of above, the 7,7'-disubstituted BINAP ligands ( 1-5 ) were easily prepared from the 7,7'-disubstituted BINOLs with high total yields (up to 64% of 5 steps from the BINOLs ).To demonstrate the efficiency of ligands 1-5, we applied their ruthenium complexes for asymmetric hydrogenation of simple ketones with high activity (S/C up to 5000 ), high converation (up to 100%) and moderate enantioselectivity (ee up to 88.3% ) under mild conditions. In addition, in the asymmetric 1,4-addition of arylboronic acids, these ligands also provide excellent enantioselectivity (ee up to 99%) and yield ( up to 99%).

  8. Visualizing a Catalyst at Work during the Ignition of the Catalytic Partial Oxidation of Methane

    DEFF Research Database (Denmark)

    Kimmerle, Bertram; Grunwaldt, Jan-Dierk; Baiker, Alfons;

    2009-01-01

    We present a spatiotemporal operando X-ray absorption study of a highly dynamic process, the ignition of the noble metal catalyzed partial oxidation of methane. Evolvement and propagation of the platinum component's structural changes are investigated with a high-speed X-ray camera, which in comb...... in combination with temperature profiling by IR-thermography and catalytic activity measurements by online mass spectrometry gives insight into the first stages of the ignition of the reaction toward hydrogen and carbon monoxide.......We present a spatiotemporal operando X-ray absorption study of a highly dynamic process, the ignition of the noble metal catalyzed partial oxidation of methane. Evolvement and propagation of the platinum component's structural changes are investigated with a high-speed X-ray camera, which...

  9. Catalytic wet peroxide oxidation of phenol solutions over CuO/CeO{sub 2} systems

    Energy Technology Data Exchange (ETDEWEB)

    Massa, Paola, E-mail: pamassa@fi.mdp.edu.ar [Division Catalizadores y Superficies, INTEMA, Universidad Nacional de Mar del Plata/CONICET, Juan B. Justo 4302, 7600 Mar del Plata, Buenos Aires (Argentina); Ivorra, Fernando; Haure, Patricia; Fenoglio, Rosa [Division Catalizadores y Superficies, INTEMA, Universidad Nacional de Mar del Plata/CONICET, Juan B. Justo 4302, 7600 Mar del Plata, Buenos Aires (Argentina)

    2011-06-15

    Three 5% CuO/CeO{sub 2} catalysts were synthesized by sol-gel, precipitation and combustion methods, followed by incipient wetness impregnation with copper nitrate. The samples were characterized by XRD, TPR, BET and tested for the catalytic wet peroxide oxidation of a phenol solution (5 g/L). The reaction took place in a batch reactor at atmospheric pressure, in a temperature range of 60-80{sup Degree-Sign }C , during 4 h. Phenol conversion, H{sub 2}O{sub 2} consumption, pH and chemical oxygen demand were determined. The reaction temperature and the catalyst loading did improve the phenol and the H{sub 2}O{sub 2} conversions. The effect on the selectivity towards complete mineralization was less marked, with levels among 60-70%. Stepwise addition of H{sub 2}O{sub 2} was also tested.

  10. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  11. Effects of Gas Velocity and Temperature on Nitric Oxide Conversion in Simulated Catalytic Converter

    Directory of Open Access Journals (Sweden)

    Sathaporn Chuepeng

    2012-01-01

    Full Text Available Problem statement: Gaseous emissions from gasoline engine such as carbon monoxide, unburned hydrocarbon and nitrogen oxides were usually reduced in three-way catalytic converter simultaneously around theoretical fuel and air combustion. Engine speed and load and other parameters were varied over a wide range of operating conditions, resulting in different exhaust gas composition and condition intake into catalytic converter. This work was studied the conversion of Nitric Oxide (NO in exhaust gas catalytic converter affected by gas velocity and inlet temperature using numerical modeling. Approach: The simulation was based on a one-dimensional time-dependent model within a single monolith channel of the converter. Upon certain assumptions, the study was considered heterogeneous combustion reaction between gas and solid phases based on lumped kinetic reactions. In this study, constants and variables used for mass and heat transfers were dependent on gas or solid phase temperature and mole fraction. Finite difference scheme incorporated with the generated computer code was established for solving species and energy balances within gas and solid phases. Results: The NO conversion was increased with transient period in initial and reached steady state at different values. The lower inlet gas temperature was resulted in lesser NO conversion at the same inlet NO concentration and gas velocity. The light-off temperatures were up to 520 K and a sudden rise in NO conversion was from 550-605 K and decreasing onwards, generating working temperature window. NO conversion increased throughout the catalyst bed from the inlet and the conversion decreased as the gas velocity increased. Conclusion/Recommendations: Gas space velocity and gas temperature intake to the converter affected the NO conversion over the time and the axial distance from the catalyst bed inlet. The numerical results have summarily demonstrated a good approximation compared to experimental

  12. Photocatalytic Water-Splitting Reaction from Catalytic and Kinetic Perspectives

    KAUST Repository

    Hisatomi, Takashi

    2014-10-16

    Abstract: Some particulate semiconductors loaded with nanoparticulate catalysts exhibit photocatalytic activity for the water-splitting reaction. The photocatalysis is distinct from the thermal catalysis because photocatalysis involves photophysical processes in particulate semiconductors. This review article presents a brief introduction to photocatalysis, followed by kinetic aspects of the photocatalytic water-splitting reaction.Graphical Abstract: [Figure not available: see fulltext.

  13. Catalytic oxidative conversion of alkanes to olefines and oxygenates

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-12-31

    All of the direct reaction schemes described and the corresponding process schemes are still in an exploratory state. Ethylene by oxidative coupling of methane could become competitive if process schemes are developed with significantly less expenditures for separation of the product from unconverted feed. No encouragement for formaldehyde from methane can be presently derived from the existing knowledge. Liquid-phase oxidation of methane to methanol appears to be attractive but no final judgement is possible at present. Oxidative dehydrogenation of ethylene and propane look promising although further catalyst improvement is required. Acetic acid from ethane and acrylonitrile from propane have a certain potential as an alternative to present technology. The outlook for acrolein and acrylic acid from propane is less favourable; new concepts for catalyst design are necessary. (orig.)

  14. Mass transfer during catalytic reaction in electroosmotically driven flow in a channel microreactor

    Science.gov (United States)

    Sharma, Himanshu; Vasu, Nadapana; de, Sirshendu

    2011-05-01

    Analytical solution for concentration profile in a microreactor is obtained during heterogeneous catalytic reaction. Reaction occurs in rectangular microchannel with catalyst-coated walls. Flow is induced electroosmotically in the microchannel. A general solution is obtained for first order reaction using a power series solution. Profiles of conversion, cup-mixing concentration of reactant, etc. and variation of Sherwood number is analyzed as function of operating variables. Analytical solution is compared with numerical results.

  15. Catalytic application of an organosuperbasedenderon grafted on mesoporous SBA-15 and related palladium complex in the aerobic oxidation of alcohols

    Directory of Open Access Journals (Sweden)

    Hojat Veisi

    2014-02-01

    Full Text Available An efficient synthetic method for successful application of amine denderon on SBA-15 and related Pd (II complex has been developed by employing aerobic oxidation of alcohols as model reactions. The yields of the products were in the range from 75% to 92%. The catalyst can be readily recovered and reused at least 5 consecutive cycles without significant leaching and loss its catalytic activity.

  16. Catalytic Spectrophotometry for Vanadium Determination Based on Oxidation of Arsenazo Ⅲ by Bichromate

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    A catalytic spectrophotometry for the determination of trace amount of vanadium was developed based on its catalytic effect on the oxidation of arsenazo Ⅲ by potassium bichromate in weak acidic medium. The optimized conditions for determinations are: cK2Cr2O7=3.0×10-5 mol·L-1, carsenazo Ⅲ=3.0×10-5 mol·L-1, pH=4.0, t=90℃. The calibration graph is linear for 0.02~0.2 μg·ml-1, and the detection limit is 0.02 μg·ml-1 V. The apparent active energy of this catalytic reaction is 21.72 kJ·mol-1. Most foreign ions do not interfere with the determination of vadadium, except for Fe(Ⅱ) and Co(Ⅱ), and their interferences could be eliminated by ion exchange. The present method has been used to make the determination of vanadium in human hair, tea, potato and wastewater, and the results were satisfactory.

  17. Catalytic propane dehydrogenation over In₂O₃–Ga₂O₃ mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Shuai; Gil, Laura Briones; Subramanian, Nachal; Sholl, David S.; Nair, Sankar; Jones, Christopher W.; Moore, Jason S.; Liu, Yujun; Dixit, Ravindra S.; Pendergast, John G. (Dow); (GIT)

    2015-08-26

    We have investigated the catalytic performance of novel In₂O₃–Ga₂O₃ mixed oxides synthesized by the alcoholic-coprecipitation method for propane dehydrogenation (PDH). Reactivity measurements reveal that the activities of In₂O₃–Ga₂O₃ catalysts are 1–3-fold (on an active metal basis) and 12–28-fold (on a surface area basis) higher than an In₂O₃–Al₂O₃ catalyst in terms of C₃H₈ conversion. The structure, composition, and surface properties of the In₂O₃–Ga₂O₃ catalysts are thoroughly characterized. NH₃-TPD shows that the binary oxide system generates more acid sites than the corresponding single-component catalysts. Raman spectroscopy suggests that catalysts that produce coke of a more graphitic nature suppress cracking reactions, leading to higher C₃H₆ selectivity. Lower reaction temperature also leads to higher C₃H₆ selectivity by slowing down the rate of side reactions. XRD, XPS, and XANES measurements, strongly suggest that metallic indium and In₂O₃ clusters are formed on the catalyst surface during the reaction. The agglomeration of In₂O₃ domains and formation of a metallic indium phase are found to be irreversible under O₂ or H₂ treatment conditions used here, and may be responsible for loss of activity with increasing time on stream.

  18. Development of Ag dendrites-reduced graphene oxide composite catalysts via galvanic replacement reaction

    Science.gov (United States)

    Fu, Li; Sokiransky, Mika Matsunaka; Wang, James; Lai, Guosong; Yu, Aimin

    2016-09-01

    Silver dendrites/reduced graphene oxide (AgD/RGO) composites were synthesized via a facile galvanic replacement method. The successful formation of Ag dendrites and the graphene oxide reduction were proved by a series of characterization techniques. The possible formation mechanism of Ag dendrites during the galvanic replacement reaction was discussed. The catalytic activity of the as-synthesized AgD/RGO composite was evaluated by its performance on the chemical reduction of an organic dye methylene blue. The AgD/RGO composite showed a much higher catalytic performance and stability than that of Ag dendrites.

  19. The catalytic reaction mechanism of drosophilid alcohol dehydrogenases

    Directory of Open Access Journals (Sweden)

    Imin Wushur

    2015-03-01

    Full Text Available The present review describes the current knowledge about the reaction mechanism of drosophilid alcohol dehydrogenases (DADH, a member of the short chain dehydrogenase/reductase (SDR superfamily. Included is the binding order of the substrates to the enzyme, rate limiting steps, stereochemistry of the reaction, active site topology, role of important amino acids and water molecules in the reaction and pH dependence of kinetic coefficients. We focus on the contribution from steady state kinetics where alternative substrates, dead end and product inhibitors, isotopes and mutated DADHs have been used as well as on the contributions from X-ray crystallography, NMR and theoretical calculations. Furthermore, we also raise some open questions in order to fully understand the reaction mechanism of this enzyme.

  20. Synthesis, characterization, and catalytic application of ordered mesoporous carbon–niobium oxide composites

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Juan-Li; Gao, Shuang; Liu, Chun-Ling; Liu, Zhao-Tie; Dong, Wen-Sheng, E-mail: wsdong@snnu.edu.cn

    2014-11-15

    Graphical abstract: The ordered mesoporous carbon–niobium oxide composites have been synthesized by a multi-component co-assembly method associated with a carbonization process. - Highlights: • Ordered mesoporous carbon–niobium oxide composites were synthesized. • The content of Nb{sub 2}O{sub 5} in the composites could be tuned from 38 to 75%. • Niobium species were highly dispersed in amorphous carbon framework walls. • The composites exhibited good catalytic performance in the dehydration of fructose. - Abstract: Ordered mesoporous carbon–niobium oxide composites have been synthesized by a multi-component co-assembly method associated with a carbonization process using phenolic resol as carbon source, niobium chloride as precursor and amphiphilic triblock copolymer Pluronic F127 as template. The resulting materials were characterized using a combination of techniques including differential scanning calorimetry–thermogravimetric analysis, N{sub 2} physical adsorption, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results show that with increasing the content of Nb{sub 2}O{sub 5} from 38 to 75% the specific surface area decreases from 306.4 to 124.5 m{sup 2} g{sup −1}, while the ordered mesoporous structure is remained. Niobium species is well dispersed in the amorphous carbon framework. The mesoporous carbon–niobium oxide composites exhibit high catalytic activity in the dehydration of fructose to 5-hydroxymethylfurfural. A 100% conversion of fructose and a 76.5% selectivity of 5-hydroxymethylfurfural were obtained over the carbon–niobium oxide composite containing 75% Nb{sub 2}O{sub 5} under the investigated reaction conditions.

  1. Key parameters when developing carbonaceous materials for catalytic wet peroxide oxidation

    OpenAIRE

    Ribeiro, Rui; Silva, Adrián; Pastrana-Martínez, Luisa; Figueiredo, José; Faria, Joaquim; Gomes, Helder

    2014-01-01

    Catalytic wet peroxide oxidation (CWPO) is an advanced oxidation process, operated using simple equipment and mild operating conditians, in which highly oxidizing hydraxyl radicaIs (HO') are generated fram the catalytic decompasition af hydrogen peroxide (H,O,) [L 2). Sinee the report of Lüeking el ai. in 1998 [3], the develapment af suitab-Ie -carbonaceous materials (without any added metal phase) for CWPO has been intensively explored [4). lhe influenee of struetUfal and surr...

  2. Research of Hydrogen Preparation with Catalytic Steam-Carbon Reaction Driven by Photo-Thermochemistry Process

    Directory of Open Access Journals (Sweden)

    Xiaoqing Zhang

    2013-01-01

    Full Text Available An experiment of hydrogen preparation from steam-carbon reaction catalyzed by K2CO3 was carried out at 700°C, which was driven by the solar reaction system simulated with Xenon lamp. It can be found that the rate of reaction with catalyst is 10 times more than that without catalyst. However, for the catalytic reaction, there is no obvious change for the rate of hydrogen generation with catalyst content range from 10% to 20%. Besides, the conversion efficiency of solar energy to chemical energy is more than 13.1% over that by photovoltaic-electrolysis route. An analysis to the mechanism of catalytic steam-carbon reaction with K2CO3 is given, and an explanation to the nonbalanced [H2]/[CO + 2CO2] is presented, which is a phenomenon usually observed in experiment.

  3. Effects of Morphology of Cerium Oxide Catalysts for Reverse Water Gas Shift Reaction

    OpenAIRE

    Kovasevic, M.; Mojet, B.L.; Ommen, van, B.; Lefferts, L.

    2016-01-01

    Reverse water gas shift reaction (RWGS) was investigated over cerium oxide catalysts of distinct morphologies: cubes, rods and particles. Catalysts were characterized by X-ray diffraction, Raman spectroscopy and temperature programmed reduction (TPR) in hydrogen. Nanoshapes with high concentration of oxygen vacancies contain less surface oxygen removable in TPR. Cerium oxide cubes exhibited two times higher activity per surface area as compared to rods and particles. Catalytic activity of the...

  4. Role of iron oxide catalysts in selective catalytic reduction of NOx and soot from vehicular emission

    International Nuclear Information System (INIS)

    This study deals with Iron containing catalysts i.e Iron oxide Fe/sub 2/O/sub 3/) Iron potassium oxide Fe/sub 1.9/K/sub 0.1/O/sub 3/, copper iron oxide Cu/sub 0.9/K/sub 0.1/, Fe/sub 2/O/sub 3/, nickel iron oxide Ni Fe/sub 2/O/sub 4/, and Nickel potassium iron oxide Ni/sub 0.95/K/sub 0.05/ Fe/sub 2/O/sub 4/ catalyst were synthesized by using PVA technique. By X-ray Diffraction technique these catalysts were characterized to ensure the formation of crystalline structure. Energy Dispersive X-rays analysis (EDX) was used for the confirmation of presence of different metals and Scanning Electron Microscopy (SEM) for Surface Morphology. Then the catalytic investigations of the prepared catalyst were carried out for their activity measurement toward simultaneous conversion of NOx and Soot from an engine exhaust. Some Iron containing oxide catalysts were partially modified by alkali metal potassium and were used for NOx -Soot reaction in a model exhaust gas. Fe/sub 1.9 K /sub 0.1/O/sub 3/ show high catalytic performance for N/sub 2/ formation in the prepared catalyst. Further studies have shown that Fe/sub 1.9/ K/sub 0.1/ O/sub 3/ was deactivated in a substantial way after about 20 Temperature. Temperature Programmed Reaction (TPR) experiments due to agglomeration of the promoter potassium. Experiments carried out over the aged Fe/sub 1.9/K/sub 0.1/O/sub 3/ catalyst have shown that NOx-soot reaction was suppressed at higher oxygen concentration, since O/sub 2/-soot conversion was kindly favored. More over nitrite species formed at the catalyst surface might play an important role in NOx-soot conversion. (author)

  5. Tuning size and catalytic activity of nano-clusters of cobalt oxide

    Indian Academy of Sciences (India)

    R Venkat Narayan; Vinod Kanniah; Aruna Dhathathreyan

    2006-03-01

    Cobalt oxides were prepared by three different methods: (1) by reacting cobalt nitrate with oxalic acid, (2) co-precipitating cobalt nitrate with sodium carbonate, and (3) using sodium dodecyl sulphate as organic surfactant. All three samples were characterized before and after calcination by solvent extraction and the resulting products examined by IR spectroscopy. In the case of method 3, the removal of surfactant was followed by TGA studies. Products from all three methods were identified by XRD. Peaks in low angle XRD indicate the porous nature of the oxides. The morphology of the pores was studied by transmission electron microscopy. Some irregular pore structures were obtained for samples from methods 1 and 2, with an average size of 4-6 nm. Only the product from method 3 using SDS as template showed ordered structure and optimum size, and Brunauer-Emmet-Teller surface areas of the as-prepared, as well as the treated samples, exhibited H3 type hysteresis. The samples from the three methods were used as catalysts in the oxidation reaction of cyclohexane under mild conditions and the catalytic efficiency of the cobalt oxide was comparable with mesoporous cobalt oxides.

  6. Oxidation of diesel-generated volatile organic compounds in the selective catalytic reduction process

    Energy Technology Data Exchange (ETDEWEB)

    Koebel, M.; Elsener, M. [Paul Scherrer Inst., Villigen (Switzerland). Combustion Research

    1998-10-01

    The main part of the VOCs (volatile organic compounds) contained in diesel exhaust ({approx}80%) is oxidized to CO and CO{sub 2} over an SCR (selective catalytic reduction) catalyst. CO is the major product of this oxidation, representing about 50--70% of the formed products (CO + CO{sub 2}). This preferential formation of CO leads to a pronounced increase of CO emissions when an SCR process is added to a diesel engine. A small fraction of the VOCs is selectively oxidized to carboxylic acids over the SCR catalyst. This selectivity is due to the acidic properties of the catalyst causing the preferential desorption at the oxidation state of the acid. The main products of these oxidation reactions are the lower monocarboxylic acids and some dicarboxylic acids forming stable anhydrides, especially maleic and phthalic acid. The highest emissions of these acids are found at low temperatures; they decrease at higher temperatures. Formic acid is preferentially decomposed into carbon monoxide and water. It must therefore be assumed that the strong increase of CO mentioned above is due to a mechanism involving the thermal decomposition of formic acid formed from various primary VOCs.

  7. Catalytic combustion of diesel soot over K2NiF4-type oxides La2-xKxCuO4

    Institute of Scientific and Technical Information of China (English)

    ZHU Ling; WANG Xuezhong; LIANG Cunzhen

    2008-01-01

    Nanostructure K2NiF4 type oxides La2-xKxCuO4 complex oxides were prepared using the Sol-Gel method, characterized by X-Ray Diffraction (XRD), Fourier Transform Infrared (FT-IR), and Scanning Electron Microscopy (SEM). The catalytic activity for soot combustion was evaluated by the Temperature-Programmed Reaction (TPO) technique. The results demonstrated that the substitution quality of K+ for La3+ at the A-site would increase the catalytic activities of La2-xKxCuO4 for soot combustion greatly; the substitution quality affected the structure and catalytic activity obviously. The La1.8K0.2CuO4 complex oxides with tetrahedral structures had the best catalytic activity for soot combustion, and the ignition temperature of soot combustion was lowered from 490 to 320 °C.

  8. Surface Acidity as Descriptor of Catalytic Activity for Oxygen Evolution Reaction in Li-O2 Battery.

    Science.gov (United States)

    Zhu, Jinzhen; Wang, Fan; Wang, Beizhou; Wang, Youwei; Liu, Jianjun; Zhang, Wenqing; Wen, Zhaoyin

    2015-10-28

    Unraveling the descriptor of catalytic activity, which is related to physical properties of catalysts, is a major objective of catalysis research. In the present study, the first-principles calculations based on interfacial model were performed to study the oxygen evolution reaction mechanism of Li2O2 supported on active surfaces of transition-metal compounds (TMC: oxides, carbides, and nitrides). Our studies indicate that the O2 evolution and Li(+) desorption energies show linear and volcano relationships with surface acidity of catalysts, respectively. Therefore, the charging voltage and desorption energies of Li(+) and O2 over TMC could correlate with their corresponding surface acidity. It is found that certain materials with an appropriate surface acidity can achieve the high catalytic activity in reducing charging voltage and activation barrier of rate-determinant step. According to this correlation, CoO should have as active catalysis as Co3O4 in reducing charging overpotential, which is further confirmed by our comparative experimental studies. Co3O4, Mo2C, TiC, and TiN are predicted to have a relatively high catalytic activity, which is consistent with the previous experiments. The present study enables the rational design of catalysts with greater activity for charging reactions of Li-O2 battery.

  9. Conversion of the refractory ammonia and acetic acid in catalytic wet air oxidation of animal byproducts

    Institute of Scientific and Technical Information of China (English)

    Virginie Fontanier; Sofiane Zalouk; Stéphane Barbati

    2011-01-01

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) of slaughtered animal byproducts (ABPs) were investigated.Two step experiment was carried out consisting ofa non-catalysed WAO run followed by a CWAO run at 170-275℃, 20 MPa, and reaction time 180 min.The WAO (1st step) of sample (5 g/L total organic carbon (TOC)) yielded (82.0 ± 4)% TOC removal and (78.4 ± 13.2)%conversion of the initial organic-N into NH4+-N.Four metal catalysts (Pd, Pt, Rh, Ru) supported over alumina have been tested in catalytic WAO (2nd step) at elevated pH to enhance ammonia conversion and organic matter removal, particularly acetic acid.It was found that the catalysts Ru, Pt, and Rh had significant effects on the TOC removal (95.1%, 99.5% and 96.7%, respectively) and on the abatement of ammonia (93.4%, 96.7% and 96.3%, respectively) with high nitrogen selectivity.The catalyst Pd was found to have the less activity while Pt had the best performance.The X-Ray diffraction analysis showed that the support of catalyst was not stable under the experimental conditions since it reacted with phosphate present in solution.Nitrite and nitrate ions were monitored during the oxidation reaction and it was concluded that CWAO of ammonia in real waste treatment framework was in good agreement with the results obtained from the literature for ideal solutions of ammonia.

  10. Catalytic pleat filter bags for combined particulate separation and nitrogen oxides removal from flue gas streams

    International Nuclear Information System (INIS)

    The development of a high temperature catalytically active pleated filter bag with hybrid filter equipment for the combined removal of particles and nitrogen oxides from flue gas streams is presented. A special catalyst load in stainless steel mesh cartridge with a high temperature pleated filter bag followed by optimized catalytic activation was developed to reach the required nitrogen oxides levels and to maintain the higher collection efficiencies. The catalytic properties of the developed high temperature filter bags with hybrid filter equipment were studied and demonstrated in a pilot scale test rig and a demonstration plant using commercial scale of high temperature catalytic pleated filter bags. The performance of the catalytic pleated filter bags were tested under different operating conditions, such as filtration velocity and operating temperature. Moreover, the cleaning efficiency and residual pressure drop of the catalyst loaded cartridges in pleated filter bags were tested. As result of theses studies, the optimum operating conditions for the catalytic pleated filter bags are determined. (author)

  11. Evidence for the powerful catalytic ability of imidozirconocene complex from its epoxide ring cleavage reactions - A DFT mechanistic view

    Indian Academy of Sciences (India)

    Dhurairajan Senthilnathan; Rajadurai Vijay Solomon; Ponnambalam Venuvanalingam

    2012-01-01

    Imidozirconocene complex is known for its bifunctional reactivity and catalytic ability and this complex mediates ring cleavage of epoxides. Cyclooctene oxide (1) Norbornene oxide (2) and 2,5-dimethyl cyclohexene oxide (3) undergo ring cleavage in the presence of imidozirconocene complex. Epoxide 1 has accessible -hydrogens (type I) while epoxide 2 and 3 do not have them (type II). Normally type I epoxides undergo elimination while type II epoxides prefer insertion. All the insertion reactions lead to five-membered metallacycle formation and elimination results in thermodynamically stable allyl-alkoxy product. The insertion is a two-step process following either diradical or zwitterionic pathway, while elimination is a one-step concerted reaction. DFT (density functional theory) modelling of these reactions at B3LYP/LANL2DZ level show that epoxide 1 undergoes elimination in agreement with experiment. However, calculations indicate that epoxide (2) proceeds through diradical intermediate in contrast to experimental observations. Surprisingly, epoxide (3) that has both the positions blocked by methyl groups undergoes elimination rather than insertion. AIM and EDA analyses offer further insights on the reaction mechanism and bifunctional reactivity of imidozirconozene complex.

  12. Efficient Catalytic Ozonation over Reduced Graphene Oxide for p-Hydroxylbenzoic Acid (PHBA) Destruction: Active Site and Mechanism.

    Science.gov (United States)

    Wang, Yuxian; Xie, Yongbing; Sun, Hongqi; Xiao, Jiadong; Cao, Hongbin; Wang, Shaobin

    2016-04-20

    Nanocarbons have been demonstrated as promising environmentally benign catalysts for advanced oxidation processes (AOPs) upgrading metal-based materials. In this study, reduced graphene oxide (rGO) with a low level of structural defects was synthesized via a scalable method for catalytic ozonation of p-hydroxylbenzoic acid (PHBA). Metal-free rGO materials were found to exhibit a superior activity in activating ozone for catalytic oxidation of organic phenolics. The electron-rich carbonyl groups were identified as the active sites for the catalytic reaction. Electron spin resonance (ESR) and radical competition tests revealed that superoxide radical ((•)O2(-)) and singlet oxygen ((1)O2) were the reactive oxygen species (ROS) for PHBA degradation. The intermediates and the degradation pathways were illustrated from mass spectroscopy. It was interesting to observe that addition of NaCl could enhance both ozonation and catalytic ozonation efficiencies and make ·O2(-) as the dominant ROS. Stability of the catalysts was also evaluated by the successive tests. Loss of specific surface area and changes in the surface chemistry were suggested to be responsible for catalyst deactivation. PMID:27007603

  13. Modular, Catalytic Enantioselective Construction of Quaternary Carbon Stereocenters by Sequential Cross-Coupling Reactions.

    Science.gov (United States)

    Potter, Bowman; Edelstein, Emma K; Morken, James P

    2016-07-01

    The catalytic Suzuki-Miyaura cross-coupling with chiral γ,γ-disubstituted allylboronates in the presence of RuPhos ligand occurs with high regioselectivity and enantiospecificity, furnishing nonracemic compounds with quaternary centers. Mechanistic experiments suggest that the reaction occurs by transmetalation with allyl migration, followed by rapid reductive elimination.

  14. Catalytic Hydrotreatment of Fast Pyrolysis Oil : Model Studies on Reaction Pathways for the Carbohydrate Fraction

    NARCIS (Netherlands)

    Wildschut, J.; Arentz, J.; Rasrendra, C. B.; Venderbosch, R. H.; Heeres, H. J.

    2009-01-01

    Fast pyrolysis oil can be upgraded by a catalytic hydrotreatment (250-400 degrees C, 100-200 bar) using heterogeneous catalysts such as Ru/C to hydrocarbon-like products that can serve as liquid transportation fuels. Insight into the complex reaction pathways of the various component fractions durin

  15. Session 6: Catalytic Dechlorination Reaction of Chlorinated Hydrocarbons with Water Using nano-structured Alumina

    Energy Technology Data Exchange (ETDEWEB)

    Abbas, Khaleel [United Arab Emirates Univ., Dept. of Chemistry, Al-Ain (United States)

    2004-07-01

    Herein, we report our recent results from a study on the catalytic dechlorination reactions of 1,2-dichloroethane (DCE) and carbon tetrachloride (CTC) with water using HSA-Al{sub 2}O{sub 3} as the catalyst. The obtained experimental results are explained. (O.M.)

  16. Process Intensification. Continuous Two-Phase Catalytic Reactions in a Table-Top Centrifugal Contact Separator

    NARCIS (Netherlands)

    Kraai, Gerard N.; Schuur, Boelo; van Zwol, Floris; Haak, Robert M.; Minnaard, Adriaan J.; Feringa, Ben L.; Heeres, Hero J.; de Vries, Johannes G.; Prunier, ML

    2009-01-01

    Production of fine chemicals is mostly performed in batch reactors. Use of continuous processes has many advantages which may reduce the cost of production. We have developed the use of centrifugal contact separators (CCSs) for continuous two-phase catalytic reactions. This equipment has previously

  17. Catalytic reaction of cytokinin dehydrogenase : preference for quinones as electron acceptors

    NARCIS (Netherlands)

    Frébortová, Jitka; Fraaije, Marco W.; Galuszka, Petr; Šebela, Marek; Peč, Pavel; Hrbáč, Jan; Novák, Ondřej; Bilyeu, Kristin D.; English, James T.; Frébort, Ivo; Sebela, M.; Pec, P.; Hrbac, J.; Frebort, [No Value

    2004-01-01

    The catalytic reaction of cytokinin oxidase/dehydrogenase (EC 1.5.99.12) was studied in detail using the recombinant flavoenzyme from maize. Determination of the redox potential of the covalently linked flavin cofactor revealed a relatively high potential dictating the type of electron acceptor that

  18. In-situ scanning transmission X-ray microscopy of catalytic materials under reaction conditions

    NARCIS (Netherlands)

    de Smit, E.; Creemer, J.F.; Zandbergen, H.W.; Weckhuysen, B.M.; de Groot, F.M.F.

    2009-01-01

    In-situ Scanning X-ray Transmission Microscopy (STXM) allows the measurement of the soft X-ray absorption spectra with 10 to 30 nm spatial resolution under realistic reaction conditions. We show that STXM-XAS in combination with a micromachined nanoreactor can image a catalytic system under relevant

  19. Nitrated Confined Imidodiphosphates Enable a Catalytic Asymmetric Oxa-Pictet-Spengler Reaction.

    Science.gov (United States)

    Das, Sayantani; Liu, Luping; Zheng, Yiying; Alachraf, M Wasim; Thiel, Walter; De, Chandra Kanta; List, Benjamin

    2016-08-01

    The development of a highly enantioselective catalytic oxa-Pictet-Spengler reaction has proven a great challenge for chemical synthesis. We now report the first example of such a process, which was realized by utilizing a nitrated confined imidodiphosphoric acid catalyst. Our approach provides substituted isochroman derivatives from both aliphatic and aromatic aldehydes with high yields and excellent enantioselectivities. DFT calculations provide insight into the reaction mechanism. PMID:27457383

  20. Study of catalytic effect of ammonium molybdate on the bisphthalonitrile resins curing reaction with aromatic amine

    Institute of Scientific and Technical Information of China (English)

    Wen Ting Li; Fang Zuo; Kun Jia; Xiao Bo Liu

    2009-01-01

    A kind of catalyst, ammonium molybdate was developed in this paper to promote the curing reaction of bisphthalonitrile resins with aromatic amine as curing agent, and the catalytic effect was studied by differential scanning calorimetry (DSC), rheometric measurements and thermogravimetric analysis (TGA). The results indicated that the catalyst could improve the curing rate and increase the curing degree, which could be regulated by the content of the catalyst used in the reaction.

  1. The Self-catalytic Esterification Reaction of O-Phosphoryl Serine Derivative

    Institute of Scientific and Technical Information of China (English)

    Jin Tang DU; Yan Mei LI; Zhong Zhou CHEN; Shi Zhong LUO; Yu Fen ZHAO

    2005-01-01

    O-Phosphoryl serine derivative can perform self-catalytic esterification reaction in the mixture of CH3OH and CHCl3 at the room temperature. The phosphoryl group participation was the key step of the esterification. This type of reactions were proposed through an intermediate of mixed phosphoric-carboxylic anhydride that might provide a clue to the function of the phosphoryl group in the phosphorylated enzymes and in the prebiotic synthesis of protein.

  2. Oscillatory three-phase flow reactor for studies of bi-phasic catalytic reactions

    OpenAIRE

    Abolhasani, Milad; Bruno, Nicholas C.; Jensen, Klavs F.

    2015-01-01

    A multi-phase flow strategy, based on oscillatory motion of a bi-phasic slug within a fluorinated ethylene propylene (FEP) tubular reactor, under inert atmosphere, is designed and developed to address mixing and mass transfer limitations associated with continuous slug flow chemistry platforms for studies of bi-phasic catalytic reactions. The technique is exemplified with C–C and C–N Pd catalyzed coupling reactions.

  3. In-situ scanning transmission X-ray microscopy of catalytic materials under reaction conditions

    OpenAIRE

    E. Smit; Creemer, J.F.; Zandbergen, H. W.; Weckhuysen, B. M.; Groot, F.M.F. de

    2009-01-01

    In-situ Scanning X-ray Transmission Microscopy (STXM) allows the measurement of the soft X-ray absorption spectra with 10 to 30 nm spatial resolution under realistic reaction conditions. We show that STXM-XAS in combination with a micromachined nanoreactor can image a catalytic system under relevant reaction conditions, and provide detailed information on the morphology and composition of the catalyst material. The nanometer resolution combined with powerful chemical speciation by XAS and the...

  4. Catalytic wet-air oxidation of lignin in a three-phase reactor with aromatic aldehyde production

    OpenAIRE

    Sales F.G.; Abreu C.A.M.; Pereira J. A. F. R.

    2004-01-01

    In the present work a process of catalytic wet air oxidation of lignin obtained from sugar-cane bagasse is developed with the objective of producing vanillin, syringaldehyde and p-hydroxybenzaldehyde in a continuous regime. Palladium supported on g-alumina was used as the catalyst. The reactions in the lignin degradation and aldehyde production were described by a kinetic model as a system of complex parallel and series reactions, in which pseudo-first-order steps are found. For the purpose o...

  5. Microreactor for the Catalytic Partial Oxidation of Methane

    Institute of Scientific and Technical Information of China (English)

    Widodo Wahyu Puwanto; Yuswan Muharam

    2006-01-01

    Fixed-bed reactors for the partial oxidation of methane to produce synthetic gas still pose hotspot problems. An alternative reactor, which is known as the shell-and-tube-typed microreactor, has been developed to resolve these problems. The microreactor consists of a 1 cm outside-diameter, 0.8 cm insidediameter and 11 cm length tube, and a 1.8 cm inside-diameter shell. The tube is made of dense alumina and the shell is made of quartz. Two different methods dip and spray coating were performed to line the tube side with the LaNixOy catalyst. Combustion and reforming reactions take place simultaneously in this reactor. Methane is oxidized in the tube side to produce flue gases (CO2 and H2O) which flow counter-currently and react with the remaining methane in the shell side to yield synthesis gas. The methane conversion using the higher-loading catalyst spray-coated tube reaches 97% at 700 ℃, whereas that using the lower-loading catalyst dip-coated tube reaches only 7.78% because of poor adhesion between the catalyst film and the alumina support. The turnover frequencies (TOFs) using the catalyst spray-and 900 ℃ provides better performance than that at 1250 ℃ because sintering reduces the surface-area. The hydrogen to carbon monoxide ratio produced by the spray-coated catalyst is greater than the stoichiometric ratio, which is caused by carbon deposition through methane cracking or the Boudouard reaction.

  6. Catalytic oxidative desulfurization of diesel utilizing hydrogen peroxide and functionalized-activated carbon in a biphasic diesel-acetonitrile system

    Energy Technology Data Exchange (ETDEWEB)

    Haw, Kok-Giap; Bakar, Wan Azelee Wan Abu; Ali, Rusmidah; Chong, Jiunn-Fat [Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia); Kadir, Abdul Aziz Abdul [Department of Petroleum Engineering, Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia)

    2010-09-15

    This paper presents the development of granular functionalized-activated carbon as catalysts in the catalytic oxidative desulfurization (Cat-ODS) of commercial Malaysian diesel using hydrogen peroxide as oxidant. Granular functionalized-activated carbon was prepared from oil palm shell using phosphoric acid activation method and carbonized at 500 C and 700 C for 1 h. The activated carbons were characterized using various analytical techniques to study the chemistry underlying the preparation and calcination treatment. Nitrogen adsorption/desorption isotherms exhibited the characteristic of microporous structure with some contribution of mesopore property. The Fourier Transform Infrared Spectroscopy results showed that higher activation temperature leads to fewer surface functional groups due to thermal decomposition. Micrograph from Field Emission Scanning Electron Microscope showed that activation at 700 C creates orderly and well developed pores. Furthermore, X-ray Diffraction patterns revealed that pyrolysis has converted crystalline cellulose structure of oil palm shell to amorphous carbon structure. The influence of the reaction temperature, the oxidation duration, the solvent, and the oxidant/sulfur molar ratio were examined. The rates of the catalytic oxidative desulfurization reaction were found to increase with the temperature, and H{sub 2}O{sub 2}/S molar ratio. Under the best operating condition for the catalytic oxidative desulfurization: temperature 50 C, atmospheric pressure, 0.5 g activated carbon, 3 mol ratio of hydrogen peroxide to sulfur, 2 mol ratio of acetic acid to sulfur, 3 oxidation cycles with 1 h for each cycle using acetonitrile as extraction solvent, the sulfur content in diesel was reduced from 2189 ppm to 190 ppm with 91.3% of total sulfur removed. (author)

  7. Elucidating molecular iridium water oxidation catalysts using metal-organic frameworks: a comprehensive structural, catalytic, spectroscopic, and kinetic study.

    Science.gov (United States)

    Wang, Cheng; Wang, Jin-Liang; Lin, Wenbin

    2012-12-01

    As a new class of porous, crystalline, molecular materials, metal-organic frameworks (MOFs) have shown great promise as recyclable and reusable single-site solid catalysts. Periodic order and site isolation of the catalytic struts in MOFs facilitate the studies of their activities and reaction mechanisms. Herein we report the construction of two highly stable MOFs (1 and 2) using elongated dicarboxylate bridging ligands derived from Cp*Ir(L)Cl complexes (L = dibenzoate-substituted 2,2'-bipyridine, bpy-dc, or dibenzoate-substituted 2-phenylpyridine, ppy-dc) and Zr(6)O(4)(OH)(4)(carboxylate)(12) cuboctahedral secondary building units (SBUs) and the elucidation of water oxidation pathways of the Cp*Ir(L)Cl catalysts using these MOFs. We carried out detailed kinetic studies of Ce(4+)-driven water oxidation reactions (WORs) catalyzed by the MOFs using UV-vis spectroscopy, phosphorescent oxygen detection, and gas chromatographic analysis. These results confirmed not only water oxidation activity of the MOFs but also indicated oxidative degradation of the Cp* rings during the WOR. The (bpy-dc)Ir(H(2)O)(2)XCl (X is likely a formate or acetate group) complex resulted from the oxidative degradation process was identified as a competent catalyst responsible for the water oxidation activity of 1. Further characterization of the MOFs recovered from WORs using X-ray photoelectron, diffuse-reflectance UV-vis absorption, luminescence, and infrared spectroscopies supported the identity of (bpy-dc)Ir(H(2)O)(2)XCl as an active water oxidation catalyst. Kinetics of MOF-catalyzed WORs were monitored by Ce(4+) consumptions and fitted with a reaction-diffusion model, revealing an intricate relationship between reaction and diffusion rates. Our work underscores the opportunity in using MOFs as well-defined single-site solid catalytic systems to reveal mechanistic details that are difficult to obtain for their homogeneous counterparts. PMID:23136923

  8. A comparative theoretical study of CO oxidation reaction by O2 molecule over Al- or Si-decorated graphene oxide.

    Science.gov (United States)

    Esrafili, Mehdi D; Sharifi, Fahimeh; Nematollahi, Parisa

    2016-09-01

    Using density functional theory calculations, the probable CO oxidation reaction mechanisms are investigated over Al- or Si-decorated graphene oxide (GO). The equilibrium geometry and electronic structure of these metal decorated-GOs along with the O2/CO adsorption configurations are studied in detail. The relatively large adsorption energies reveal that both Al and Si atoms can disperse on GO quite stably without clustering problem. Hence, both Al- and Si-decorated GOs are stable enough to be utilized in catalytic oxidation of CO by molecular O2. The two possible reaction pathways proposed for the oxidation of CO with O2 molecule are as follows: O2+CO→CO2+Oads and CO+Oads→CO2. The estimated energy barriers of the first oxidation reaction on Si-decorated GOs, following the Eley-Rideal (ER) reaction, are lower than that on Al-decorated ones. This is most likely due to the larger atomic charge on the Si atom than the Al one, which tends to stabilize the corresponding transition state structure. The results of this study can be useful for better understanding the chemical properties of Al- and Si-decorated GOs, and are valuable for the development of an automobile catalytic converter in order to remove the toxic CO molecule.

  9. Electrochemical study on the cationic promotion of the catalytic SO2 oxidation in pyrosulfate melts

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bjerrum, Niels; Cappeln, Frederik Vilhelm

    1998-01-01

    The electrochemical behavior of the molten V2O5-M2S2O7 (M = K, Cs, or Na) system was studied using a gold working electrode at 440 degrees C in argon and air atmosphere. The aim of the present investigation was to find a possible correlation between the promoting effect of Cs+ and Na+ ions...... on the catalytic oxidation of SO2 in the V2O5-M2S2O7 system and the effect of these alkali cations on the electrochemical behavior of V2O5 in the alkali pyrosulfate melts It has been shown that Na+ ions had a promoting effect on the V(V) reversible arrow V(IV) electrochemical reaction. Sodium ions accelerate both...

  10. Influence of size-induced oxidation state of platinum nanoparticles on selectivity and activity in catalytic methanol oxidation in the gas phase.

    Science.gov (United States)

    Wang, Hailiang; Wang, Yihai; Zhu, Zhongwei; Sapi, Andras; An, Kwangjin; Kennedy, Griffin; Michalak, William D; Somorjai, Gabor A

    2013-06-12

    Pt nanoparticles with various sizes of 1, 2, 4, and 6 nm were synthesized and studied as catalysts for gas-phase methanol oxidation reaction toward formaldehyde and carbon dioxide under ambient pressure (10 Torr of methanol, 50 Torr of oxygen, and 710 Torr of helium) at a low temperature of 60 °C. While the 2, 4, and 6 nm nanoparticles exhibited similar catalytic activity and selectivity, the 1 nm nanoparticles showed a significantly higher selectivity toward partial oxidation of methanol to formaldehyde, but a lower total turnover frequency. The observed size effect in catalysis was correlated to the size-dependent structure and oxidation state of the Pt nanoparticles. X-ray photoelectron spectroscopy and infrared vibrational spectroscopy using adsorbed CO as molecular probes revealed that the 1 nm nanoparticles were predominantly oxidized while the 2, 4, and 6 nm nanoparticles were largely metallic. Transmission electron microscopy imaging witnessed the transition from crystalline to quasicrystalline structure as the size of the Pt nanoparticles was reduced to 1 nm. The results highlighted the important impact of size-induced oxidation state of Pt nanoparticles on catalytic selectivity as well as activity in gas-phase methanol oxidation reactions. PMID:23701488

  11. Size Effect of Gold Sol/γ-Alumina on the Catalytic Activities of CO Oxidation

    Institute of Scientific and Technical Information of China (English)

    WANG Wei-Hua; GAO Geng-Yu

    2006-01-01

    The relationship between particle size and catalytic activity of gold nanoparticle catalysts with γ-Al2O3 as support has been investigated. The catalysts were prepared via the gold sol with different particle sizes by micelle method, and their structures were characterized by HRTEM and XRD, respectively. Furthermore, the catalytic activities were tested by CO oxidation. Experimental results showed that the catalytic activity became much weaker when gold particles were increased from 3.2 to 6.6 nm. Additionally, the particle size was also a key factor to govern catalytic activity with regard to gold supported on TiO2 prepared by the methods of deposition-precipitation.

  12. Effects of Gas Velocity and Temperature on Nitric Oxide Conversion in Simulated Catalytic Converter

    OpenAIRE

    Sathaporn Chuepeng

    2012-01-01

    Problem statement: Gaseous emissions from gasoline engine such as carbon monoxide, unburned hydrocarbon and nitrogen oxides were usually reduced in three-way catalytic converter simultaneously around theoretical fuel and air combustion. Engine speed and load and other parameters were varied over a wide range of operating conditions, resulting in different exhaust gas composition and condition intake into catalytic converter. This work was studied the conversion of Nitric Oxide (NO) in exhaust...

  13. CATALYTIC WET AIR OXIDATION OF INDUSTRIAL EFFLUENTS USING A Pt CATALIST SUPPORTED ON MULTIWALLED CARBON NANOTUBES

    OpenAIRE

    Gabriel Ovejero; José L. Sotelo; Araceli Rodríguez; Ana Vallet; Juan García

    2011-01-01

    In this work, catalytic wet air oxidation in a batch reactor was studied by catalytic wet air oxidation to treat industrial wastewater. Basic Yellow 11, a basic dye, was employed as a model compound and platinum supported over multi-walled nanotubes (Pt/MWNT) was used as catalyst. Additionally, two different industrial wastewaters were tested. The results prove the high effectivity of this treatment, showing high extents of total organic carbon and toxicity removal of the final effluent. We c...

  14. Interactions Between Surface Reactions and Gas-phase Reactions in Catalytic Combustion and Their Influence on Ignition of HCCI Engine

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The catalytic combustion of methane in a microchannel whose surface was coated with platinum(Pt)catalyst was studied by numerical-simulation. The effects of gas-phase reactions on the whole catalytic combustion process were analyzed at a high inlet pressure. A sensitivity analysis of the detailed mechanisms of the surface reaction of methane on Pt revealed that the most sensitive reactions affecting the heterogeneous ignition are oxygen adsorption/desorption and methane adsorption, and the most sensitive reactions affecting the homogeneous ignition are OH and H2O adsorption/desorption. The combustion process of the homogeneous charge compression ignition(HCCI) engine whose piston face was coated with Pt catalyst was simulated. The effects of catalysis and the most sensitive reactions on the ignition timing and the concentration of the main intermediate species during the HCCI engine combustion are discussed. The results show that the ignition timing of the HCCI engine can be increased by catalysis, and the most sensitive reactions affecting the ignition timing of the HCCI engine are OH and H2O adsorption/desorption.

  15. The effect of microstructural properties of CoCr2O4 spinel oxides on catalytic combustion of dichloromethane

    Science.gov (United States)

    Liu, Jing-Di; Zhang, Ting-Ting; Jia, Ai-Pin; Luo, Meng-Fei; Lu, Ji-Qing

    2016-04-01

    It was found that a series of spinel CoCr2O4 oxides were very active and selective for dichloromethane combustion, and the best performance was obtained on a catalyst calcined at 600 °C (with a areal specific reaction rate of 3.41 × 10-8 molCH2Cl2 s-1 m-2 at 220 °C). Quantitative analyses revealed that Cr3+/Cr6+ cations could partially substitute Co3+ cations in the octahedral sites of the spinel oxide at high-temperature calcination and thus to enhanced reducibility and surface acidity of the oxide, which synergistically governed the observed catalytic behaviors. Moreover, it was found that high valent Cr species (Cr6+) played very important role in the reaction, with a much higher turnover frequency (2.2 × 10-3 s-1) than that of the Cr3+ (0.56 × 10-3 s-1).

  16. Catalytic Activity of Iridium Dioxide With Different Morphologies for Oxygen Reduction Reaction

    Institute of Scientific and Technical Information of China (English)

    WANG Guangjin; HUANG Fei; XU Tian; YU Yi; CHENG Feng; ZHANG Yue; PAN Mu

    2015-01-01

    Iridium dioxide with different morphologies (nanorod and nanogranular) is successfully prepared by a modiifed sol-gel and Adams methods. The catalytic activity of both samples for oxygen reduction reaction is investigated in an alkaline solution. The electrochemical results show that the catalytic activity of the nanogranular IrO2 sample is superior to that of the nanorod sample due to its higher onset potential for oxygen reduction reaction and higher electrode current density in low potential region. The results of Koutecky-Levich analysis indicate that the oxygen reduction reaction catalyzed by both samples is a mixture transfer pathway. It is dominated by four electron transfer pathway for both samples in high overpotential area, while it is controlled by two electron transfer process for both samples in low overpotential area.

  17. A non-chemically selective top-down approach towards the preparation of hierarchical TS-1 zeolites with improved oxidative desulfurization catalytic performance.

    Science.gov (United States)

    Du, Shuting; Chen, Xiaoxin; Sun, Qiming; Wang, Ning; Jia, Mingjun; Valtchev, Valentin; Yu, Jihong

    2016-02-28

    Hierarchical TS-1 zeolites with secondary macropores have been successfully prepared by using two different fluoride-containing chemical etching post-treated routes. Hierarchical TS-1 zeolites exhibited a chemical composition similar to that of the parent material and showed remarkably enhanced catalytic activity in oxidative desulfurization reaction. PMID:26846586

  18. Iridium ultrasmall nanoparticles, worm-like chain nanowires, and porous nanodendrites: One-pot solvothermal synthesis and catalytic CO oxidation activity

    Science.gov (United States)

    Zhang, Tao; Li, Shuai-Chen; Zhu, Wei; Ke, Jun; Yu, Jing-Wen; Zhang, Zhi-Ping; Dai, Lin-Xiu; Gu, Jun; Zhang, Ya-Wen

    2016-06-01

    We report a facile one-pot solvothermal synthesis of monodisperse iridium (Ir) ultrasmall (1.5-2.5 nm in diameter) nanoparticles (NPs), worm-like chain nanowires (NWs), and porous nanodendrites (NDs), for which CO oxidation reaction has been employed as a probe reaction to investigate the effects of nanoparticle size and surface-capping organics on the catalytic activities. Time-dependent experiments revealed that an oriented attachment mechanism induced by the strong adsorption of halide anions (Br- and I-) on specific facet of Ir nanoclusters or by decreasing the reduction rate of Ir precursors with changing their concentrations during the synthesis was responsible for the formation of Ir NWs and NDs. Annealing tests indicated that an O2-H2 atmosphere treatment turned out to be an effective measure to clean up the surface-capping organics of Ir NPs supported on commercial SiO2. Catalytic CO oxidation reaction illustrated that a significant improvement in the catalytic activity of CO oxidation reaction was achieved together with the changing of activation energies after such atmosphere treatment for the supported catalysts of the ultrasmall Ir NPs. It is noteworthy that this enhancement in catalytic activity could be ascribed to the changes in the surface status (including populations of Ir species in metallic and oxidized states, removal of surface capping organics, the variety of active sites, and total effective active site number) for the supported nanocatalysts during the atmosphere treatment.

  19. Catalytic Systems Containing p-Toluenesulfonic Acid for the Coupling Reaction of Formaldehyde and Methyl Formate

    Institute of Scientific and Technical Information of China (English)

    Kebing Wang; Jie Yao; Yue Wang; Gongying Wang

    2007-01-01

    The coupling reaction of formaldehyde (FA) and methyl formate (MF) to form methyl glycolate (MG) and methyl methoxy acetate(MMAc),catalyzed by p-toluenesulfonic acid(p-TsOH) as well as assisted by different kinds of solvents or Ni-containing compounds.had been investigated.The results showed that when the reaction was carried out at 140℃ with a molar ratio of FA to MF of 0.65:1,molar fraction of p-TsOH to total feedstock of 11.0%,and reaction time of 3 h,the yield of MG and MMAc Was 31.1% and 17.1%.respectively.p-TsOH catalyzed the coupling reaction by means of the synergistic catalysis of protonic acidity and soft basicity.Adding extra solvents to the reaction system Was unfavorable for the reaction.The composite catalytic system consisting of p-TsOH and NiX2(X=Cl,Br,I)exhibited a high catalytic performance for the coupling reaction,and NiX2 acted as a promoter in the reaction,whose promotion for the catalysis increased in the following order:NiCl2<NiBr2<NiI2.The present system is less corrosive when compared with the previous system,in which strong inorganic liquid acids were used as catalysts.

  20. Effects of carrier and Mn loading on supported manganese oxide catalysts for catalytic combustion of methane

    Institute of Scientific and Technical Information of China (English)

    Jinyan Hu; Wei Chu; Limin Shi

    2008-01-01

    Supported manganese oxide catalysts were prepared by incipient wetness impregnation method for methane cat-alytic combustion, and effects of the support (Al2O3, SiO2 and TiO2) and Mn loading were investigated. These catalysts were characterized with N2 adsorption, X-ray diffraction, X-ray photoelectron spectroscopy and temperature-programmed reduction techniques. Methane conversion varied in a large range depending on supports or Mn loading. Al2O3 supported 15% Mn cata-lyst exhibited better activity toward methane catalytic oxidation. The manganese state and oxygen species played an important role in the catalytic performance.

  1. UV-Shielding and Catalytic Characteristics of Nanoscale Zinc-Cerium Oxides

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Fine particles of zinc-cerium oxides (ZCO) used as an ultraviolet filter were prepared via combustion synthesis route. The catalytic activity, UV-shielding performance, surface modification and application of ZCO in polyester varnish were discussed in detail. The experimental results indicate that the photo-catalytic activity of ZCO is much smaller than these of ZnO and TiO2; the oxidation catalytic activity of ZCO is far lower than that of CeO2; the ZCO has shown excellent ultraviolet absorption in the range of UV;addition modified ZCO (MZCO) into polyester will enhance the UV-shielding capability of polyester.

  2. Superior Fe-ZSM-5 catalyst for selective catalytic reduction of nitric oxide by ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Long, R.Q.; Yang, R.T. [Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemical Engineering

    1999-06-16

    Nitrogen oxides in the exhaust gases from combustion of fossil fuels remain a major source for air pollution and acid rain. The current technology for reducing NO{sub x} (NO + NO{sub 2}) emissions from power plants is selective catalytic reduction (SCR) with ammonia in the presence of oxygen. For the SCR reaction, V{sub 2}O{sub 5} + WO{sub 3} (or MoO{sub 3}) supported on TiO{sub 2} are the commercial catalysts. The mechanism of the reaction on the vanadia catalysts has been studied extensively, and several different mechanisms have been proposed. Ion-exchanged zeolite catalysts have also been studied, e.g., Fe-Y, Cu-ZSM-5, and Fe-ZSM-5, but the reported activities were lower than that of the commercial vanadia catalysts. The SCR technology based on vanadia catalysts is being used in Europe and Japan and is being quickly adopted in the US. However, problems associated with vanadia catalysts remain, e.g., high activity for oxidation of SO{sub 2} to SO{sub 3}, toxicity of vanadia, and formation of N{sub 2}O at high temperature. Hence, there are continuing efforts in developing new catalysts. In this paper, the authors report a superior Fe-ZSM-5 catalyst that is much more active than the commercial vanadia catalysts and does not have the deficiencies that are associated with the vanadia catalysts.

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

    Energy Technology Data Exchange (ETDEWEB)

    Larsson, Per-Olof

    1999-05-01

    can be due to an epitaxial relationship during reaction conditions, or that the CeO{sub 2}(001) surface has a greater ability, compared with the CeO{sub 2}(111) surface, to assist the copper oxide in changing valences and supplying oxygen to the CO. A CuO{sub x}-CeO{sub 2}/Al{sub 2}O{sub 3} catalyst was more active than a CuMn{sub 2}O{sub 4}/Al{sub 2}O{sub 3} catalyst for CO oxidation, but the CuMn{sub 2}O{sub 4}/Al{sub 2}O{sub 3} catalyst was more active for combustion of ethyl acetate and ethanol. This shows that the activity order for complete oxidation over different metal oxide catalysts depends on the combustible component. In addition, these metal oxide catalysts were found to be more active than a Pt/Al{sub 2}O{sub 3} catalyst for the combustion of ethyl acetate and ethanol. However, for methanol and formaldehyde combustion the Pt/Al{sub 2}O{sub 3} catalyst was the best alternative. Consequently, catalytic waste gas incineration can be more efficient by using the right type of catalyst in each application. By-products as acetaldehyde and acetic acid were observed during catalytic combustion of an ethyl acetate/ethanol mixture. However, in stationary catalytic incineration it is easy to secure complete oxidation to CO{sub 2} and H{sub 2}O 61 refs, 29 figs, 4 tabs

  4. Bio-inspired immobilization of metal oxides on monolithic microreactor for continuous Knoevenagel reaction.

    Science.gov (United States)

    Song, Wentong; Shi, Da; Tao, Shengyang; Li, Zhaoliang; Wang, Yuchao; Yu, Yongxian; Qiu, Jieshan; Ji, Min; Wang, Xinkui

    2016-11-01

    A facile method is reported to construct monolithic microreactor with high catalytic performance for Knoevenagel reaction. The microreactor is based on hierarchically porous silica (HPS) which has interconnected macro- and mesopores. Then the HPS is surface modified by pyrogallol (PG) polymer. Al(NO3)3 and Mg(NO3)2 are loaded on the surface of HPS through coordination with -OH groups of PG. After thermal treatment, Al(NO3)3 and Mg(NO3)2 are converted Al2O3 and MgO. The as-synthesized catalytic microreactor shows a high and stable performance in Knoevenagel reaction. The microreactor possess large surface area and interconnected pore structures which are beneficial for reactions. Moreover, this economic, facile and eco-friendly surface modification method can be used in loading more metal oxides for more reactions. PMID:27459172

  5. Thermal catalytic oxidation of octachloronaphthalene over anatase TiO2 nanomaterial and its hypothesized mechanism

    Science.gov (United States)

    Su, Guijin; Li, Qianqian; Lu, Huijie; Zhang, Lixia; Huang, Linyan; Yan, Li; Zheng, Minghui

    2015-12-01

    As an environmentally-green technology, thermal catalytic oxidation of octachloronaphthalene (CN-75) over anatase TiO2 nanomaterials was investigated at 300 °C. A wide range of oxidation intermediates, which were investigated using various techniques, could be of three types: naphthalene-ring, single-benzene-ring, and completely ring-opened products. Reactive oxygen species on anatase TiO2 surface, such as O2-• and O2-, contributed to oxidative degradation. Based on these findings, a novel oxidation degradation mechanism was proposed. The reaction at (101) surface of anatase TiO2 was used as a model. The naphthalene-ring oxidative products with chloronaphthols and hydroxyl-pentachloronaphthalene-dione, could be formed via attacking the carbon of naphthalene ring at one or more positions by nucleophilic O2-. Lateral cleavage of the naphthalene ring at different C1-C10 and C4-C9, C1-C2 and C4-C9, C1-C2 or and C3-C4 bond positions by electrophilic O2-• could occur. This will lead to the formation of tetrachlorophenol, tetrachloro-benzoic acid, tetrachloro-phthalaldehyde, and tetrachloro-acrolein-benzoic acid, partially with further transformation into tetrachlorobenzene-dihydrodiol and tetrachloro-salicylic acid. Unexpectedly, the symmetric half section of CN-75 could be completely remained with generating the intricate oxidative intermediates characteristically containing tetrachlorobenzene structure. Complete cleavage of naphthalene ring could produce the ring-opened products, such as formic and acetic acids.

  6. The effect of outside conditions on anaerobic ammonia oxidation reaction

    Institute of Scientific and Technical Information of China (English)

    YANG Min; WANG Shu-bo

    2016-01-01

    Organic carbon, inorganic carbon, temperature, pH and ORP are all to have a certain influence on the anaerobic ammonia oxidation reaction. We can draw some conclusions on the optimum conditions of anaerobic ammonia oxidation reaction. The optimum temperature of the anaerobic ammonia oxidation reaction is 30-35℃. And the optimum pH of the anaerobic ammonia reaction is 7.5-8.3. The presence of organic matters can affect the anaerobic ammonia reaction, and different organic matters have different influence on it. The concentration of the inorganic carbon also exist great influence on the reaction. High inorganic carbon concentration also can inhibit anaerobic ammonia oxidation reaction.

  7. Effect of Mg/Al atom ratio of support on catalytic performance of Co-Mo/MgO-Al2O3 catalyst for water gas shift reaction

    Institute of Scientific and Technical Information of China (English)

    Yixin Lian; Huifang Wang; Quanxing Zheng; Weiping Fang; Yiquan Yang

    2009-01-01

    Co-Mo-based catalysts supported on mixed oxide supports MgO-Al2O3 with different Mg/Al atom ratios for water gas shift reaction were studied by means of TPR, Raman, XPS and ESR. It was found that the octahedral Mo species in oxidized Co-Mo/MgO(x)-Al2O3 catalyst and the contents of Mo5+, Mo4+, S2- and S2-2 species in the functioning catalysts increased with increasing the Mg/Al atom ratio of the support under the studied experimental conditions. This is favorable for the formation of the active Co-Mo-S phase of the catalysts. Catalytic performance testing results showed that the catalysts Co-Mo/MgO-Al2O3 with the Mg/Al atom ratio of the support in the range of 0.475-0.525 exhibited optimal catalytic activity for the reaction.

  8. Pretreatment of apramycin wastewater by catalytic wet air oxidation

    Institute of Scientific and Technical Information of China (English)

    YANG Shao-xia; FENG Yu-jie; WAN Jia-feng; LIN Qing-ying; ZHU Wan-peng; JIANG Zhan-peng

    2005-01-01

    The pretreatment technology of wet air oxidation(WAO) and coagulation and acidic hydrolysis for apramycin wastewater was investigated in this paper. The COD, apramycin, NH4+ concentration, and the ratio of BOD5/COD were analyzed, and the color and odor of the effluent were observed. WAO of apramycin wastewater, without catalyst and with RuO2/Al2 O3 and RuO2-CeO2/Al2 O3 catalysts, was carried out at degradation temperature of 200℃ and the total pressure of 4 MPa in a 1 L batch reactor. The result showed that the apramycin removals were respectively 50.2% and 55.0%, COD removals were 40.0% and 46.0%, and the ratio of BOD5/COD was increased to 0.49 and 0.54 with RuO2/Al2 O3 and RuO2-CeO2/Al2 O3 catalysts in catylytic wet air oxidation(CWAO) after the reaction of 150 min. With the pretreatment of coagulation and acidic hydrolysis, COD and apramycin removals were slight decreased, and the ratio of BOD5/COD was increased to 0.45, and the effluents was not suitable to biological treatment. The color and odor of the wastewater were the apramycin wastewater. The addition of CeO2 could promote the activity and stability of RuO2/Al2 O3 in WAO of apramycin wastewater.

  9. Catalytic defluorination of perfluorinated aromatics under oxidative conditions using N-bridged diiron phthalocyanine.

    Science.gov (United States)

    Colomban, Cédric; Kudrik, Evgenij V; Afanasiev, Pavel; Sorokin, Alexander B

    2014-08-13

    Carbon-fluorine bonds are the strongest single bonds in organic chemistry, making activation and cleavage usually associated with organometallic and reductive approaches particularly difficult. We describe here an efficient defluorination of poly- and perfluorinated aromatics under oxidative conditions catalyzed by the μ-nitrido diiron phthalocyanine complex [(Pc)Fe(III)(μ-N)Fe(IV)(Pc)] under mild conditions (hydrogen peroxide as the oxidant, near-ambient temperatures). The reaction proceeds via the formation of a high-valent diiron phthalocyanine radical cation complex with fluoride axial ligands, [(Pc)(F)Fe(IV)(μ-N)Fe(IV)(F)(Pc(+•))], which was isolated and characterized by UV-vis, EPR, (19)F NMR, Fe K-edge EXAFS, XANES, and Kβ X-ray emission spectroscopy, ESI-MS, and electrochemical techniques. A wide range of per- and polyfluorinated aromatics (21 examples), including C6F6, C6F5CF3, C6F5CN, and C6F5NO2, were defluorinated with high conversions and high turnover numbers. [(Pc)Fe(III)(μ-N)Fe(IV)(Pc)] immobilized on a carbon support showed increased catalytic activity in heterogeneous defluorination in water, providing up to 4825 C-F cleavages per catalyst molecule. The μ-nitrido diiron structure is essential for the oxidative defluorination. Intramolecular competitive reactions using C6F3Cl3 and C6F3H3 probes indicated preferential transformation of C-F bonds with respect to C-Cl and C-H bonds. On the basis of the available data, mechanistic issues of this unusual reactivity are discussed and a tentative mechanism of defluorination under oxidative conditions is proposed.

  10. Selective Production of Aromatic Aldehydes from Heavy Fraction of Bio-oil via Catalytic Oxidation

    International Nuclear Information System (INIS)

    High value-added aromatic aldehydes (e. g. vanillin and syringaldehyde) were produced from heavy fraction of bio-oil (HFBO) via catalytic oxidation. The concept is based on the use of metalloporphyin as catalyst and hydrogen peroxide (H2O2) as oxidant under alkaline condition. The biomimetic catalyst cobalt(II)-sulfonated tetraphenylporphyrin (Co(TPPS4)) was prepared and characterized. It exhibited relative high activity in the catalytic oxidation of HFBO. 4.57 wt % vanillin and 1.58 wt % syringaldehyde were obtained from catalytic oxidation of HFBO, compared to 2.6 wt % vanillin and 0.86 wt % syringaldehyde without Co(TPPS4). Moreover, a possible mechanism of HFBO oxidation using Co(TPPS4)/H2O2 was proposed by the research of model compounds. The results showed that this is a promising and environmentally friendly method for production of aromatic aldehydes from HFBO under Co(TPPS4)/H2O2 system

  11. Magnetic carbon xerogels for the catalytic wet peroxide oxidation of 4-nitrophenol solutions

    OpenAIRE

    Ribeiro, R; Silva, Adrián; Faria, Joaquim; Gomes, Helder

    2015-01-01

    Catalytic wet peroxide oxidation (CWPO) is a well-known advanced oxidation process for the removal of organic pollutants from industrial process waters and wastewater. Specifically, CWPO employs hydrogen peroxide (H2O2) as oxidation source and a suitable catalyst to promote its decomposition via formation of hydroxyl radicals (HO•), which exhibit high oxidizing potential and serve as effective species in the destruction of a huge range of organic pollutants

  12. Preparation of rare-earth metal complex oxide catalysts for catalytic wet air oxidation

    Institute of Scientific and Technical Information of China (English)

    LI Ning; LI Guangming; YAO Zhenya; ZHAO Jianfu

    2007-01-01

    Catalytic wet air oxidation(CWAO)is one of the most promising technologies for pollution abatement.Developing catalysts with high activity and stability is crucial for the application of the CWAO process.The Mn/Ce complex oxide catalyrsts for CWAO of high concentration phenol containing wastewater were prepared by coprecipitation.The catalyst preparation conditions were optimized by using an orthogonal layout method and single-factor experimental analysis.The Mn/Ce serial catalysts were characterized by Brunauer-Emmett-Teller(BET)analysis and the metal cation leaching was measured by inductively coupled plasma torch-atomic emission spectrometry(ICP-AES).The results show that the catalysts have high catalytic activities even at a low temperature(80℃)and low oxygen partial pressure(0.5 MPa)in a batch reactor.The metallic ion leaching is comparatively low(Mn<6.577 mg/L and Ce<0.6910 mg/L,respectively)in the CWAO process.The phenol,CODCD and TOC removal efficiencies in the solution exceed 98.5% using the optimal catalyst(named CSP).The new catalyst would have a promising application in CWAO treatment of high concentration organic wastewater.

  13. Chemical oxidation of anthracite with hydrogen peroxide via the Fenton reaction

    Science.gov (United States)

    Heard, I.; Senftle, F.E.

    1984-01-01

    Solutions of 30% H2O2 ranging from pH = 0 to pH = 11.5 have been used to oxidize anthracite at room temperature. The inorganic impurities, primarily pyrite, catalysed the oxidation and reduction of H2O2 (the Fenton reaction) to form the hydroxyl radical; the oxidation of the organic matter was minimal and was observed only in strong acidic solutions (pH reactions were completed in a much shorter time, the oxidation mechanism must have been of a different nature than that for the untreated anthracite. A qualitative model based on the catalytic decomposition of H2O2 by activated carbon sites in the coal surface is used to explain the oxidation of the demineralized anthracite. ?? 1984.

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

    Science.gov (United States)

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

    2016-08-01

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

  15. Catalytic performance and structural characterization of ferric oxide and its composite oxides supported gold catalysts for low-temperature CO oxidation

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The preparation and catalytic activity of ferric oxide and its composite oxides supported gold catalysts for Iow-temperature CO oxidation were investigated detailedly, and characterized extensively by XRD, XPS, TPR, EC and XAFS techniques. It was found that containing highly dis persed Au of partially oxidized state, these nano-structured oxides supported Au/Fe2O3 and Au/NiFe2O4 catalysts had higher Iow-temperature activities. The possible catalytic active center is the gold of partially oxidized state (Auζ+).

  16. Catalytic oxidation with Al-Ce-Fe-PILC as a post-treatment system for coffee wet processing wastewater.

    Science.gov (United States)

    Sanabria, Nancy R; Peralta, Yury M; Montañez, Mardelly K; Rodríguez-Valencia, Nelson; Molina, Rafael; Moreno, Sonia

    2012-01-01

    The effluent from the anaerobic biological treatment of coffee wet processing wastewater (CWPW) contains a non-biodegradable compound that must be treated before it is discharged into a water source. In this paper, the wet hydrogen peroxide catalytic oxidation (WHPCO) process using Al-Ce-Fe-PILC catalysts was researched as a post-treatment system for CWPW and tested in a semi-batch reactor at atmospheric pressure and 25 °C. The Al-Ce-Fe-PILC achieved a high conversion rate of total phenolic compounds (70%) and mineralization to CO(2) (50%) after 5 h reaction time. The chemical oxygen demand (COD) of coffee processing wastewater after wet hydrogen peroxide catalytic oxidation was reduced in 66%. The combination of the two treatment methods, biological (developed by Cenicafé) and catalytic oxidation with Al-Ce-Fe-PILC, achieved a 97% reduction of COD in CWPW. Therefore, the WHPCO using Al-Ce-Fe-PILC catalysts is a viable alternative for the post-treatment of coffee processing wastewater. PMID:22907449

  17. Catalytic performance of cerium iron complex oxides for partial oxidation of methane to synthesis gas

    Institute of Scientific and Technical Information of China (English)

    LI Kongzhai; WANG Hua; WEI Yonggang; LIU Mingchun

    2008-01-01

    The cerium iron complex oxides oxygen carder was prepared by the co-precipitation method. The reactions between methane and lattice oxygen from the complex oxides were investigated in a fixed micro-reactor system. The reduced oxygen carrier could be re-oxidized by air and its initial state could be restored. The characterizations of the oxygen carriers were studied using XRD, O2-TPD, and H2-TPR. The results showed that the bulk lattice oxygen of CeO2-Fe2O3 was found to be suitable for the partial oxidation of methane to synthesis gas. There were two kinds of oxygen species on the oxygen carder: the stronger oxygen species that was responsible for the complete oxidation of methane, and the weaker oxygen species (bulk lattice oxygen) that was responsible for the selective oxidation of methane to CO and H2 at a higher temperature. Then, the lost bulk lattice oxygen could be selectively supplemented by air re-oxidation at an appropriate reaction con-dition. CeFeO3 appeared on the oxygen carrier after 10 successive redox cycles, however, it was not bad for the selectivity of CO and H2.

  18. Atomization energy approach to the quantitative evaluation of catalytic activities of metal oxides during dehydrogenation of MgH{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Hirate, H., E-mail: hirate@silky.numse.nagoya-u.ac.jp [Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya University, Furo-Cho, Chikusa-Ku, Nagoya 464-8603 (Japan); Morinaga, M.; Yukawa, H. [Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya University, Furo-Cho, Chikusa-Ku, Nagoya 464-8603 (Japan); Nakai, H. [Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, Okubo, Shinjuku-ku, Tokyo, 169-8555 (Japan)

    2011-09-15

    Research highlights: > Study of catalytic reaction on MgH{sub 2} and NaAlH{sub 4} using atomization energy concept. > Quantitative evaluation of catalytic activities of metal oxide for MgH{sub 2}. > Quantitative evaluation of catalytic activities of metal chlorides for NaAlH{sub 4}. > Observation of the O-H stretching mode on Nb{sub 2}O{sub 5}-catalyzed MgH{sub 2} in FT-IR. - Abstract: The hydrogen desorption reaction of magnesium hydride (MgH{sub 2}), MgH{sub 2} {yields} Mg + H{sub 2}, is accelerated by mixing catalytic metal oxides (e.g., Nb{sub 2}O{sub 5}). This catalytic effect is evaluated quantitatively using the atomization energy concept. The measured hydrogen desorption rate increases monotonously with increasing y x {Delta}E{sub O} values of metal oxides, M{sub x}O{sub y}. Here, {Delta}E{sub O,} is the atomization energy for the oxide ion in M{sub x}O{sub y}. This indicates that the oxide ion interacts mainly with hydrogen atom in MgH{sub 2}, in agreement with the observation of the O-H stretching mode in the FT-IR spectra during the dehydrogenation of the Nb{sub 2}O{sub 5}-catalyzed MgH{sub 2}. This approach is also proved to be useful for the catalytic analysis of metal chlorides (e.g., TiCl{sub 3}) on the decomposition reaction of NaAlH{sub 4} expressed as, NaAlH{sub 4} {yields} (1/3)Na{sub 3}AlH{sub 6} + (2/3)Al + H{sub 2}

  19. Catalytic combustion of soot over Ru-doped mixed oxides catalysts

    Institute of Scientific and Technical Information of China (English)

    LF Nascimento; RF Martins; OA Serra

    2014-01-01

    We employed modified substrates as outer heterogeneous catalysts to reduce the soot originating from the incomplete die-sel combustion. Here, we proposed that ceria (CeO2)-based catalysts could lower the temperature at which soot combustion occurred from 610 ºC to values included in the operation range of diesel exhausts (270-400 ºC). Here, we used the sol-gel method to synthesize catalysts based on mixed oxides (ZnO:CeO2) deposited on cordierite substrates, and modified by ruthenium nanoparticles. The presence of ZnO in these mixed oxides produced defects associated with oxygen vacancies, improving thermal stability, redox potential, sulfur resistance, and oxygen storage. We evaluated the morphological and structural properties of the material by X-ray diffraction (XRD), Brumauer-emmett-teller method (BET), temperature programmed reduction (H2-TPR), scanning electron micros-copy (SEM), and transmission electron microscopy (TEM). We investigated how the addition of Ru (0.5 wt.%) affected the catalytic activity of ZnO:CeO2 in terms of soot combustion. Thermogravimetric analysis (TG/DTA) revealed that presence of the catalyst de-creased the soot combustion temperature by 250 ºC, indicating that the oxygen species arose at low temperatures, which was the main reason for the high reactivity of the oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy (DRS) showed that the catalyst containing Ru on the mixed oxide-impregnated cordierite samples efficiently oxidized soot in a diesel stationary motor:soot emission decreased 80%.

  20. Catalytic Oxidative Conversion from Naphthol to 2-Hydroxy-1, 4-naphthoquinone over Iron Porphyrin Catalysts by Molecular Oxygen in an Alkaline 2-Propanol Solution

    Institute of Scientific and Technical Information of China (English)

    YANG Ke-er; TONG Shan-ling; YAN Yan; KANG En-hua; XIAO Feng-shou; LI Qing; CHANG Xin; FANG Chi-guang

    2005-01-01

    In an alkaline 2-propanol solution with 5,10,15,20-tetra(4-methoxyl phenyl) porphyrin iron chloride(TOMPPFeCl) as a catalyst and oxygen as a cheap green oxidant, 2-naphthol was conversed to 2-hydroxy-1,4-naphthoquinone(HNQ) with a yield of 62.17% and a selectivity of 100%, and the conversion number of TMOPPFeCl catalyst was 8.32/min. The catalytic oxidation products were characterized by means of UV-Vis, IR, GC-MS, 1H NMR and melting point determination. In this catalytic oxidation, the catalytic activity of TMOPPFeCl was researched in detail and the reacting conditions were optimized. A possible reaction mechanism is summarized based on in situ EPR determination.

  1. Modeling the Catalysis of Anti-Cocaine Catalytic Antibody: Competing Reaction Pathways and Free Energy Barriers

    OpenAIRE

    Pan, Yongmei; Gao, Daquan; Zhan, Chang-Guo

    2008-01-01

    The competing reaction pathways and the corresponding free energy barriers for cocaine hydrolysis catalyzed by an anti-cocaine catalytic antibody, mAb 15A10, were studied by using a novel computational strategy based on the binding free energy calculations on the antibody binding with cocaine and transition states. The calculated binding free energies were used to evaluate the free energy barrier shift from the cocaine hydrolysis in water to the antibody-catalyzed cocaine hydrolysis for each ...

  2. Heterogeneous catalytic oxidative dehydrogenation of ethylbenzene to styrene with carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Badstube, T.; Papp, H. [Leipzig Univ. (Germany). Inst. fuer Technische Chemie; Kustrowski, P.; Dziembaj, R. [Jagiellonian Univ., Crakow (Poland). Faculty of Chemistry

    1998-12-31

    Alkaline promoted active carbon supported iron catalysts are very active in the oxidative dehydrogenation of ethylbenzene to styrene in the presence of carbon dioxide. The best results were obtained at 550 C for a Li-promoted catalyst with a conversion of ethylbenzene of 75% and a selectivity towards styrene of nearly 95%. These results are better than those obtained with industrial catalysts which perform the dehydrogenation process with an excess of water. The main product of the dehydrogenation reaction with CO{sub 2} was styrene, but the following by-products were detected - benzene and toluene. The selectivity towards toluene was always higher than towards benzene. We observed also the formation of carbon monoxide and water, which were produced with a constant molar ratio of about 0.8. The weight of the catalysts increased up to 20% during the reaction due to deposition of carbon. Using a too large excess of CO{sub 2} (CO{sub 2}/EB>10) was harmful for the styrene yield. The most favorable molar ratio of CO{sub 2} to EB was 10:1. No correlation between the molar ratios of reactants and the amount of deposited coke on the surface of catalysts was observed. The highest catalytic activity showed iron loaded D-90 catalysts which were promoted with alkali metals in a molar ratio of 1:10. Iron, nickel and cobalt loaded carbonized PPAN, PC, inorganic supports like Al{sub 2}O{sub 3}, SiO{sub 2}/ZrO{sub 2} or TiO{sub 2} respectively and commercial iron catalysts applied for styrene production did not show comparable catalytic activity in similar conditions. (orig.)

  3. Advances and perspectives in catalytic oxidation of hydrocarbons in liquid phase

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    This review article summarizes recent advances in catalytic oxidation of hydrocarbons, especially presents two strategies for activation of C-H bonds or molecular oxygen. Based on our own research results, the applications of the two methods in the oxidation of cyclohexane, toluene and ethyl benzene, etc. are introduced, and the perspectives of the two methods are also discussed.

  4. Method and apparatus for a catalytic firebox reactor

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Lance L. (North Haven, CT); Etemad, Shahrokh (Trumbull, CT); Ulkarim, Hasan (Hamden, CT); Castaldi, Marco J. (Bridgeport, CT); Pfefferle, William C. (Madison, CT)

    2001-01-01

    A catalytic firebox reactor employing an exothermic catalytic reaction channel and multiple cooling conduits for creating a partially reacted fuel/oxidant mixture. An oxidation catalyst is deposited on the walls forming the boundary between the multiple cooling conduits and the exothermic catalytic reaction channel, on the side of the walls facing the exothermic catalytic reaction channel. This configuration allows the oxidation catalyst to be backside cooled by any fluid passing through the cooling conduits. The heat of reaction is added to both the fluid in the exothermic catalytic reaction channel and the fluid passing through the cooling conduits. After discharge of the fluids from the exothermic catalytic reaction channel, the fluids mix to create a single combined flow. A further innovation in the reactor incorporates geometric changes in the exothermic catalytic reaction channel to provide streamwise variation of the velocity of the fluids in the reactor.

  5. Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

    Science.gov (United States)

    Dang-Long, T.; Quang-Tuyen, T.; Shiratori, Y.

    2016-06-01

    Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH4 and CO2 and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidate for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO2 reforming of CH4 and electrochemical oxidation of the produced syngas (H2-CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH4-CO2 mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO2 had strong influences on both reaction processes. The increase in CO2 partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH4-CO2 mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.

  6. Direct Formation of Oxocarbenium Ions under Weakly Acidic Conditions: Catalytic Enantioselective Oxa-Pictet-Spengler Reactions.

    Science.gov (United States)

    Zhao, Chenfei; Chen, Shawn B; Seidel, Daniel

    2016-07-27

    Two catalysts, an amine HCl salt and a bisthiourea, work in concert to enable the generation of oxocarbenium ions under mild conditions. The amine catalyst generates an iminium ion of sufficient electrophilicity to enable 1,2-attack by an alcohol. Catalyst turnover is achieved by amine elimination with concomitant formation of an oxocarbenium intermediate. The bisthiourea catalyst accelerates all of the steps of the reaction and controls the stereoselectivity via anion binding/ion pair formation. This new concept was applied to direct catalytic enantioselective oxa-Pictet-Spengler reactions of tryptophol with aldehydes. PMID:27396413

  7. Continuous-flow stereoselective organocatalyzed Diels-Alder reactions in a chiral catalytic "homemade" HPLC column.

    Science.gov (United States)

    Chiroli, Valerio; Benaglia, Maurizio; Cozzi, Franco; Puglisi, Alessandra; Annunziata, Rita; Celentano, Giuseppe

    2013-07-19

    Continuous-flow organocatalyzed Diels-Alder reactions have been performed with excellent enantioselectivity for the first time in a chiral "homemade" HPLC column, packed with silica on which a MacMillan catalyst has been supported by a straightforward immobilization procedure. The versatility of the system was also proven by running with the same column continuous-flow stereoselective reactions with three different substrates, showing that the catalytic reactor may efficiently work in continuo for more than 150 h; the regeneration of the HPLC column was also demonstrated, allowing to further extend the activity of the reactor to more than 300 operating hours. PMID:23808663

  8. In-situ Scanning Transmission X-ray Microscopy of catalytic materials under reaction conditions

    Science.gov (United States)

    de Smit, Emiel; Creemer, J. Fredrik; Zandbergen, Henny W.; Weckhuysen, Bert M.; de Groot, Frank M. F.

    2009-11-01

    In-situ Scanning X-ray Transmission Microscopy (STXM) allows the measurement of the soft X-ray absorption spectra with 10 to 30 nm spatial resolution under realistic reaction conditions. We show that STXM-XAS in combination with a micromachined nanoreactor can image a catalytic system under relevant reaction conditions, and provide detailed information on the morphology and composition of the catalyst material. The nanometer resolution combined with powerful chemical speciation by XAS and the ability to image materials under realistic conditions opens up new opportunities to study many chemical processes.

  9. In-situ Scanning Transmission X-ray Microscopy of catalytic materials under reaction conditions

    Energy Technology Data Exchange (ETDEWEB)

    Smit, Emiel de; Weckhuysen, Bert M; Groot, Frank M F de [Inorganic Chemistry and Catalysis group, Debye Institute for Nanomaterials Science, Utrecht University, Sorbonnelaan 16, 3584 CA Utrecht (Netherlands); Creemer, J Fredrik [DIMES-ECTM, Delft University of Technology, 2600 GB Delft (Netherlands); Zandbergen, Henny W, E-mail: e.desmit@uu.n [Kavli Institute of NanoScience, National Centre for High Resolution Electron Microscopy, Delft University of Technology, 2600 GA Delft (Netherlands)

    2009-11-15

    In-situ Scanning X-ray Transmission Microscopy (STXM) allows the measurement of the soft X-ray absorption spectra with 10 to 30 nm spatial resolution under realistic reaction conditions. We show that STXM-XAS in combination with a micromachined nanoreactor can image a catalytic system under relevant reaction conditions, and provide detailed information on the morphology and composition of the catalyst material. The nanometer resolution combined with powerful chemical speciation by XAS and the ability to image materials under realistic conditions opens up new opportunities to study many chemical processes.

  10. Catalytic wet-air oxidation of lignin in a three-phase reactor with aromatic aldehyde production

    Directory of Open Access Journals (Sweden)

    Sales F.G.

    2004-01-01

    Full Text Available In the present work a process of catalytic wet air oxidation of lignin obtained from sugar-cane bagasse is developed with the objective of producing vanillin, syringaldehyde and p-hydroxybenzaldehyde in a continuous regime. Palladium supported on g-alumina was used as the catalyst. The reactions in the lignin degradation and aldehyde production were described by a kinetic model as a system of complex parallel and series reactions, in which pseudo-first-order steps are found. For the purpose of producing aromatic aldehydes in continuous regime, a three-phase fluidized reactor was built, and it was operated using atmospheric air as the oxidizer. The best yield in aromatic aldehydes was of 12%. The experimental results were compatible with those values obtained by the pseudo-heterogeneous axial dispersion model (PHADM applied to the liquid phase.

  11. Synthesis, Characterization, and Catalytic Applications of Transition Metal Oxide/Carbonate Nanomaterials

    Science.gov (United States)

    Jin, Lei

    2011-12-01

    This thesis contains two parts: 1) Studies of novel synthesis methods and characterization of advanced functional manganese oxide octahedral molecular sieves (OMS) and their applications in Li/Air batteries, solvent free toluene oxidations, and ethane oxydehydrogenation (ODH) in the presence of CO2, recycling the green house gas. 2) Development of unique Ln2O2CO3 (Ln = rare earth) layered materials and ZnO/La2O2CO3 composites as clean energy biofuel catalysts. These parts are separated into five different focused topics included in this thesis. The first topic presents studies of catalytic activities of a single step synthesized gamma-MnO2 octahedral molecular sieve nano fiber in solvent free atmospheric oxidation of toluene with molecular oxygen. Solvent free atmospheric oxidation of toluene is a notoriously difficult liquid phase oxidation process due to the challenge of oxidizing sp³ hybridized carbon in inactive hydrocarbons. The synthesized gamma-MnO2 showed excellent catalytic activity and good selectivity under the mild atmospheric reflux system. Under optimized conditions, a 47.8% conversion of toluene, along with 57% selectivity of benzoic acid and 15% of benzaldehyde were obtained. The effects of reaction time, amount of catalyst and initiator, and the reusability of the catalyst were investigated. The second topic involves developing titanium containing gamma-MnO 2 (TM) hollow spheres as electrocatalysts in Li/Air Batteries. Li/air batteries have recently attracted interest because they have the largest theoretical specific energy (11,972 Wh.kg-1) among all practical electrochemical couples. In this study, unique hollow aspheric materials were prepared for the first time using a one-step synthesis method and fully characterized by various techniques. These prepared materials were found to have excellent electrocatalytic activation as cathode materials in lithium-air batteries with a very high specific capacity (up to 2.3 A.h/g of carbon). The third

  12. Synthesis, characterization, crystal structure determination and catalytic activity in epoxidation reaction of two new oxidovanadium(IV) Schiff base complexes

    Science.gov (United States)

    Tahmasebi, Vida; Grivani, Gholamhossein; Bruno, Giuseppe

    2016-11-01

    The five coordinated vanadium(IV) Schiff base complexes of VOL1 (1) and VOL2 (2), HL1 = 2-{(E)-[2-bromoethyl)imino]methyl}-2- naphthol, HL2 = 2-{(E)-[2-chloroethyl)imino]methyl}-2- naphthol, have been synthesized and they were characterized by using single-crystal X-ray crystallography, elemental analysis (CHN) and FT-IR spectroscopy. Crystal structure determination of these complexes shows that the Schiff base ligands (L1 and L2) act as bidentate ligands with two phenolato oxygen atoms and two imine nitrogen atoms in the trans geometry. The coordination geometry around the vanadium(IV) is distorted square pyramidal in which vanadium(IV) is coordinated by two nitrogen and two oxygen atoms of two independent ligands in the basal plane and by one oxygen atom in the apical position. The catalytic activity of the Schiff base complexes of 1 and 2 in the epoxidation of alkenes were investigated using different reaction parameters such as solvent effect, oxidant, alkene/oxidant ratio and the catalyst amount. The results showed that in the presence of TBHP as oxidant in 1: 4 and 1:3 ratio of the cyclooctene/oxidant ratio, high epoxide yield was obtained for 1 (76%) and 2 (80%) with TON(= mole of substrate/mole of catalyst) of 27 and 28.5, respectively, in epoxidation of cyclooctene.

  13. Understanding Catalytic Activity Trends for NO Decomposition and CO Oxidation using Density Functional Theory and Microkinetic Modeling

    DEFF Research Database (Denmark)

    Falsig, Hanne

    towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional theory calculations. We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition......The main aim of this thesis is to understand the catalytic activity of transition metals and noble metals for the direct decomposition of NO and the oxidation of CO. The formation of NOx from combustion of fossil and renewable fuels continues to be a dominant environmental issue. We take one step......-metal surfaces by combining a database of adsorption energies on stepped metal surfaces with known Brønsted–Evans–Polanyi (BEP) relations for the activation barriers of dissociation of diatomic molecules over stepped transition- and noble-metal surfaces. The potential energy diagram directly points to why Pd...

  14. Selective catalytic reduction of nitrogen oxides with ammonia over microporous zeolite catalysts

    OpenAIRE

    VENNESTROM, PETER NICOLAI RAVNBORG

    2014-01-01

    With increasing legislative demands to remove nitrogen oxides (NOx) from automotive diesel exhaust, new catalyst systems are investigated and intensely studied in industry as well in academia. The most prevailing catalytic method of choice is the selective catalytic reduction (SCR) where non-toxic urea is used as a reductant for practical reasons. Usually urea is stored in a separate tank and once injected into the exhaust system it hydrolyses into the more aggressive reductant NH3 and CO2. ...

  15. Preparation of thin film gold based catalysts for oxidation reactions in liquid and gas phases

    International Nuclear Information System (INIS)

    This work deals with the preparation of gold on titania catalysts to make catalytic films in the less than 100 nm thickness area and its comparison with usual powder catalyst in catalytic oxidation reactions in gas and liquid phases. Titania was coated on glass plates with different thicknesses, but with ultra-low surface roughness (< 5 Å). Gold deposition was performed with usual chemical method for catalysts preparation, that is deposition–precipitation with urea. Transmission electron microscopy showed that planar samples are decorated with a high quantity (> 10 wt.% with respect to TiO2) of gold nanoparticles smaller than 2.5 nm, with a narrow size distribution. Activity in CO oxidation demonstrates the catalytic behavior of the planar samples, although they are less active than powder catalyst because of the different geometries of the reactors and catalysts. In contrast, their catalytic performances in liquid phase, benzyl alcohol oxidation, are comparable. These results validate the concept that gold planar catalysts prepared by chemical methods can present similar catalytic behavior as real powder gold catalysts. Such planar catalysts could be useful for bridging the material gap between real and model catalysts in advanced techniques, such as scanning tunnelling microscopy and spectroscopy or high-pressure photoelectron spectroscopy. - Highlights: ► Preparation of thin film of TiO2 (pure anatase) on glass with a low roughness (< 5 Å) ► High density of small gold nanoparticles on planar substrates by a chemical method ► Planar catalysts active in both gas and liquid phase oxidation reactions ► Bridging of the material gap between real and model catalysts

  16. Biodiesel by catalytic reactive distillation powered by metal oxides

    NARCIS (Netherlands)

    A.A. Kiss; A.C. Dimian; G. Rothenberg

    2008-01-01

    The properties and use of biodiesel as a renewable fuel as well as the problems associated with its current production processes are outlined. A novel sustainable esterification process based on catalytic reactive distillation is proposed. The pros and cons of manufacturing biodiesel via fatty acid

  17. The Significance of Lewis Acid Sites for the Selective Catalytic Reduction of Nitric Oxide on Vanadium-Based Catalysts.

    Science.gov (United States)

    Marberger, Adrian; Ferri, Davide; Elsener, Martin; Kröcher, Oliver

    2016-09-19

    The long debated reaction mechanisms of the selective catalytic reduction (SCR) of nitric oxide with ammonia (NH3 ) on vanadium-based catalysts rely on the involvement of Brønsted or Lewis acid sites. This issue has been clearly elucidated using a combination of transient perturbations of the catalyst environment with operando time-resolved spectroscopy to obtain unique molecular level insights. Nitric oxide reacts predominantly with NH3 coordinated to Lewis sites on vanadia on tungsta-titania (V2 O5 -WO3 -TiO2 ), while Brønsted sites are not involved in the catalytic cycle. The Lewis site is a mono-oxo vanadyl group that reduces only in the presence of both nitric oxide and NH3 . We were also able to verify the formation of the nitrosamide (NH2 NO) intermediate, which forms in tandem with vanadium reduction, and thus the entire mechanism of SCR. Our experimental approach, demonstrated in the specific case of SCR, promises to progress the understanding of chemical reactions of technological relevance.

  18. The Significance of Lewis Acid Sites for the Selective Catalytic Reduction of Nitric Oxide on Vanadium-Based Catalysts.

    Science.gov (United States)

    Marberger, Adrian; Ferri, Davide; Elsener, Martin; Kröcher, Oliver

    2016-09-19

    The long debated reaction mechanisms of the selective catalytic reduction (SCR) of nitric oxide with ammonia (NH3 ) on vanadium-based catalysts rely on the involvement of Brønsted or Lewis acid sites. This issue has been clearly elucidated using a combination of transient perturbations of the catalyst environment with operando time-resolved spectroscopy to obtain unique molecular level insights. Nitric oxide reacts predominantly with NH3 coordinated to Lewis sites on vanadia on tungsta-titania (V2 O5 -WO3 -TiO2 ), while Brønsted sites are not involved in the catalytic cycle. The Lewis site is a mono-oxo vanadyl group that reduces only in the presence of both nitric oxide and NH3 . We were also able to verify the formation of the nitrosamide (NH2 NO) intermediate, which forms in tandem with vanadium reduction, and thus the entire mechanism of SCR. Our experimental approach, demonstrated in the specific case of SCR, promises to progress the understanding of chemical reactions of technological relevance. PMID:27553251

  19. Water oxidation catalysis: an amorphous quaternary Ba-Sr-Co-Fe oxide as a promising electrocatalyst for the oxygen-evolution reaction.

    Science.gov (United States)

    Zhang, Cuijuan; Berlinguette, Curtis P; Trudel, Simon

    2016-01-25

    We present an amorphous quaternary Ba-Sr-Co-Fe oxide (a-BSCF) with a specific stoichiometry, readily fabricated via a photochemical decomposition method. a-BSCF demonstrates high catalytic activity towards the oxygen-evolution reaction (OER). PMID:26659269

  20. System and method for selective catalytic reduction of nitrogen oxides in combustion exhaust gases

    Science.gov (United States)

    Sobolevskiy, Anatoly; Rossin, Joseph A

    2014-04-08

    A multi-stage selective catalytic reduction (SCR) unit (32) provides efficient reduction of NOx and other pollutants from about 50-550.degree. C. in a power plant (19). Hydrogen (24) and ammonia (29) are variably supplied to the SCR unit depending on temperature. An upstream portion (34) of the SCR unit catalyzes NOx+NH.sub.3 reactions above about 200.degree. C. A downstream portion (36) catalyzes NOx+H.sub.2 reactions below about 260.degree. C., and catalyzes oxidation of NH.sub.3, CO, and VOCs with oxygen in the exhaust above about 200.degree. C., efficiently removing NOx and other pollutants over a range of conditions with low slippage of NH.sub.3. An ammonia synthesis unit (28) may be connected to the SCR unit to provide NH.sub.3 as needed, avoiding transport and storage of ammonia or urea at the site. A carbonaceous gasification plant (18) on site may supply hydrogen and nitrogen to the ammonia synthesis unit, and hydrogen to the SCR unit.

  1. Influences of Reaction Parameters on the Product of a Geothermite Reaction: A Multi-Component Oxidation-Reduction Reaction Study

    OpenAIRE

    Faierson, Eric J.

    2009-01-01

    This study investigated an oxidation-reduction reaction involving a mixture of minerals, glass, and aluminum that exhibited thermite-type reaction behavior. Thermite reactions are a class of Self-propagating High-temperature Synthesis (SHS) reactions. Chemical reactions between raw minerals and a reducing agent, which exhibit thermite-type reaction behavior, are termed geothermite reactions by the author. Geothermite reactions have the potential for use in In-Situ Resource Utilization (ISRU...

  2. Enhancing catalytic performance of palladium in gold and palladium alloy nanoparticles for organic synthesis reactions through visible light irradiation at ambient temperatures.

    Science.gov (United States)

    Sarina, Sarina; Zhu, Huaiyong; Jaatinen, Esa; Xiao, Qi; Liu, Hongwei; Jia, Jianfeng; Chen, Chao; Zhao, Jian

    2013-04-17

    The intrinsic catalytic activity of palladium (Pd) is significantly enhanced in gold (Au)-Pd alloy nanoparticles (NPs) under visible light irradiation at ambient temperatures. The alloy NPs strongly absorb light and efficiently enhance the conversion of several reactions, including Suzuki-Miyaura cross coupling, oxidative addition of benzylamine, selective oxidation of aromatic alcohols to corresponding aldehydes and ketones, and phenol oxidation. The Au/Pd molar ratio of the alloy NPs has an important impact on performance of the catalysts since it determines both the electronic heterogeneity and the distribution of Pd sites at the NP surface, with these two factors playing key roles in the catalytic activity. Irradiating with light produces an even more profound enhancement in the catalytic performance of the NPs. For example, the best conversion rate achieved thermally at 30 °C for Suzuki-Miyaura cross coupling was 37% at a Au/Pd ratio of 1:1.86, while under light illumination the yield increased to 96% under the same conditions. The catalytic activity of the alloy NPs depends on the intensity and wavelength of incident light. Light absorption due to the Localized Surface Plasmon Resonance of gold nanocrystals plays an important role in enhancing catalyst performance. We believe that the conduction electrons of the NPs gain the light absorbed energy producing energetic electrons at the surface Pd sites, which enhances the sites' intrinsic catalytic ability. These findings provide useful guidelines for designing efficient catalysts composed of alloys of a plasmonic metal and a catalytically active transition metal for various organic syntheses driven by sunlight. PMID:23566035

  3. In situ infrared study of adsorbed species during catalytic oxidation and carbon dioxide adsorption

    Science.gov (United States)

    Khatri, Rajesh A.

    2005-11-01

    Hydrogen is considered to be the fuel of the next century. Hydrogen can be produced by either water splitting using the solar or nuclear energy or by catalytic cracking and reforming of the fossil fuels. The water splitting process using solar energy and photovoltaics is a clean way to produce hydrogen, but it suffers from very low efficiency. A promising scheme to produce H 2 from natural gas involves following steps: (i) partial oxidation and reforming of natural gas to syngas, (ii) water-gas shift reaction to convert CO in the syngas to additional H2, (iii) separation of the H2 from CO2, and (iv) CO2 sequestration. The requirements for the above scheme are (i) a highly active coke resistant catalyst for generation of syngas by direct partial oxidation, (ii) a highly active sulfur tolerant catalyst for the water-gas shift reaction, and (iii) a low cost sorbent with high CO2 adsorption capacity for CO2 sequestration. This dissertation will address the mechanisms of partial oxidation, CO2 adsorption, and water-gas shift catalysis using in situ IR spectroscopy coupled with mass spectrometry (MS). The results from these studies will lead to a better understanding of the reaction mechanism and design of both the catalyst and sorbent for production of hydrogen with zero emissions. Partial oxidation of methane is studied over Rh/Al2O 3 catalyst to elucidate the reaction mechanism for synthesis gas formation. The product lead-lag relationship observed with in situ IR and MS results revealed that syngas is produced via a two-step reforming mechanism: the first step involving total oxidation of CH4 to CO2 and H 2O and the second step involving the reforming of unconverted methane with CO2 and H2O to form syngas. Furthermore, the Rh on the catalyst surface remains predominantly in the partially oxidized state (Rhdelta+ and Rh0). For the water-gas shift reaction, addition of Re to the Ni/CeO2 catalyst enhanced the water gas shift activity by a factor of three. The activity

  4. Catalytic activity of pyrite for coal liquefaction reaction; Tennen pyrite no shokubai seino ni kansuru kento

    Energy Technology Data Exchange (ETDEWEB)

    Hirano, K.; Kozu, M.; Okada, T.; Kobayashi, M. [Nippon Coal Oil Co. Ltd., Tokyo (Japan)

    1996-10-28

    Since natural pyrite is easy to obtain and cheap as coal liquefaction catalyst, it is to be used for the 150 t/d scale NEDOL process bituminous coal liquefaction pilot plant. NEDO and NCOL have investigated the improvement of catalytic activity of pulverized natural pyrite for enhancing performance and economy of the NEDOL process. In this study, coal liquefaction tests were conducted using natural pyrite catalyst pulverized by dry-type bowl mill under nitrogen atmosphere. Mechanism of catalytic reaction of the natural pyrite was discussed from relations between properties of the catalyst and liquefaction product. The natural pyrite provided an activity to transfer gaseous hydrogen into the liquefaction product. It was considered that pulverized pyrite promotes the hydrogenation reaction of asphaltene because pulverization increases its contact rate with reactant and the amount of active points on its surface. It was inferred that catalytic activity of pyrite is affected greatly by the chemical state of Fe and S on its surface. 3 refs., 4 figs., 1 tab.

  5. Some Aspects of the Catalytic Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    Anil; K.Saikia

    2007-01-01

    1 Results Catalytic reactions are gaining importance due to its low cost, operational simplicity, high efficiency and selectivity. It is also getting much attention in green synthesis. Many useful organic reactions, including the acylation of alcohols and aldehydes, carbon-carbon, carbon-nitrogen, carbon-sulfur bond forming and oxidation reactions are carried out by catalyst. We are exploring the catalytic acylation of alcohols and aldehydes in a simple and efficient manner. Catalytic activation of unr...

  6. Catalytic combustion of toluene over a copper-Manganese-silver mixed-oxide catalyst supported on a washcoated ceramic monolith

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, J.C.; Jiang, W. [School of Chemistry and Chemical Engineering, Southeast University, Nanjing (China); Li, Y.D. [Tianjin Key Laboratory of Applied Catalysis Science and Technology and State Key Laboratory for Chemical Engineering (Tianjin University), Tianjin University, Tianjin (China); Wu, D.F.

    2009-10-15

    Monolithic catalysts were prepared by washcoating an alumina sol and then impregnating Cu-Mn-Ag mixed oxides onto cordierite substrates. The effects of the preparation parameters including the Ag/Cu/Mn ratio, the total amount of active phase and the loading of washcoat, and the reaction conditions, e.g., the space velocity and the oxygen/toluene ratio on the catalytic performance for the combustion of toluene were investigated. It is shown that the Cu-Mn-Ag oxides are very active for the combustion of toluene and that the highest catalytic activity is achieved over a monolithic catalyst containing 14.7 wt % of washcoat and 21.2 wt % of active phase with a Ag/Cu/Mn molar ratio of 13.8/43.1/43.1. It is also seen that the optimum catalyst has a good catalytic stability and exhibits an excellent activity not only at a rather high space velocity but also within a wide range of oxygen/toluene ratios. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  7. Session 6: Water depollution from aniline and phenol by air oxidation and adsorptive-catalytic oxidation in liquid phase

    Energy Technology Data Exchange (ETDEWEB)

    Dobrynkin, N.M.; Batygina, M.V.; Noskov, A.S. [Boreskov Institute of Catalysis of Siberian Branch of Russian Academy of Sciences, Pr. Ak. Lavrentieva (Russian Federation)

    2004-07-01

    This paper is devoted to development of carbon catalysts and application of catalytic wet air oxidation for deep cleaning of polluted waters. The described catalysts and method are solving the problem of development environmentally reliable method for fluids treatment and allow carrying out the adsorption of pollutants on carbon CAPM (catalytically active porous material) with following regeneration of the CAPM without the loss of adsorptive qualities. The experiments have shown a principal capability simultaneously to use carbon CAPM as adsorbent and either as catalyst, or as a catalyst support for oxidation of aniline and phenol in water solutions. (authors)

  8. Steady-state kinetics with nitric oxide reductase (NOR): new considerations on substrate inhibition profile and catalytic mechanism.

    Science.gov (United States)

    Duarte, Américo G; Cordas, Cristina M; Moura, José J G; Moura, Isabel

    2014-03-01

    Nitric oxide reductase (NOR) from denitrifying bacteria is an integral membrane protein that catalyses the two electron reduction of NO to N2O, as part of the denitrification process, being responsible for an exclusive reaction, the NN bond formation, the key step of this metabolic pathway. Additionally, this class of enzymes also presents residual oxidoreductase activity, reducing O2 to H2O in a four electron/proton reaction. In this work we report, for the first time, steady-state kinetics with the Pseudomonas nautica NOR, either in the presence of its physiological electron donor (cyt. c552) or immobilised on a graphite electrode surface, in the presence of its known substrates, namely NO or O2. The obtained results show that the enzyme has high affinity for its natural substrate, NO, and different kinetic profiles according to the electron donor used. The kinetic data, as shown by the pH dependence, is modelled by ionisable amino acid residues nearby the di-nuclear catalytic site. The catalytic mechanism is revised and a mononitrosyl-non-heme Fe complex (FeB(II)-NO) species is favoured as the first catalytic intermediate involved on the NO reduction. PMID:24412239

  9. Highly efficient degradation of 4-nitrophenol over the catalyst of Mn2O3/AC by microwave catalytic oxidation degradation method.

    Science.gov (United States)

    Yin, Cheng; Cai, Jinjun; Gao, Lingfei; Yin, Jingya; Zhou, Jicheng

    2016-03-15

    A new microwave catalytic oxidation process based on two kinds of catalysts, the commercially available activated carbon (AC) and Mn2O3 nanoparticle modified AC (Mn2O3/AC), was reported for the degradation of 4-nitrophenol (4-NP) without adding any oxidant. Effects of microwave power, catalyst dosage, irradiation time, and initial concentration for the degradation efficiency were studied. Results indicated that catalyst of Mn2O3/AC showed much higher catalytic activity than pure AC and Mn2O3 particles. Significantly, 4-NP degradation efficiency reached 99.6%, corresponding to 93.5% TOC removal under optimal conditions with microwave power of 400W, Mn2O3/AC dosage of 2g, reaction time of 5min, and initial concentration of 100mg/L. Hydroxyl radicals (OH) generated during catalytic reaction is the main oxidant, and O2 can not effectively improve removal rate. We proposed the microwave 'photoelectric effect' to interpret the generation of OH in view that microwave irradiation can directly excite the catalyst to produce electron-hole pairs and then transform H2O into OH on the surface of catalyst in solution. The obtained kinetic equation for microwave catalytic oxidation degradation of 4-NP was in line with pseudo-first-order kinetic model, that is, apparent rate constant increased as microwave power density increase.

  10. Supported catalysts based on layered double hydroxides for catalytic oxidation and hydrogenation: general functionality and promising application prospects.

    Science.gov (United States)

    Feng, Junting; He, Yufei; Liu, Yanan; Du, Yiyun; Li, Dianqing

    2015-08-01

    Oxidation and hydrogenation catalysis plays a crucial role in the current chemical industry for the production of key chemicals and intermediates. Because of their easy separation and recyclability, supported catalysts are widely used in these two processes. Layered double hydroxides (LDHs) with the advantages of unique structure, composition diversity, high stability, ease of preparation and low cost have shown great potential in the design and synthesis of novel supported catalysts. This review summarizes the recent progress in supported catalysts by using LDHs as supports/precursors for catalytic oxidation and hydrogenation. Particularly, partial hydrogenation of acetylene, hydrogenation of dimethyl terephthalate, methanation, epoxidation of olefins, elimination of NOx and SOx emissions, and selective oxidation of biomass have been chosen as representative reactions in the petrochemical, fine chemicals, environmental protection and clean energy fields to highlight the potential application and the general functionality of LDH-based catalysts in catalytic oxidation and hydrogenation. Finally, we concisely discuss some of the scientific challenges and opportunities of supported catalysts based on LDH materials. PMID:25962432

  11. Rare earth oxide aero- and xerogels. Tuning porosity and catalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Neumann, Bjoern

    2013-11-15

    Heterogeneous catalysts to this day are still largely developed on the basis of trial and error. This is due to the great difficulty of creating custom-designed structures at the nanometer scale using traditional preparation methods. In the course of recent rapid developments in the material sciences, however, it has become possible to create materials with custom-designed properties from the macroscopic down into the nanometer range. The purpose of the present study was to make use of this potential for catalysis. The task was to modify the porosity and composition of selected rare earth oxides that promise well as catalysts with the goal of obtaining good results in terms of oxidative reactions and oxidative coupling. One major focus was on chemical sol-gel methods and in particular on what is referred to as the epoxide addition method. Extensive work was put into the characterisation and catalytic testing of aerogels and xerogels of pure rare earth oxides as well as of hybrid systems of rare earth oxides and aluminium oxide. Furthermore, thin xerogel films and macroporous monoliths were produced, the latter using a direct foaming method. The results of this work confirm the high potential of sol-gel chemistry for making porous materials of variable and controllable porosity and composition available for heterogeneous catalysis and creating more powerful catalysts. [German] Bis heute werden heterogene Katalysatoren ueberwiegend per ''trial and error'' entwickelt. Dies liegt daran, dass es mit Hilfe der traditionellen Herstellungsmethoden sehr schwierig ist, auf der Nanometerskala Strukturen gezielt herzustellen. Im Zuge der rasanten Entwicklungen in den Materialwissenschaften ist es jedoch moeglich geworden, verschiedenste Materialen mit massgeschneiderten Eigenschaften vom makroskopischen bis hinein in den Nanometerbereich herzustellen. Ziel dieser Arbeit war es, dieses Potential fuer die Katalyse zu nutzen. Dabei bestand die Aufgabe darin

  12. Influence of method of preparation of Pt Ru/C electrocatalysts on the catalytic activity for the ethanol oxidation reaction in acidic medium; Influencia do metodo de preparacao de eletrocatalisadores PtRu/C sobre a atividade catalitica frente a reacao de oxidacao de etanol em meio acido

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, Walber dos Santos; Silva, Uriel Lean Valente; Souza, Jose Pio Iudice de, E-mail: jpio@ufpa.br [Universidade Federal do Para, (UFPA), Belem, PA (Brazil). Instituto de Ciencias Exatas e Naturais. Faculdade de Quimica

    2013-09-01

    In this work the influence of variations in the borohydrate reduction method on the properties of Pt Ru/C electrocatalysts was investigated. The electrocatalysts were prepared using 1:1 ; 2:1; 5:1; 50:1 and 250:1 molar ratios of NaBH{sub 4} to metals. The reduction was also performed by dripping or by fast addition of the solution. The results showed that Pt Ru nanoparticles obtained by fast addition had the smallest crystallite sizes. It was also noted that the catalytic activity increased as the borohydrate:metal molar ratio increased. The Pt Ru/C electrocatalysts (50:1) obtained by fast addition presented the best catalytic activity for ethanol electro-oxidation. (author)

  13. Preparation of Molecular Sieve Catalyst and Application in the Catalytic Oxidation Treatment of Waste Water

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Citric acid is an important additive in foods, cosmetics, medicine and so on, but it discharges about 10 ton of factory effluent when 1 ton of citric acid is produced. The COD of the factory effluent is near 20000 mg/L. The treatment of citric acid factory effluent is a serious problem in environmental chemistry. It is found that molecular sieve support metal complexes have high catalytic activity in aerobic oxidation of alkene [1,2]. In this paper, a kind of molecular sieve catalyst was prepared. The catalyst was used for the treatment of citric acid factory effluent by method of catalytic oxygen oxidation.

  14. Electrode Reaction Pathway in Oxide Anode for Solid Oxide Fuel Cells

    Science.gov (United States)

    Li, Wenyuan

    Oxide anodes for solid oxide fuel cells (SOFC) with the advantage of fuel flexibility, resistance to coarsening, small chemical expansion and etc. have been attracting increasing interest. Good performance has been reported with a few of perovskite structure anodes, such as (LaSr)(CrMn)O3. However, more improvements need to be made before meeting the application requirement. Understanding the oxidation mechanism is crucial for a directed optimization, but it is still on the early stage of investigation. In this study, reaction mechanism of oxide anodes is investigated on doped YCrO 3 with H2 fuel, in terms of the origin of electrochemical activity, rate-determining steps (RDS), extension of reactive zone, and the impact from overpotential under service condition to those properties. H2 oxidation on the YCs anodes is found to be limited by charge transfer and H surface diffusion. A model is presented to describe the elementary steps in H2 oxidation. From the reaction order results, it is suggested that any models without taking H into the charge transfer step are invalid. The nature of B site element determines the H2 oxidation kinetics primarily. Ni displays better adsorption ability than Co. However, H adsorption ability of such oxide anode is inferior to that of Ni metal anode. In addition, the charge transfer step is directly associated with the activity of electrons in the anode; therefore it can be significantly promoted by enhancement of the electron activity. It is found that A site Ca doping improves the polarization resistance about 10 times, by increasing the activity of electrons to promote the charge transfer process. For the active area in the oxide anode, besides the traditional three-phase boundary (3PB), the internal anode surface as two-phase boundary (2PB) is proven to be capable of catalytically oxidizing the H2 fuel also when the bulk lattice is activated depending on the B site elements. The contribution from each part is estimated by switching

  15. Catalytic Activity of Dual Metal Cyanide Complex in Multi-component Coupling Reactions

    Institute of Scientific and Technical Information of China (English)

    Anaswara RAVINDRAN; Rajendra SRIVASTAVA

    2011-01-01

    Several dual metal cyanide catalysts were prepared from potassium ferrocyanide,metal chloride (where metal =Zn2+,Mn2+,Ni2+,Co2+ and Fe2+),t-butanol (complexing agent) and PEG-4000 (co-complexing agent).The catalysts were characterized by elemental analysis (CHN and X-ray fluorescence),X-ray diffraction,N2 adsorption-desorption,scanning electron microscopy,Fourier-transform infiared spectroscopy,and UV-Visible spectroscopy.The dual metal cyanide catalysts were used in several acid catalyzed multi-component coupling reactions for the synthesis of pharmaceutically important organic derivatives.In all these reactions,the Fe-Fe containing dual metal cyanide catalyst was the best catalyst.The catalysts can be recycled without loss in catalytic activity.The advantage of this method is the use of mild,efficient and reusable catalysts for various reactions,which makes them candidates for commercial use.

  16. Surface composition and catalytic activity of La-Fe mixed oxides for methane oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Fengxiang [School of Chemistry, Beijing Institute of Technology, Liangxiang East Road, Beijing 102488 (China); Li, Zhanping [Analysis Center, Tsinghua University, Beijing 100084 (China); Ma, Hongwei [School of Chemistry, Beijing Institute of Technology, Liangxiang East Road, Beijing 102488 (China); Gao, Zhiming, E-mail: zgao@bit.edu.cn [School of Chemistry, Beijing Institute of Technology, Liangxiang East Road, Beijing 102488 (China)

    2015-10-01

    Graphical abstract: - Highlights: • The sample with La/Fe atomic ratio of 0.94 is single phase perovskite La{sub 0.94}FeO{sub 3−d}. • The excess ironic oxide exists on the surface of the perovskite crystallites. • La{sup 3+} ions are enriched on surface of the oxides even for the La{sub 0.68}Fe sample. - Abstract: Four La-Fe oxide samples with La/Fe atomic ratio y = 1.02 ∼ 0.68 (denoted as LayFe) were prepared by the citrate method. The samples had a decreased specific surface area with the La/Fe atomic ratio decreasing. XRD pattern proved that the sample La{sub 0.94}Fe is single phase perovskite La{sub 0.94}FeO{sub 3−d}. Phase composition of the samples was estimated by the Rietveld refinement method. XPS analyses indicate that La{sup 3+} ions are enriched on surface of crystallites for all the samples, and surface carbonate ions are relatively abundant on the samples La{sub 1.02}Fe and La{sub 0.94}Fe. Catalytic activity for methane oxidation per unit surface area of the samples is in the order of La{sub 0.68}Fe > La{sub 0.76}Fe > La{sub 0.94}Fe > La{sub 1.02}Fe both in the presence and in the absence of gaseous oxygen. A reason for this order would be the higher concentration of Fe{sup 3+} ion on the surface of the samples La{sub 0.68}Fe and La{sub 0.76}Fe.

  17. Efficient oxidation of benzyl alcohol with heteropolytungstate as reaction-controlled phase-transfer catalyst

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A series of heteropolytungstates has been synthesized and utilized as catalysts to catalyze oxidation of benzyl alcohol with aqueous hydrogen peroxide. The results indicated that three of these catalysts showed the properties of reaction-controlled phasetransfer catalysis, and they had excellent catalytic ability to the oxidation of benzyl alcohol. No other by-products were detected by gas chromatography. Once the hydrogen peroxide was consumed completely, the catalyst precipitated from solvent, and the results of the catalyst recycle showed that the catalyst had high stability.

  18. Problems in Catalytic Oxidation of Hydrocarbons and Detailed Simulation of Combustion Processes

    Science.gov (United States)

    Xin, Yuxuan

    This dissertation research consists of two parts, with Part I on the kinetics of catalytic oxidation of hydrocarbons and Part II on aspects on the detailed simulation of combustion processes. In Part I, the catalytic oxidation of C1--C3 hydrocarbons, namely methane, ethane, propane and ethylene, was investigated for lean hydrocarbon-air mixtures over an unsupported Pd-based catalyst, from 600 to 800 K and under atmospheric pressure. In Chapter 2, the experimental facility of wire microcalorimetry and simulation configuration were described in details. In Chapter 3 and 4, the oxidation rate of C1--C 3 hydrocarbons is demonstrated to be determined by the dissociative adsorption of hydrocarbons. A detailed surface kinetics model is proposed with deriving the rate coefficient of hydrocarbon dissociative adsorption from the wire microcalorimetry data. In Part II, four fundamental studies were conducted through detailed combustion simulations. In Chapter 5, self-accelerating hydrogen-air flames are studied via two-dimensional detailed numerical simulation (DNS). The increase in the global flame velocity is shown to be caused by the increase of flame surface area, and the fractal structure of the flame front is demonstrated by the box-counting method. In Chapter 6, skeletal reaction models for butane combustion are derived by using directed relation graph (DRG) and DRG-aided sensitivity analysis (DRGASA), and uncertainty minimization by polynomial chaos expansion (MUM-PCE) mothodes. The dependence of model uncertainty is subjected to the completeness of the model. In Chapter 7, a systematic strategy is proposed to reduce the cost of the multicomponent diffusion model by accurately accounting for the species whose diffusivity is important to the global responses of the combustion systems, and approximating those of less importance by the mixture-averaged model. The reduced model is validated in an n-heptane mechanism with 88 species. In Chapter 8, the influence of Soret

  19. Copper(II)–imida‐salen Complexes Encapsulated into NaY Zeolite for Oxidations Reactions

    DEFF Research Database (Denmark)

    Kuźniarska‐Biernacka, Iwona; Carvalho, M. Alice; Rasmussen, Søren Birk;

    2013-01-01

    The oxidation of phenol, cychohexanol and hydroquinone has been screened in the presence of copper(II) complexes with the Schiff‐base salen ligand, 1,5‐bis[(E)‐5‐chloro‐2‐hydroxybenzylideneamino]‐1H‐imidazole‐4‐carbonitrile, and encapsulated into NaY zeolite by using two different methods. The ne...... with their homogeneous counterparts. The results show higher or similar substrate conversion when compared with the free complex in all the reactions tested. After their use in catalytic reaction, these catalysts were found to be reusable without loss of activity....

  20. Preparation of hierarchical layer-stacking Mn-Ce composite oxide for catalytic total oxidation of VOCs

    Institute of Scientific and Technical Information of China (English)

    唐文翔; 武晓峰; 刘刚; 李双德; 李东艳; 李文辉; 陈运法

    2015-01-01

    Hierarchical layer-stacking Mn-Ce composite oxide with mesoporous structure was firstly prepared by a simple precipita-tion/decomposition procedure with oxalate precursor and the complete catalytic oxidation of VOCs (benzene, toluene and ethyl ace-tate) were examined. The Mn-Ce oxalate precursor was obtained from metal salt and oxalic acid without any additives. The resulting materials were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), en-ergy dispersive X-ray spectroscopy (EDX), hydrogen temperature programmed reduction (H2-TPR) and X-ray photoelectron spec-troscopy (XPS). Compared with Mn-Ce composite oxide synthesized through a traditional method (Na2CO3 route), the hierarchical layer-stacking Mn-Ce composite oxide exhibited higher catalytic activity in the complete oxidation of volatile organic compounds (VOCs). By means of testing, the data revealed that the hierarchical layer-stacking Mn-Ce composite oxide possessed superior physiochemical properties such as good low-temperature reducibility, high manganese oxidation state and rich adsorbed surface oxy-gen species which resulted in the enhancement of catalytic abilities.

  1. Deuterium–tritium catalytic reaction in fast ignition: Optimum parameters approach

    Indian Academy of Sciences (India)

    B Khanbabaei; A Ghasemizad; S Khoshbinfar

    2014-09-01

    One of the main concerns about the currentworking on nuclear power reactors is the potential hazard of their radioactive waste. There is hope that this issue will be reduced in next generation nuclear fusion power reactors. Reactors will release nuclear energy through microexplosions that occur in a mixture of hydrogen isotopes of deuterium and tritium. However, there exist radiological hazards due to the accumulation of tritium in the blanket layer. A catalytic fusion reaction of DT mixture may stand between DD and an equimolar DT approach in which the fusion process continues with a small amount of tritium seed. In this paper, we investigate the possibility of DT reaction in the fast ignition (FI) scheme. The kinematic study of the main mechanism of the energy gain–loss term, which may disturb the ignition and burn process, was performed in FI and the optimum values of precompressed fuel and proton beam driver were derived. The recommended values of fuel parameters are: areal density $ρ R ≥ 5\\cdot$cm-2 and initial tritium fraction ≤ 0.025. For the proton beam, the corresponding optimum interval values are proton average energy $3≤ E_p ≤ 10$ MeV, pulse duration $5 ≤ t_p ≤ 15$ ps and power $5≤ W_p ≤ 12 × 10^{22}$ (keV$\\cdot$cm3$\\cdot$ps-1). It was proved that under the above conditions, a fast ignition DT reaction stays in the catalytic regime.

  2. Preparation of birnessite-supported pt nanoparticles and their application in catalytic oxidation of formaldehyde.

    Science.gov (United States)

    Liu, Linlin; Tian, Hua; He, Junhui; Wang, Donghui; Yang, Qiaowen

    2012-01-01

    Flaky and nanospherical birnessite and birnessite-supported Pt catalysts were successfully prepared and characterized by means of Xray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) and N2 adsorption-desorption. Effects of the birnessite morphology and Pt reduction method on the catalytic activity for the complete oxidation of formaldehyde (HCHO) were investigated. It was found that flaky birnessite exhibited higher catalytic activity than nanospherical birnessite. The promoting effect of Pt on the birnessite catalyst indicated that the reduction method of the Pt precursor greatly influenced the catalytic performance. Flaky birnessite-supported Pt nanoparticles reduced by KBH4 showed the highest catalytic activity and could completely oxidize HCHO into CO2 and H20 at 50 degreesC, whereas the sample reduced using H2-plasma showed lower activity for HCHO oxidation. The differences in catalytic activity of these materials were jointly attributed to the effects of pore structure, surface active sites exposed to HCHO and the dispersion of Pt nanoparticles.

  3. Catalytic Oxidation of Benzene Over LaCoO3 Perovskite-Type Oxides Prepared Using Microwave Process.

    Science.gov (United States)

    Jung, Won Young; Song, Young In; Lim, Kwon Taek; Lee, Gun Dae; Lee, Man Sig; Hong, Seong-Soo

    2015-01-01

    LaCoO3 perovskite type oxides were successfully prepared using microwave-assisted method, characterized by TG/DTA, XRD, XPS and H2-TPR and their catalytic activities for combustion of benzene were determined. Almost of catalyst showed perovskite crystalline phase and 13-84 nm particle size. LaCoO3 catalysts prepared by microwave-assisted method showed the highest activity and the conversion reached almost 100% at 360 degrees C. In the LaCoO3-type catalyst, the partial substitution of Sr into site A enhanced the catalytic activity on the combustion of benzene. The higher amount of the chemisorbed oxygen was, the better the performance of the combustion catalyst. The catalytic activity of perovskite-type oxides showed a good relationship with the results of H2-TPR and XPS measurement.

  4. Performance of a Novel Hydrophobic Mesoporous Material for High Temperature Catalytic Oxidation of Naphthalene

    Directory of Open Access Journals (Sweden)

    Guotao Zhao

    2014-01-01

    Full Text Available A high surface area, hydrophobic mesoporous material, MFS, has been successfully synthesized by a hydrothermal synthesis method using a perfluorinated surfactant, SURFLON S-386, as the single template. N2 adsorption and TEM were employed to characterize the pore structure and morphology of MFS. Static water adsorption test indicates that the hydrophobicity of MFS is significantly higher than that of MCM-41. XPS and Py-GC/MS analysis confirmed the existence of perfluoroalkyl groups in MFS which led to its high hydrophobicity. MFS was used as a support for CuO in experiments of catalytic combustion of naphthalene, where it showed a significant advantage over MCM-41 and ZSM-5. SEM was helpful in understanding why CuO-MFS performed so well in the catalytic combustion of naphthalene. Experimental results indicated that MFS was a suitable support for catalytic combustion of large molecular organic compounds, especially for some high temperature catalytic reactions when water vapor was present.

  5. Synthesis of p-Hydroxybenzaldehyde by Liquid-phase Catalytic Oxidation of p-Cresol over PVDF Modified Cobalt Pyrophosphate

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yi-bo; WANG De-qiang; MIAO Zhen-zhen; PAN Xi-qiang; ZHANG Zhen-dong; YANG Xiang-guang

    2013-01-01

    The influence of the wettability of a catalyst on the performance of the liquid phase oxidation of p-cresol was investigated.It was found that the surface hydrophobicity of a catalyst,which can be changed by modification with various loadings of polyvinylidene fluoride(PVDF),has a promotion effect on the catalytic performance.At the same time,the reaction parameters such as oxygen pressure,molar ratio of NaOH to p-cresol,reaction temperature and time on the catalytic performance in the liquid-phase oxidation of p-cresol were optimized.As a result,10%(mass fraction) PVDF modified cobalt pyrophosphate gave the highest conversion of 94.2% of p-cresol with a selectivity of 94.4% for p-hydroxybenzaldehyde at 348 K and a molar ratio of 4:1 of NaOH/p-cresol and an oxygen pressure of 1.0 MPa for 3 h.

  6. Influence of basic properties of Mg,Al-mixed oxides on their catalytic activity in knoevenagel condensation between benzaldehyde and phenylsulfonylacetonitrile

    Directory of Open Access Journals (Sweden)

    Caridad Noda Pérez

    2009-01-01

    Full Text Available The catalytic performance of Mg,Al-mixed oxides (MO20, MO25 and MO33 derived from hydrotalcites was evaluated in the Knoevenagel reaction between benzaldehyde and phenylsulfonylacetonitrile at 373 and 383 K. The best results were obtained for the sample MO20 that presented the highest basic sites density and external area and the smallest crystallite sizes. The relative amount of basic sites with weak to intermediate strength also played an important role on catalytic performance. By increasing the catalyst content from 1 to 5 wt.% at 383 K, a complete conversion of the reactants is attained, producing α-phenylsulfonylcinnamonitrile with a selectivity of 100%.

  7. Synthesis of Novel Chiral Dibenzo [ a, c ] cycloheptadiene Bis(oxazoline) and Catalytic Asymmetric Reactions

    Institute of Scientific and Technical Information of China (English)

    FU Bin; DU Da-Ming; WANG Jian-Bo

    2003-01-01

    @@ Over the last decade, C2-symmetric chiral oxazoline metal complexes have been recognized as an effective classof chiral catalyst in a variety of transition metal catalyzed asymmetric reactions. [1] High catalytic activities and enantiomeric excesses have been obtained using C2-symmetric chiral ligands in conjunction with suitable transition metal ion, for example, the hydrosilylation of ketone, allylic alkylation, Michael addition, Diels-Alder cycloaddition, and cyclopropanation. Thus, the design and synthesis of new chiral oxazoline ligands have inspired many scientists to work with great efforts.

  8. Electrochemical Synthesis of Mo2C Catalytical Coatings for the Water-Gas Shift Reaction

    Science.gov (United States)

    Kuznetsov, Sergey A.; Dubrovskiy, Anton R.; Rebrov, Evgeny V.; Schouten, Jaap C.

    2007-11-01

    The electroreduction of CO32- ions on a molybdenum cathode in a NaCl-KCl-Li2CO3 melt was studied by cyclic voltammetry. The electrochemical synthesis of Mo2C on molybdenum substrates has been performed at 1123 K for 7 h with a cathodic current density of 5 mA cm-2. If molybdenum carbide is present as a thin (ca. 500 nm) film on a molybdenum substrate (Mo2C/Mo), its catalytic activity in the water gas-shift reaction is enhanced by at least an order of magnitude compared to that of the bulk Mo2C phase.

  9. A study on the photo catalytic decomposition reactions of organics dissolved in water (II)

    International Nuclear Information System (INIS)

    Experiments on aqueous TiO2 photo catalytic reaction of nitrogen containing organic compounds such as ethylamine, phenylhydrazine, pyridine, urea and EDTA were carried out. Based on the values calculated for the distribution of ionic species and atomic charge, the characteristics of their photo catalytic decomposition were estimated. It was shown that the decomposition characteristics was linearly proportional to nitrogen atomic charge value. On the other hand, the effects of aqueous pH, oxygen content and concentration on the TiO2 photo catalytic characteristics of EDTA, EDTA-Cu(II) and EDTA-Fe(III) were experimentally investigated. All EDTA systems were decomposed better in the pH range of 2.5-3.0 and with more dissolved oxygen. These results could be applied to construction of a process for removal of organic impurities dissolved in a source of system water, or for treatment of EDTA-containing liquid waste produced by a chemical cleaning in the domestic NPPs. (author)

  10. Heteropolymolybdate as a New Reaction-controlled Phase-transfer Catalyst for Efficient Alcohol Oxidation with Hydrogen Peroxide

    Institute of Scientific and Technical Information of China (English)

    Zhi Huan WENG; Jin Yan WANG; Xi Gao JIAN

    2006-01-01

    A new catalytic process for the synthesis of aldehyde from alcohol by oxidation with H2O2 with high selectivity was studied. In this system, heteropolymolybdate [C7H7N(CH3)3]3{PO4[MoO(O2)2]4} was utilized as the reaction-controlled phase-transfer catalyst to catalyze oxidation of benzyl and aliphatic alcohols. The molar ratio of H2O2 and alcohol was 0.75, no other by-products were detected by gas chromatography, the results of oxidation reaction indicated that the catalyst has high activity and stability.

  11. Importance of the oxygen bond strength for catalytic activity in soot oxidation

    DEFF Research Database (Denmark)

    Christensen, Jakob M.; Grunwaldt, Jan-Dierk; Jensen, Anker D.

    2016-01-01

    (loose contact) the rate constants for a number of catalytic materials outline a volcano curve when plotted against their heats of oxygen chemisorption. However, the optima of the volcanoes correspond to different heats of chemisorption for the two contact situations. In both cases the activation...... oxidation. The optimum of the volcano curve in loose contact is estimated to occur between the bond strengths of α-Fe2O3 and α-Cr2O3. Guided by an interpolation principle FeaCrbOx binary oxides were tested, and the activity of these oxides was observed to pass through an optimum for an FeCr2Ox binary oxide...

  12. Correlation between the microstructures of graphite oxides and their catalytic behaviors in air oxidation of benzyl alcohol.

    Science.gov (United States)

    Geng, Longlong; Wu, Shujie; Zou, Yongcun; Jia, Mingjun; Zhang, Wenxiang; Yan, Wenfu; Liu, Gang

    2014-05-01

    A series of graphite oxide (GO) materials were obtained by thermal treatment of oxidized natural graphite powder at different temperatures (from 100 to 200 °C). The microstructure evolution (i.e., layer structure and surface functional groups) of the graphite oxide during the heating process is studied by various characterization means, including XRD, N2 adsorption, TG-DTA, in situ DRIFT, XPS, Raman, TEM and Boehm titration. The characterization results show that the structures of GO materials change gradually from multilayer sheets to a transparent ultrathin 2D structure of the carbon sheets. The concentration of surface COH and HOCO groups decrease significantly upon treating temperature increasing. Benzyl alcohol oxidation with air as oxidant source was carried out to detect the catalytic behaviors of different GO materials. The activities of GO materials decrease with the increase of treating temperatures. It shows that the structure properties, including ultrathin sheets and high specific surface area, are not crucial factors affecting the catalytic activity. The type and amount of surface oxygen-containing functional groups of GO materials tightly correlates with the catalytic performance. Carboxylic groups on the surface of GO should act as oxidative sites for benzyl alcohol and the reduced form could be reoxidized by molecular oxygen.

  13. Catalytic and mechanistic insights of the low-temperature selective oxidation of methane over Cu-promoted Fe-ZSM-5.

    Science.gov (United States)

    Hammond, Ceri; Jenkins, Robert L; Dimitratos, Nikolaos; Lopez-Sanchez, Jose Antonio; ab Rahim, Mohd Hasbi; Forde, Michael M; Thetford, Adam; Murphy, Damien M; Hagen, Henk; Stangland, Eric E; Moulijn, Jacob M; Taylor, Stuart H; Willock, David J; Hutchings, Graham J

    2012-12-01

    The partial oxidation of methane to methanol presents one of the most challenging targets in catalysis. Although this is the focus of much research, until recently, approaches had proceeded at low catalytic rates (<10 h(-1)), not resulted in a closed catalytic cycle, or were unable to produce methanol with a reasonable selectivity. Recent research has demonstrated, however, that a system composed of an iron- and copper-containing zeolite is able to catalytically convert methane to methanol with turnover frequencies (TOFs) of over 14,000 h(-1) by using H(2)O(2) as terminal oxidant. However, the precise roles of the catalyst and the full mechanistic cycle remain unclear. We hereby report a systematic study of the kinetic parameters and mechanistic features of the process, and present a reaction network consisting of the activation of methane, the formation of an activated hydroperoxy species, and the by-production of hydroxyl radicals. The catalytic system in question results in a low-energy methane activation route, and allows selective C(1)-oxidation to proceed under intrinsically mild reaction conditions. PMID:23150452

  14. The variation of cationic microstructure in Mn-doped spinel ferrite during calcination and its effect on formaldehyde catalytic oxidation.

    Science.gov (United States)

    Liang, Xiaoliang; Liu, Peng; He, Hongping; Wei, Gaoling; Chen, Tianhu; Tan, Wei; Tan, Fuding; Zhu, Jianxi; Zhu, Runliang

    2016-04-01

    In this study, a series of Mn substituted spinel ferrites calcinated at different temperatures were used as catalysts for the oxidation of formaldehyde (HCHO). X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and H2 temperature-programmed reduction were conducted to characterize the structure and physico-chemical properties of catalysts, which were affected by calcination in the range of 200-600°C. Results show that all the ferrites were with spinel structure, and those calcinated in the range of 300-600°C were in the phase of maghemite. The calcination changed the valence and distribution of Mn and Fe on the ferrite surface, and accordingly the reducibility of ferrites. The HCHO catalytic oxidation test showed that with the increase of calcination temperature, the activity was initially improved until 400°C, but then decreased. The variation of HCHO conversion performance was well positively correlated to the variation of reduction temperature of surface Mn(4+) species. The remarkable effect of calcination on the catalytic activity of Mn-doped spinel ferrites for HCHO oxidation was discussed in view of reaction mechanism and variations in cationic microstructure of Mn-doped ferrites. PMID:26774985

  15. Catalytic wet oxidation of the pretreated synthetic pulp and paper mill effluent under moderate conditions.

    Science.gov (United States)

    Garg, Anurag; Mishra, I M; Chand, Shri

    2007-01-01

    In the present study, catalytic wet oxidation (CWO) was investigated for the destruction of organic pollutants in the thermally pretreated effluent from a pulp and paper mill under moderate temperature and pressure conditions. The thermal pretreatment studies were conducted at atmospheric pressure and 368K using copper sulfate as a catalyst. The thermal pretreatment reduced COD by about 61%. The filtrate of the thermal pretreatment step was used at pH 8.0 for CWO at 383-443K temperature and a total pressure of 0.85MPa for 4h. Catalysts used for the reaction include copper sulfate, 5% CuO/95% activated carbon, 60% CuO/40% MnO(2), and 60% CuO/40% CeO(2). Maximum COD reduction was found to be 89% during CWO step using 5% CuO/95% activated carbon with a catalyst loading of 8gl(-1) at 443K and 0.85MPa total pressure. Overall COD reduction for the pretreatment and the CWO was found to be 96%. Besides this, 60% CuO/40% CeO(2) catalyst also exhibited the similar activity as that of obtained with 5% CuO/95% activated carbon catalyst at 423K temperature and 0.85MPa total pressure. The pH of the solution during the experimental runs decreases initially due to the formation of carboxylic acid and then increases due to the decomposition of acids. PMID:16934854

  16. Catalytic oxidation at surfaces: insight from first-principles statistical mechanics (abstract only)

    Science.gov (United States)

    Rogal, Jutta

    2008-02-01

    Accomplishing a first-principles modeling of heterogeneous catalysis that allows for a quantitative description of the catalytic activity over a wide range of relevant environmental conditions (e.g. elevated temperatures and ambient pressures) poses an enormous challenge. Detailed insight into the elementary processes taking place on a microscopic level can nowadays often be obtained by employing ab initio electronic structure theory calculations. The statistical interplay between these processes, however, which is decisive for the functionality of a material only evolves in the mesoscopic to macroscopic regime. Here we apply a multiscale modeling approach to achieve a predictive modeling of macroscopic material properties on the basis of a microscopic understanding. Within this approach we use density-functional theory to accurately describe the elementary processes in the microscopic regime and we then combine these results with concepts from thermodynamics and statistical mechanics to obtain an appropriate linking to the mesoscopic and macroscopic regimes. Employing this approach to the field of heterogeneous catalysis we investigate CO oxidation over the Pd(100) surface as an example, particularly focusing on the relevance of the surrounding gas phase as well as the reaction kinetics on the structure and composition of the catalyst surface.

  17. Orange II removal by catalytic wet peroxide oxidation using activated carbon xerogels

    OpenAIRE

    Pinho, Maria; Silva, Adrián; Fathy, Nady; Attia, Amina; Gomes, Helder; Faria, Joaquim

    2013-01-01

    Orange II is a synthetic dye widely employed in the textile industry and responsible for serious environrnentaI cancerns. Dyes like this urge the development af new technologies for the treatment af wastewaters generated in this industrial activity. Those include catalytic wet peroxide oxidation (CWPO), which is an advanced oxidation process (AOP) based on the generation of hydroxyl radicais (I-lO·) from hydrogen peroxide with tlle aid ofa suitable catalysl [I].

  18. Catalytic catechol oxidation by copper complexes : development of a structure-activity relationship

    NARCIS (Netherlands)

    Ording-Wenker, Erica C M; Siegler, Maxime A; Lutz, Martin; Bouwman, Elisabeth

    2015-01-01

    A large library of Cu(II) complexes with mononucleating and dinucleating ligands was synthesized to investigate their potential as catalysts for the catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC). X-ray structure determination for a number of these complexes revealed relatively large Cu

  19. Silica-gel Supported V Complexes:Preparation, Characterization and Catalytic Oxidative Desulfurization

    Institute of Scientific and Technical Information of China (English)

    黎俊波; 刘习文; 曹灿灿; 郭嘉; 潘志权

    2013-01-01

    In this manuscript, a series of catalyst SGn-[VVO2-PAMAM-MSA] (SG=silica gel, PAMAM=poly-amidoamine, MSA=5-methyl salicylaldehyde, n=0, 1, 2, 3) was prepared and their structures were fully charac-terized by Fourier transform-infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), X-ray photoelec-tron spectroscopy (XPS) and inductive coupled plasma emission spectrometer (ICP) etc. XPS revealed that the metal V and SGn-PAMAM-MSA combined more closely after the formation of Schiff base derivatives. Their cata-lytic activities for oxidation of dibenzothiophene were evaluated using tert-butyl hydroperoxide as oxidant. The results showed that the catalyst SG2.0-[VVO2-PAMAM-MSA] presented good catalytic activity and recycling time. Mean-while, the optimal condition for the catalytic oxidation of SG2.0-[VVO2-PAMAM-MSA] was also investigated, which showed that when the oxidation temperature was 90 °C, time was 60 min, the O/S was 3︰1, and the mass content of catalyst was 1%, the rate of desulfurization could reach 85.2%. Moreover, the catalyst can be recycled several times without significant decline in catalytic activity.

  20. Bulk Preparation of Holey Graphene via Controlled Catalytic Oxidation

    Science.gov (United States)

    Watson, Kent (Inventor); Lin, Yi (Inventor); Ghose, Sayata (Inventor); Connell, John (Inventor)

    2015-01-01

    A scalable method allows preparation of bulk quantities of holey carbon allotropes with holes ranging from a few to over 100 nm in diameter. Carbon oxidation catalyst nanoparticles are first deposited onto a carbon allotrope surface in a facile, controllable, and solvent-free process. The catalyst-loaded carbons are then subjected to thermal treatment in air. The carbons in contact with the carbon oxidation catalyst nanoparticles are selectively oxidized into gaseous byproducts such as CO or CO.sub.2, leaving the surface with holes. The catalyst is then removed via refluxing in diluted nitric acid to obtain the final holey carbon allotropes. The average size of the holes correlates strongly with the size of the catalyst nanoparticles and is controlled by adjusting the catalyst precursor concentration. The temperature and time of the air oxidation step, and the catalyst removal treatment conditions, strongly affect the morphology of the holes.

  1. The applicability of the catalytic wet-oxidation to CELSS

    Science.gov (United States)

    Takahashi, Y.; Nitta, K.; Ohya, H.; Oguchi, M.

    1987-01-01

    The wet oxidation catalysis of Au, Pd, Pt, Rh or Ru on a ceramic honeycomb carrier was traced in detail by 16 to 20 repetitive batch tests each. As a result, Pt or Pd on a honeycomb carrier was shown to catalyze complete nitrogen gasification as N2. Though the catalysts which realize both complete nitrogen gasification and complete oxidation could not be found, the Ru+Rh catalyst was found to be most promising. Ru honeycomb catalyzed both nitrification and nitrogen gasification.

  2. Catalytic Performance of Zeolite-Supported Vanadia in the Aerobic Oxidation of 5-hydroxymethylfurfural to 2,5- diformylfuran

    DEFF Research Database (Denmark)

    Sádaba, Irantzu; Gorbanev, Yury; Kegnæs, Søren;

    2013-01-01

    /Vis spectrophotometry. The H-beta zeolite catalysts were found to contain highly dispersed vanadium oxide species at all loadings, and provided the highest reaction selectivity towards DFF and the lowest metal leaching of the examined systems. In particular, 1 wt % V2O5/H-beta was found to be a stable, recyclable......The catalytic performance of zeolite-supported vanadia catalysts was examined for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) in organic solvents such as N,N-dimethylformamide (DMF), methyl isobutyl ketone, toluene, trifluorotoluene and DMSO. Catalysts based...... on the four different zeolite supports H-beta, H-Y, H-mordenite, and H-ZSM-5 with 1–10 wt% vanadia loading were prepared and characterized by nitrogen physisorption, X-ray powder diffraction, scanning electron  microscopy, ammonia temperature-programmed desorption, Raman spectroscopy and UV...

  3. Laccase-Functionalized Graphene Oxide Assemblies as Efficient Nanobiocatalysts for Oxidation Reactions

    NARCIS (Netherlands)

    Patila, Michaela; Kouloumpis, Antonios; Gournis, Dimitrios; Rudolf, Petra; Stamatis, Haralambos

    2016-01-01

    Multi-layer graphene oxide-enzyme nanoassemblies were prepared through the multi-point covalent immobilization of laccase from Trametes versicolor (TvL) on functionalized graphene oxide (fGO). The catalytic properties of the fGO-TvL nanoassemblies were found to depend on the number of the graphene o

  4. Preparation and characterization of Ce1-xFexO2 complex oxides and its catalytic activity for methane selective oxidation

    Institute of Scientific and Technical Information of China (English)

    LI Kongzhai; WANG Hua; WEI Yonggang; LIU Mingchun

    2008-01-01

    A series of Ce1-xFexO2 (x=0, 0.2, 0.4, 0.6, 0.8, 1) complex oxide catalysts were prepared using the coprecipitation method. The catalysts were characterized by means of XRD and H2-TPR. The reactions between methane and lattice oxygen from the complex oxides were investigated. The characteristic results revealed that the combination of Ce and Fe oxide in the catalysts could lower the temperature necessary to reduce the cerium oxide. The catalytic activity for selective CH4 oxidation was strongly influenced by dropped Fe species. Adding the appropriate amount of Fe2O3 to CeO2 could promote the action between CH4 and CeO2. Dispersed Fe2O3 first returned to the original state and would then virtually form the Fe species on the catalyst, which could be considered as the active site for selective CH4 oxidation. The appearance of carbon formation was significant and the oxidation of carbon appeared to be the rate-determining step; the amounts of surface reducible oxygen species in CeO2 were also relevant to the activity. Among all the catalysts, Ce0.6Fe0.4O2 exhibited the best activity, which converted 94.52% of CH4 at 900 °C.

  5. Selective catalytic reduction of nitric oxide with acetaldehyde over NaY zeolite catalyst in lean exhaust feed

    International Nuclear Information System (INIS)

    Steady-state selective catalytic reduction (SCR) of nitric oxide (NO) was investigated under simulated lean-burn conditions using acetaldehyde (CH3CHO) as the reductant. This work describes the influence of catalyst space velocity and the impact of nitric oxide, acetaldehyde, oxygen, sulfur dioxide, and water on NOx reduction activity over NaY zeolite catalyst. Results indicate that with sufficient catalyst volume 90% NOx conversion can be achieved at temperatures relevant to light-duty diesel exhaust (150-350C). Nitric oxide and acetaldehyde react to form N2, HCN, and CO2. Oxygen is necessary in the exhaust feed stream to oxidize NO to NO2 over the catalyst prior to reduction, and water is required to prevent catalyst deactivation. Under conditions of excess acetaldehyde (C1:N>6:1) and low temperature (x conversion is apparently very high; however, the NOx conversion steadily declines with time due to catalytic oxidation of some of the stored (adsorbed) NO to NO2, which can have a significant impact on steady-state NOx conversion. With 250ppm NO in the exhaust feed stream, maximum NOx conversion at 200C can be achieved with =400ppm of acetaldehyde, with higher acetaldehyde concentrations resulting in production of acetic acid and breakthrough of NO2 causing lower NOx conversion levels. Less acetaldehyde is necessary at lower NO concentrations, while more acetaldehyde is required at higher temperatures. Sulfur in the exhaust feed stream as SO2 can cause slow deactivation of the catalyst by poisoning the adsorption and subsequent reaction of nitric oxide and acetaldehyde, particularly at low temperature

  6. Treatment of phenol wastewater by microwave-induced ClO2-CuOx/Al2O3 catalytic oxidation process

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The catalyst of CuOx/Al2O3 was prepared by the dipping-sedimentation method using γ-Al2O3 as a carrier. CuO and Cu2O were loaded on the surface of γ-Al2O3, characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). In the presence of CuOx/Al2O3, the microwave-induced chlorine dioxide (ClO2) catalytic oxidation process was conducted for the treatment of synthetic wastewater containing 100 mg/L phenol. The relationships between removal percentage and initial ClO2 concentration, catalyst dosage, microwave power, contact time, initial phenol concentration and pH were investigated and the results showed that microwave-induced ClO2-CuOx/Al2O3 process could effectively degrade contaminants in a short reaction time with a low oxidant dosage, extensive pH range. Under a given condition (ClO2 concentration 80 mg/L, microwave power 50 W, contact time 5 min, catalyst dosage 50 g/L, pH 9), phenol removal percentage approached 92.24%, corresponding to 79.13% of CODCr removal. The removal of phenol by microwave-induced ClO2-CuOx/Al2O3 catalytic oxidation process was a complicated non-homogeneous solid/water reaction, which fitted pseudo-first-order by kinetics. Compared with traditional ClO2 oxidation, ClO2 catalytic oxidation and microwave-induced ClO2 oxidation, microwave-induced ClO2 catalytic oxidation system could significantly enhance the degradation efficiency. It provides an effective technology for the removal of phenol wastewater.

  7. Effect of vegetable oil oxidation on the hydrogenation reaction process

    OpenAIRE

    Kalantari, Faranak; Bahmaei, Manochehr; Ameri, Majid; Shoaei, Ehsan

    2010-01-01

    Hydrogenation has been carried out in a batch reactor with three different oxidized bleached oils in order to discover the effect of oxidation on the hydrogenation reaction process. Specifications of hydrogenated oils such as melting point, Iodine value, solid fat content and fatty acid composition of the oxidized oils were compared with their un-oxidized reference oils. Oxidized bleached sunflower oil was hydrogenated to target melting points (34, 39 and 42°C) at higher iodine values vs. its...

  8. Application of 3-Methyl-2-vinylindoles in Catalytic Asymmetric Povarov Reaction: Diastereo- and Enantioselective Synthesis of Indole-Derived Tetrahydroquinolines.

    Science.gov (United States)

    Dai, Wei; Jiang, Xiao-Li; Tao, Ji-Yu; Shi, Feng

    2016-01-01

    The first application of 3-methyl-2-vinylindoles in catalytic asymmetric Povarov reactions has been established via the three-component reactions of 3-methyl-2-vinylindoles, aldehydes, and anilines in the presence of chiral phosphoric acid, providing easy access to chiral indole-derived tetrahydroquinolines with three contiguous stereogenic centers at high yields (up to 99%) and with excellent diastereo- and enantioselectivities (all >95:5 dr, up to 96% ee). This mode of catalytic asymmetric three-component reaction offers a step-economic and atom-economic strategy for accessing enantioenriched indole-derived tetrahydroquinolines with structural diversity and complexity. PMID:26652222

  9. Catalytic performance of Metal‐Organic‐Frameworks vs. extra‐large pore zeolite UTL incondensation reactions

    Directory of Open Access Journals (Sweden)

    Mariya eShamzhy

    2013-08-01

    Full Text Available Catalytic behavior of isomorphously substituted B‐, Al‐, Ga‐, and Fe‐containing extra‐large pore UTLzeolites was investigated in Knoevenagel condensation involving aldehydes, Pechmann condensationof 1‐naphthol with ethylacetoacetate, and Prins reaction of β‐pinene with formaldehyde andcompared with large‐pore aluminosilicate zeolite BEA and representative Metal‐Organic‐FrameworksCu3(BTC2 and Fe(BTC. The yield of the target product over the investigated catalysts in Knoevenagelcondensation increases in the following sequence: (AlBEA < (AlUTL < (GaUTL < (FeUTL < Fe(BTC <(BUTL < Cu3(BTC2 being mainly related to the improving selectivity with decreasing strength ofactive sites of the individual catalysts. The catalytic performance of Fe(BTC, containing the highestconcentration of Lewis acid sites of the appropriate strength is superior over large‐pore zeolite(AlBEA and B‐, Al‐, Ga‐, Fe‐substituted extra‐large pore zeolites UTL in Prins reaction of β‐pinene withformaldehyde and Pechmann condensation of 1‐naphthol with ethylacetoacetate.

  10. Synthesis and catalytic property of Cu-Mn-Ce/ γ -Al2O3 complex oxide

    Institute of Scientific and Technical Information of China (English)

    黄可龙; 王红霞; 刘素琴; 桂客

    2002-01-01

    A new type of catalytic material for purification of automobile exhaust,Cu-Mn-Ce-O/ γ -Al2O3,has been studied.The factors affecting its catalytic activity,such as calcination temperature and the period of calcinations and so on have been investigated.Its catalytic activity after SO2-poisoning was determined in a fixed-bed reactor by exposing the sample to the atmosphere of 160 mL/min SO2/air.The study reveals that the catalyst has shown high catalytic activities for the conversion of NH3 oxidation by NO after sulfate.The conversion of NO reduction over the sulfated catalyst is somewhat higher than that over the fresh catalyst except that the optimum temperature has increased about 100 ℃.Also at the optimum process for the experiment,the selective catalytic oxidation of CO by NO is over 76% and the conversion of NO reduction is over 80% by NH3.

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

    Science.gov (United States)

    Kokate, Mangesh; Garadkar, Kalyanrao; Gole, Anand

    2016-12-01

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

  12. Precipitation and calcination synthesis methods forming nano-sized platinum catalytic particles for methanol and hydrogen oxidation

    Science.gov (United States)

    Naidoo, S.; Naidoo, Q.; Musil, E.; Linkov, V.; Vaivars, G.

    2013-03-01

    Under varying experimental conditions of calcination and precipitation reactions, different particle sizes and levels of platinum on carbon supported (Pt/C) catalysts were obtained. Rapid precipitation following a chemical reaction ensured formation of nano-sized catalytic particles using super-saturated concentrations under controlled conditions was a significant contribution in understanding the synthesis process and how it relates to an increased number of catalytic reaction sites ultimately providing superior electrochemical (EC) activity. These conditions influenced nucleation and growth rates of the catalytic particles. The super-saturation concentrations of the reactants in the reaction vessel played a direct role in producing the desired morphology of the crystallites.

  13. A New Class of Highly Dispersed VOx Catalysts on Mesoporous Silica: Synthesis, Characterization, and Catalytic Activity in the Partial Oxidation of Ethanol

    Energy Technology Data Exchange (ETDEWEB)

    Kwak, Ja Hun; Herrera, Jose E.; Hu, Jian Zhi; Wang, Yong; Peden, Charles HF

    2006-01-26

    The morphology of vanadium oxide supported on a titania-modified mesoporous silica (MCM-41), obtained by means of a careful grafting process through atomic layer deposition, was studied using a variety of characterization techniques. The XRD together with TEM, 51V-NMR, Raman, FTIR and DRS-UV-Vis results showed that the vanadia species are extremely well dispersed onto the surface of the mesoporous support; the dispersion being stable upon thermal treatments up to 400 °C. Studies of the catalytic activity of these materials were performed using the partial oxidation of ethanol as a probe reaction. The results indicate an intrinsic relationship between dispersion, the presence of a TiO2-VOx phase, and catalytic activity for oxidation and dehydration.

  14. Reaction Mechanism for m-Xylene Oxidation in the Claus Process by Sulfur Dioxide.

    Science.gov (United States)

    Sinha, Sourab; Raj, Abhijeet; Al Shoaibi, Ahmed S; Chung, Suk Ho

    2015-09-24

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation.

  15. Simultaneous catalytic removal of NOx and diesel soot particulate over perovskite-type oxides and supported Ag catalysts

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A series of perovskite-type oxides and supported Ag catalysts were prepared,and characterized by X-ray diffraction (XRD) and Xray photoelectron spectroscopy (XPS).The catalytic activities of the catalysts as well as influencing factors on catalytic activity have been investigated for the simultaneous removal of NOx and diesel soot particulate.An increase in catalytic activity for the selective reduction of NOx was observed with Ag addition in these perovskite oxides,especially with 5% Ag loading.This catalyst could be a promising candidate of catalytic material for the simultaneous elimination of NOx and diesel soot.

  16. Recombinant oxalate decarboxylase: enhancement of a hybrid catalytic cascade for the complete electro-oxidation of glycerol.

    Science.gov (United States)

    Abdellaoui, Sofiene; Hickey, David P; Stephens, Andrew R; Minteer, Shelley D

    2015-10-01

    The complete electro-oxidation of glycerol to CO2 is performed through an oxidation cascade using a hybrid catalytic system combining a recombinant enzyme, oxalate decarboxylase from Bacillus subtilis, and an organic oxidation catalyst, 4-amino-TEMPO. This system is capable of electrochemically oxidizing glycerol at a carbon electrode collecting all 14 electrons per molecule. PMID:26271633

  17. Modeling of adsorber/desorber/catalytic reactor system for ethylene oxide removal

    OpenAIRE

    ZELJKO B. GRBAVCIC; BOSKO V. GRBIC; ZORANA LJ. ARSENIJEVIC

    2004-01-01

    The removal of ethylene oxide (EtO) in a combined system adsorber/desorber/catalytic reactor has been investigated. The combined system was a modified draft tube spouted bed reactor loaded with Pt/Al2O3 catalyst. The annular region was divided into two sectons, the hot section contained about 7 % of catalyst and it behaved as a desorber and catalytic incinerator, while the cold section, with the rest of the catalyst, behaved as a sorber. The catalyst particles were circulated between the two ...

  18. Selective Production of Aromatic Aldehydes from Heavy Fraction of Bio-oil via Catalytic Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yan; Chang, Jie; Ouyang, Yong; Zheng, Xianwei [South China Univ. of Technology, Guangzhou (China)

    2014-06-15

    High value-added aromatic aldehydes (e. g. vanillin and syringaldehyde) were produced from heavy fraction of bio-oil (HFBO) via catalytic oxidation. The concept is based on the use of metalloporphyin as catalyst and hydrogen peroxide (H{sub 2}O{sub 2}) as oxidant under alkaline condition. The biomimetic catalyst cobalt(II)-sulfonated tetraphenylporphyrin (Co(TPPS{sub 4})) was prepared and characterized. It exhibited relative high activity in the catalytic oxidation of HFBO. 4.57 wt % vanillin and 1.58 wt % syringaldehyde were obtained from catalytic oxidation of HFBO, compared to 2.6 wt % vanillin and 0.86 wt % syringaldehyde without Co(TPPS{sub 4}). Moreover, a possible mechanism of HFBO oxidation using Co(TPPS{sub 4})/H{sub 2}O{sub 2} was proposed by the research of model compounds. The results showed that this is a promising and environmentally friendly method for production of aromatic aldehydes from HFBO under Co(TPPS{sub 4})/H{sub 2}O{sub 2} system.

  19. Effects of calcium substitute in LaMnO3 perovskites for NO catalytic oxidation

    Institute of Scientific and Technical Information of China (English)

    SHEN Meiqing; ZHAO Zhen; CHEN Jiahao; SU Yugeng; WANG Jun; WANG Xinquan

    2013-01-01

    La1-xCaxMnO3 (x=0-0.3) perovskite-type oxides were synthesized by citrate sol-gel method.The physical and chemical properties were characterized by X-ray diffraction (XRD),Brumauer-Emmett-Teller method (BET),X-ray photoelectron spectroscopy (XPS),NO+O2-TPD (temperature-programmed desorption),activated oxygen evaluation and H2-TPR (temperature-programmed reduction) technologies.The results showed that NO catalytic oxidation activity was significantly improved by Ca substitution,especially for lower temperature activity.The La0.9Ca0.1UnO3 sample showed the maximum conversion of 82% at 300 ℃.The monodentate nitrates played a crucial role for the formation of NO2.The reducibility of Mn4+ ions and reactivity of activated oxygen were favorable for the catalytic performances of NO oxidation.

  20. Electro-catalytic oxidative cleavage of lignin in a protic ionic liquid.

    Science.gov (United States)

    Reichert, Elena; Wintringer, Reiner; Volmer, Dietrich A; Hempelmann, Rolf

    2012-04-21

    Lignin is a component of lignocellulosic biomass and a promising matrix for recovering important renewable aromatic compounds. We present a new approach of electro-oxidative cleavage of lignin, dissolved in a special protic ionic liquid, using an anode with particular electro-catalytic activity. As appropriate ionic liquid triethylammonium methanesulfonate was identified, synthesised, explored for dissolution of alkali-lignin and used for electrolysis of 5 wt.% lignin solutions. As appropriate anode material, oxidation-stable ruthenium-vanadium-titanium mixed oxide electrodes were prepared and explored for their electro-catalytic activity. The electrolysis was performed at several potentials in the range from 1.0 V to 1.5 V (vs. an Ag pseudo reference electrode). A wide range of aromatic fragments was identified as cleavage products by means of GC-MS and HPLC measurements. PMID:22398694

  1. Synthesis, characterization and catalytic activity toward methanol oxidation of electrocatalyst Pt4+-NH2-MCM-41

    International Nuclear Information System (INIS)

    Highlights: ► It was first confirmed that the Pt4+ exhibited a good electro-catalytic property for methanol oxidation. ► The Pt4+ perfectly distributed on a mesoporous molecular sieve matrix synthesis by a facile method. ► The good performance of catalyst resistance to poisoning because of a homogeneous distribution of Pt4+ and large specific surface area. - Abstract: Mesoporous material with functional group (Pt4+-NH2-MCM-41) was prepared by grafting aminopropyl group and adsorbing platinum ions on the surface of the commercial molecular sieve (MCM-41). The characterization carried out by X-ray photoelectron spectroscopy, X-ray diffraction, and N2 adsorption–desorption measurement pointed out that Pt was adsorbed on the NH2-MCM-41 surface as the oxidation state (Pt4+) and the surface area of Pt4+-NH2-MCM-41 was up to 564 m2/g. Transmission electron microscopy and elemental mapping indicated a homogeneous distribution of Pt4+ throughout all surface of the mesoporous materials. Electro-catalytic properties of methanol oxidation on the Pt4+-NH2-MCM-41 electrode were investigated with electrochemical methods. The results showed that the Pt4+-NH2-MCM-41 electrode exhibited catalytic activity in the methanol electro-oxidation with the apparent activation energy being 49.29 kJ/mol, and the control step of methanol electro-oxidation was the mass transfer process. It is first proved that platinum ions had good electro-catalytic property for methanol oxidation and provided a new idea for developing electrode materials in future.

  2. Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions.

    Science.gov (United States)

    Feng, Zhenxing; Hong, Wesley T; Fong, Dillon D; Lee, Yueh-Lin; Yacoby, Yizhak; Morgan, Dane; Shao-Horn, Yang

    2016-05-17

    Electrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal-air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive and have shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Detailed studies of the oxide surface atomic structure and chemistry (e.g., cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts. In this Account, we focus on recent advances in characterizing strontium (Sr) cation segregation and enrichment near the surface of Sr-substituted perovskite oxides under different operating conditions (e.g., high temperature, applied potential), as well as their influence on the surface oxygen exchange kinetics at elevated temperatures. We contrast Sr segregation, which is associated with Sr redistribution in the crystal lattice near the surface, with Sr enrichment, which involves Sr redistribution via the formation of secondary phases. The newly developed coherent Bragg rod analysis (COBRA) and energy-modulated differential COBRA are uniquely powerful ways of providing information about surface and interfacial cation segregation at the atomic scale for these thin film electrocatalysts. In situ ambient pressure X-ray photoelectron spectroscopy (APXPS) studies under electrochemical operating conditions give additional insights into cation migration. Direct COBRA and APXPS evidence for surface Sr segregation was found for La1-xSrxCoO3-δ and (La1-ySry)2CoO4±δ/La1-xSrxCoO3-δ oxide thin films, and

  3. Low-temperature catalytic oxidation of NO over Mn-Ce-O_x catalyst

    Institute of Scientific and Technical Information of China (English)

    李华; 唐晓龙; 易红宏; 于丽丽

    2010-01-01

    A series of manganese-cerium oxide catalysts were prepared by different methods and used for low-temperature catalytic oxidation of NO in the presence of excess O2.Their surface properties were evaluated by means of BET and were characterized by using scanning electron microscopy(SEM) and X-ray diffractometer(XRD).The activity test of Mn-Ce-Ox catalysts showed that addition of Ce enhanced the activities of NO oxidation.The most active catalysts with a molar Ce/(Mn+Ce) ratio of 0.3 were prepared by co-precip...

  4. An Overview of Recent Advances of the Catalytic Selective Oxidation of Ethane to Oxygenates

    Directory of Open Access Journals (Sweden)

    Robert D. Armstrong

    2016-05-01

    Full Text Available The selective partial oxidation of short chain alkanes is a key challenge within catalysis research. Direct ethane oxidation to oxygenates is a difficult aim, but potentially rewarding, and it could lead to a paradigm shift in the supply chain of several bulk chemicals. Unfortunately, low C–H bond reactivity and kinetically labile products are just some reasons affecting the development and commercialisation of such processes. Research into direct ethane oxidation is therefore disparate, with approaches ranging from oxidation in the gas phase at high temperatures to enzyme catalysed hydroxylation under ambient conditions. Furthermore, in overcoming the barrier posed by the chemically inert C–H bond a range of oxidants have been utilised. Despite years of research, this remains an intriguing topic from both academic and commercial perspectives. Herein we describe some recent developments within the field of catalytic ethane oxidation focusing on the formation of oxygenated products, whilst addressing the key challenges which are still to be overcome.

  5. Catalytic Enhancement of Solid Carbon Oxidation in HDCFCs

    DEFF Research Database (Denmark)

    Deleebeeck, Lisa; Ippolito, Davide; Kammer Hansen, Kent

    2014-01-01

    was investigated using current-potential-power density curves. In the anode chamber, catalysts are mixed with the carbon-carbonate mixture. These catalysts include various manganese oxides (MnO2, Mn2O3, and Mn3O4) and dopedceria (CeO2, Ce1-xGdxO2-x/2, Ce1-xRExO2-delta (RE = Pr, Sm)), the effectiveness......Hybrid direct carbon fuel cells consisting of a solid carbon (carbon black)-molten carbonate ((62-38 wt% Li-K)(2)CO3) mixtures in the anode chamber of an anode-supported solid oxide fuel cell type full-cell are tested for their electrochemical performance between 700 and 800 degrees C. Performance...

  6. Catalytic Enhancement of Solid Carbon Oxidation in HDCFCs

    DEFF Research Database (Denmark)

    Deleebeeck, Lisa; Ippolito, Davide; Kammer Hansen, Kent

    2014-01-01

    data as a function of temperature, anode and cathode atmospheres, and their flow rates are discussed. In the anode chamber, catalysts are mixed with the carbon-carbonate mixture. These catalysts include various manganese oxides (MnO2, Mn2O3, and Mn3O4, Fig. 1) and doped-ceria (CeO2, Ce1-xGdxO2, Ce1-x......RExO2 (RE = Pr, Gd, Sm, etc.)), the effectiveness of these families of catalysts are discussed with respect to electrochemical, chemical and post-mortem analysis. Fig. 1. Current-potential-power density curves acquired for a blank (SiC) and manganese oxide (MnO2, Mn2O3, Mn3O4) catalysts suspended......Hybrid direct carbon fuel cells (HDCFCs) consisting of a solid carbon (carbon black)-molten carbonate ((62-38 wt% Li-K)2CO3) mixtures in the anode chamber of an anode-supported solid oxide fuel cell (SOFC)-type full-cell (NiO-yttria-stablized zirconia (YSZ)|YSZ|lanthanum strontium manganite (LSM...

  7. Integrated Biomass Gasification with Catalytic Partial Oxidation for Selective Tar Conversion

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lingzhi; Wei, Wei; Manke, Jeff; Vazquez, Arturo; Thompson, Jeff; Thompson, Mark

    2011-05-28

    requirement for commercial deployment of biomass-based power/heat co-generation and biofuels production. There are several commonly used syngas clean-up technologies: (1) Syngas cooling and water scrubbing has been commercially proven but efficiency is low and it is only effective at small scales. This route is accompanied with troublesome wastewater treatment. (2) The tar filtration method requires frequent filter replacement and solid residue treatment, leading to high operation and capital costs. (3) Thermal destruction typically operates at temperatures higher than 1000oC. It has slow kinetics and potential soot formation issues. The system is expensive and materials are not reliable at high temperatures. (4) In-bed cracking catalysts show rapid deactivation, with durability to be demonstrated. (5) External catalytic cracking or steam reforming has low thermal efficiency and is faced with problematic catalyst coking. Under this program, catalytic partial oxidation (CPO) is being evaluated for syngas tar clean-up in biomass gasification. The CPO reaction is exothermic, implying that no external heat is needed and the system is of high thermal efficiency. CPO is capable of processing large gas volume, indicating a very compact catalyst bed and a low reactor cost. Instead of traditional physical removal of tar, the CPO concept converts tar into useful light gases (eg. CO, H2, CH4). This eliminates waste treatment and disposal requirements. All those advantages make the CPO catalytic tar conversion system a viable solution for biomass gasification downstream gas clean-up. This program was conducted from October 1 2008 to February 28 2011 and divided into five major tasks. - Task A: Perform conceptual design and conduct preliminary system and economic analysis (Q1 2009 ~ Q2 2009) - Task B: Biomass gasification tests, product characterization, and CPO tar conversion catalyst preparation. This task will be conducted after completing process design and system economics analysis

  8. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

    Science.gov (United States)

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-08-01

    Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size.

  9. Catalytic ozonation of oxalate with a cerium supported palladium oxide: An efficient degradation not relying on hydroxyl radical oxidation

    KAUST Repository

    Zhang, Tao

    2011-11-01

    The cerium supported palladium oxide (PdO/CeO 2) at a low palladium loading was found very effective in catalytic ozonation of oxalate, a probe compound that is difficult to be efficiently degraded in water with hydroxyl radical oxidation and one of the major byproducts in ozonation of organic matter. The oxalate was degraded into CO 2 during the catalytic ozonation. The molar ratio of oxalate degraded to ozone consumption increased with increasing catalyst dose and decreasing ozone dosage and pH under the conditions of this study. The maximum molar ratio reached around 1, meaning that the catalyst was highly active and selective for oxalate degradation in water. The catalytic ozonation, which showed relatively stable activity, does not promote hydroxyl radical generation from ozone. Analysis with ATR-FTIR and in situ Raman spectroscopy revealed that 1) oxalate was adsorbed on CeO 2 of the catalyst forming surface complexes, and 2) O 3 was adsorbed on PdO of the catalyst and further decomposed to surface atomic oxygen (*O), surface peroxide (*O 2), and O 2 gas in sequence. The results indicate that the high activity of the catalyst is related to the synergetic function of PdO and CeO 2 in that the surface atomic oxygen readily reacts with the surface cerium-oxalate complex. This kind of catalytic ozonation would be potentially effective for the degradation of polar refractory organic pollutants and hydrophilic natural organic matter. © 2011 American Chemical Society.

  10. Optimization of preparation conditions of Fe-Co nanoparticles in low-temperature CO oxidation reaction by taguchi design method

    Institute of Scientific and Technical Information of China (English)

    Abolfazl Biabani; Mehran Rezaei; Zohreh Fattah

    2012-01-01

    Mixed iron-cobalt oxide (Co/Fe molar ratio=1/5) are prepared using a simple co-precipitation procedure and studied for the catalytic oxidation of carbon monoxide.In particular,the effects of a range of preparation variables such as pH value when precipitation,aging temperature,precipitation agent type and aging time are investigated on the catalytic performance of synthesized Fe-Co oxides in CO oxidation reaction.In addition,the preparation factors were optimized by Taguchi design method.The optimized sample was characterized by XRD,N2 adsorption/desorption,TEM and TGA/DTA techniques.The results reveal that the optimized sample shows a mesoporous structure with a narrow pore size distribution centered in the range of 2-7 nm.The sample prepared under optimized conditions has high activity and stability toward removal of carbon monoxide at lower temperatures.It is shown that different preparation variables influence the catalytic performance of Fe-Co oxide in CO oxidation reaction.

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

    Science.gov (United States)

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

    2016-10-01

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

  12. Synergy of CuO and CeO2 combination for mercury oxidation under low-temperature selective catalytic reduction atmosphere

    KAUST Repository

    Li, Hailong

    2016-07-19

    Synergy for low temperature Hg0 oxidation under selective catalytic reduction (SCR) atmosphere was achieved when copper oxides and cerium oxides were combined in a CuO-CeO2/TiO2 (CuCeTi) catalyst. Hg0 oxidation efficiency as high as 99.0% was observed on the CuCeTi catalyst at 200 °C, even the gas hourly space velocity was extremely high. To analyze the synergistic effect, comparisons of catalyst performance in the presence of different SCR reaction gases were systematically conducted over CuO/TiO2 (CuTi), CeO2/TiO2 (CeTi) and CuCeTi catalysts prepared by sol-gel method. The interactions between copper oxides and cerium oxides in CuCeTi catalyst yielded more surface chemisorbed oxygen, and facilitated the conversion of gas-phase O2 to surface oxygen, which are favorable for Hg0 oxidation. Copper oxides in the combination interacted with NO forming more chemisorbed oxygen for Hg0 oxidation in the absence of gas-phase O2. Cerium oxides in the combination promoted Hg0 oxidation through enhancing the transformations of NO to NO2. In the absence of NO, NH3 exhibited no inhibitive effect on Hg0 oxidation, because enough Lewis acid sites due to the combination of copper oxides and cerium oxides scavenged the competitive adsorption between NH3 and Hg0. In the presence of NO, although NH3 lowered Hg0 oxidation rate through inducing reduction of oxidized mercury, complete recovery of Hg0 oxidation activity over the CuCeTi catalyst was quickly achieved after cutting off NH3. This study revealed the synergistic effect of the combination of copper oxides and cerium oxides on Hg0 oxidation, and explored the involved mechanisms. Such knowledge would help obtaining maximum Hg0 oxidation co-benefit from SCR units in coal-fired power plants.

  13. Paramagnetic relaxation enhancement solid-state NMR studies of heterogeneous catalytic reaction over HY zeolite using natural abundance reactant.

    Science.gov (United States)

    Zhou, Lei; Li, Shenhui; Su, Yongchao; Li, Bojie; Deng, Feng

    2015-01-01

    Paramagnetic relaxation enhancement solid-state NMR (PRE ssNMR) technique was used to investigate catalytic reaction over zeolite HY. After introducing paramagnetic Cu(II) ions into the zeolite, the enhancement of longitudinal relaxation rates of nearby nuclei, i.e.(29)Si of the framework and (13)C of the absorbents, was measured. It was demonstrated that the PRE ssNMR technique facilitated the fast acquisition of NMR signals to monitor the heterogeneous catalytic reaction (such as acetone to hydrocarbon) using natural abundance reactants. PMID:25616847

  14. Selective catalytic reduction of nitric oxide by methane over cerium and silver ion-exchanged ZSM-5 zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zhijiang; Flytzani-Stephanopoulos, Maria [Department of Chemical Engineering, Tufts University, Medford, MA (United States)

    1997-12-31

    A new catalyst comprising cerium and silver ion-exchanged ZSM-5 zeolite is reported in this paper, for the reduction of nitric oxide by methane in the presence of excess oxygen. The bi-cation exchanged Ce-Ag-ZSM-5 catalyst was very active for this reaction, while either Ce-ZSM-5 or Ag-ZSM-5 alone showed low activity. The presence of oxygen in the feed gas mixture enhanced the activity of the catalyst and the NO conversion to N{sub 2} increased with the CH{sub 4}/NO ratio and Ag loading of the zeolite. The presence of water vapor had a small adverse effect on the catalyst activity. The coexistence of Ce and Ag ions in the zeolite is crucial for achieving high NO conversion to N{sub 2}. A small amount of cerium is adequate to promote the selective catalytic reduction of NO. The two main functions of Ce ions are (1) to provide the Ag ion sites with NO{sub 2} by catalyzing the oxidation of NO to NO{sub 2} and (2) to suppress the direct CH{sub 4} oxidation to CO{sub 2}. The Ag sites are the active centers where the reaction of NO{sub 2} with CH{sub 4} takes place

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

    Science.gov (United States)

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

    2016-01-01

    SBA-15 mesoporous molecular sieves modified with copper (Cu-SBA-15) were prepared by pH-adjusting hydrothermal method and characterized by X-ray diffraction, BET, transmission electron microscopy, UV-Vis and (29)Si MAS NMR. The pH of the synthesis gel has a significant effect on the amount and the dispersion of copper on SBA-15. The Cu-SBA-15(4.5) (where 4.5 denotes the pH value of the synthesis gel) modified with highly dispersed copper was used as catalyst for the oxidation of aniline by H2O2. The Cu-SBA-15(4.5) shows a higher catalytic activity compared to CuO on the surface of SBA-15. The influences of reaction conditions, such as initial pH of the aqueous solutions, temperature, as well as the dosages of H2O2 and catalyst were investigated. Under weakly alkaline aqueous solution conditions, the aniline conversion, the H2O2 decomposition and the total organic carbon (TOC) removal could be increased significantly compared to the acid conditions. The percentage of leaching Cu(2+) could be decreased from 45.0% to 3.66% when the initial pH of solution was increased from 5 to 10. The TOC removal could be enhanced with the increases of temperature, H2O2 and catalyst dosage, but the aniline conversion and H2O2 decomposition change slightly with further increasing dosage of catalyst and H2O2. At 343 K and pH 8.0, 100% aniline conversion and 66.9% TOC removal can be achieved under the conditions of 1.0 g/L catalyst and 0.05 mol/L H2O2 after 180 min. Although copper might be slightly leached from catalyst, the homogeneous Cu(2+) contribution to the whole catalytic activity is unimportant, and the highly dispersed copper on SBA-15 plays a dominant role. PMID:26227827

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

    Science.gov (United States)

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

    2016-01-01

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

  17. CATALYTIC WET PEROXIDE OXIDATION OF HYDROQUINONE WITH Co(Ⅱ)/ACTIVE CARBON CATALYST LOADED IN STATIC BED

    Institute of Scientific and Technical Information of China (English)

    LI Chunxiang; YAN Yongsheng; XU Wanzhen

    2008-01-01

    Catalysts based on Co(Ⅱ) supported on active carbon were prepared and loaded in static bed.The hydroquinone wouid be degraded completely after treated by Catalytic wet peroxide oxidation method with Co(Ⅱ)/active carbon catalyst.After activate treatment, the active carbon was immerged in cobaltoas nitrate solution, then put into a drying oven, Co(Ⅱ) could be loaded on the micro-surface of carbon.Taking the static bed as the equipment, the absorption of active carbon and catalysis of Co(Ⅱ) was used to reduce activation energy of hydroquinone.Thus hydroquinone could be drastically degraded and the effluent can be drained under the standard.Referring to Fenton reaction mechanism, experiment had been done to study the heterogeneous catalyzed oxidation mechanism of Co(Ⅱ).The degradation rate of hydroquinone effluent could be achieved to 92% when treated in four columns at H2O2 concentration 10%, reaction temperature 40℃, pH 5 and reaction time 2.5h.

  18. CATALYTIC WET PEROXIDE OXIDATION OF HYDROQUINONE WITH Co(II)/ACTIVE CARBON CATALYST LOADED IN STATIC BED

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Catalysts based on Co(II) supported on active carbon were prepared and loaded in static bed. The hydroquinone would be degraded completely after treated by Catalytic wet peroxide oxidation method with Co(II)/active carbon catalyst. After activate treatment, the active carbon was immerged in cobaltous nitrate solution, then put into a drying oven, Co(II) could be loaded on the micro-surface of carbon. Taking the static bed as the equipment, the absorption of active carbon and catalysis of Co(II) was used to reduce activation energy of hydroquinone. Thus hydroquinone could be drastically degraded and the effluent can be drained under the standard. Referring to Fenton reaction mechanism, experiment had been done to study the heterogeneous catalyzed oxidation mechanism of Co(II). The degradation rate of hydroquinone effluent could be achieved to 92% when treated in four columns at H2O2 concentration 10%, reaction temperature 40℃ , pH 5 and reaction time 2.5h.

  19. Green oxidations: Titanium dioxide induced tandem oxidation coupling reactions

    OpenAIRE

    Vineet Jeena; Robinson, Ross S.

    2009-01-01

    The application of titanium dioxide as an oxidant in tandem oxidation type processes is described. Under microwave irradiation, quinoxalines have been synthesized in good yields from the corresponding α-hydroxyketones.

  20. Advances in the development of catalytic tethering directing groups for C-H functionalization reactions.

    Science.gov (United States)

    Sun, Huan; Guimond, Nicolas; Huang, Yong

    2016-09-28

    Transition metal-catalyzed C-H bond insertion is one of the most straightforward strategies to introduce functionalities within a hydrocarbon microenvironment. For the past two decades, selective activation and functionalization of certain inert C-H bonds have been made possible with the help of directing groups (DGs). Despite the enormous advances in the field, an overwhelming majority of systems require two extra steps from their simple precursors: installation and removal of the DGs. Recently, traceless and multitasking groups were invented as a partial solution to DG release. However, installation remains largely unsolved. Ideally, a transient, catalytic DG would circumvent this problem and increase the step- and atom-economy of C-H functionalization processes. In this review, we summarize the recent development of the transient tethering strategy for C-H activation reactions. PMID:27506568

  1. Palladium nanoparticle anchored polyphosphazene nanotubes: preparation and catalytic activity on aryl coupling reactions

    Indian Academy of Sciences (India)

    V Devi; A Ashok Kumar; S Sankar; K Dinakaran

    2015-06-01

    Highly accessible-supported palladium (Pd) nanoparticles anchored polyphosphazene (PPZ) nanotubes (NTs) having average diameter of 120 nm were synthesized rapidly at room temperature and homogeneously decorated with Pd nanoparticles. The resultant PPZ–Pd nanocomposites were morphologically and structurally characterized by means of transmission electron microscope equipped with energy-dispersive X-ray spectroscopy and X-ray diffraction analysis. Characterization results showed that the Pd nanoparticles with good dispersibility could be well anchored onto the surfaces of the PPZ NTs. The PPZ–Pd NTs show enhanced catalytic activity for the Suzuki coupling of aryl bromides with arylboronic acid. In addition, these PPZ–Pd NTs show excellent behaviour as reusable catalysts of the Suzuki and Heck coupling reactions.

  2. Direct Catalytic Asymmetric Mannich-Type Reaction of α- and β-Fluorinated Amides.

    Science.gov (United States)

    Brewitz, Lennart; Arteaga, Fernando Arteaga; Yin, Liang; Alagiri, Kaliyamoorthy; Kumagai, Naoya; Shibasaki, Masakatsu

    2015-12-23

    The last two decades have witnessed the emergence of direct enolization protocols providing atom-economical and operationally simple methods to use enolates for stereoselective C-C bond-forming reactions, eliminating the inherent drawback of the preformation of enolates using stoichiometric amounts of reagents. In its infancy, direct enolization relied heavily on the intrinsic acidity of the latent enolates, and the reaction scope was limited to readily enolizable ketones and aldehydes. Recent advances in this field enabled the exploitation of carboxylic acid derivatives for direct enolization, offering expeditious access to synthetically versatile chiral building blocks. Despite the growing demand for enantioenriched fluorine-containing small molecules, α- and β-fluorinated carbonyl compounds have been neglected in direct enolization chemistry because of the competing and dominating defluorination pathway. Herein we present a comprehensive study on direct and highly stereoselective Mannich-type reactions of α- and β-fluorine-functionalized 7-azaindoline amides that rely on a soft Lewis acid/hard Brønsted base cooperative catalytic system to guarantee an efficient enolization while suppressing undesired defluorination. This protocol contributes to provide a series of fluorinated analogs of enantioenriched β-amino acids for medicinal chemistry. PMID:26652911

  3. Promotional effect of upper Ru oxides as methanol tolerant electrocatalyst for the oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Montiel, M.; Hernandez-Fernandez, P.; Ocon, P. [Departamento de Quimica-Fisica Aplicada C-II, Campus UAM, 28049 Madrid (Spain); Fierro, J.L.G.; Rojas, S. [Instituto de Catalisis y Petroleoquimica (CSIC), C/Marie Curie 2, 28049 Madrid (Spain)

    2009-06-15

    The role of Ru on the oxygen reduction reaction in the presence of methanol has been investigated. To this end a series of carbon supported Pt based electrocatalysts containing Ru and Co have been prepared and thoroughly characterized. The catalytic performance on the oxygen reduction reaction (ORR) both in the presence and in the absence of methanol by linear sweep voltammetry on rotating disk electrode has been studied. In spite of its documented ability towards methanol and CO oxidation, when Ru-containing catalysts are subjected to excursions to potentials more positive than 0.8 V vs. NHE they develop a certain tolerance to the presence of methanol. This feature is attributed to the formation of upper oxide Ru species that impede the methanol oxidation reaction to occur under the typical reaction conditions of the oxygen reduction process, i.e. potentials more positive than 0.7 V vs. NHE and oxygen saturated atmospheres. The evolution of Ru species with the applied potential has been investigated by XPS, identifying the presence of upper oxidized Ru phases. (author)

  4. Gold & silver nanoparticles supported on manganese oxide: Synthesis, characterization and catalytic studies for selective oxidation of benzyl alcohol

    Directory of Open Access Journals (Sweden)

    Saad Alabbad

    2014-12-01

    Full Text Available Nano-gold and silver particles supported on manganese oxide were synthesized by the co-precipitation method. The catalytic properties of these materials were investigated for the oxidation of benzyl alcohol using molecular oxygen as a source of oxygen. The catalyst was calcined at 300, 400 and 500 °C. They were characterized by electron microscopy, powder X-ray diffraction (XRD and surface area. It was observed that the calcination temperature affects the size of the nanoparticle, which plays a significant role in the catalytic process. The catalyst calcined at 400 °C, gave a 100% conversion and >99% selectivity, whereas catalysts calcined at 300 and 500 °C gave a conversion of 69.51% and 19.90% respectively, although the selectivity remains >99%.

  5. Benzyl alcohol oxidation in supercritical carbon dioxide: spectroscopic insight into phase behaviour and reaction mechanism.

    Science.gov (United States)

    Caravati, Matteo; Grunwaldt, Jan-Dierk; Baiker, Alfons

    2005-01-21

    Selective oxidation of benzyl alcohol to benzaldehyde with molecular oxygen over an alumina-supported palladium catalyst was performed with high rate at about 95% selectivity in supercritical carbon dioxide. The experiments in a continuous flow fixed-bed reactor showed that the pressure has a strong influence on the reaction rate. A marked increase of the rate (turnover frequency) from 900 h(-1) to 1800 h(-1) was observed when increasing the pressure from 140 to 150 bar. Video monitoring of the bulk fluid phase behavior and the simultaneous investigation by transmission and attenuated total reflection (ATR) infrared spectroscopy at two positions of the view cell showed that the sharp increase in activity is correlated to a transition from a biphasic to a monophasic reaction mixture. In the single phase region, both oxygen and benzyl alcohol are dissolved in the supercritical CO2 phase, which leads to a reduction of the mass transport resistances (both in the external fluid film and in the catalyst pores) and thus to the high reaction rate measured in the catalytic experiments. The phase transition could be effectively and easily monitored by transmission and ATR-IR spectroscopy despite the small concentration of the dense liquid like phase. Deposition of the Pd/Al2O3 catalyst on the ATR-crystal at the bottom of the view cell allowed to gain insight into the chemical changes and mass transfer processes occurring in the solid/liquid interface region during reaction. Analyzing the shift of the upsilon2 bending mode of CO2 gave information on the fluid composition in and outside the catalyst pores. Moreover, the catalytic reaction could be investigated in situ in this spectroscopic batch reactor cell by monitoring simultaneously the reaction progress, the phase behaviour and the catalytic interface. PMID:19785149

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

    Directory of Open Access Journals (Sweden)

    K. Maduna Valkaj

    2015-01-01

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

  7. Innovative Catalysis in Organic Synthesis Oxidation, Hydrogenation, and C-X Bond Forming Reactions

    CERN Document Server

    Andersson, Pher G

    2012-01-01

    Authored by a European team of leaders in the field, this book compiles innovative approaches for C-X bond forming processes frequently applied in organic synthesis. It covers all key types of catalysis, including homogeneous, heterogeneous, and organocatalysis, as well as mechanistic and computational studies. Special attention is focused on the improvement of efficiency and sustainability of important catalytic processes, such as selective oxidations, hydrogenation and cross-coupling reactions.The result is a valuable resource for both advanced researchers in academia and industry, as well a

  8. Preparation of Molecular Sieve Catalyst and Application in the Catalytic Oxidation Treatment of Waste Water

    Institute of Scientific and Technical Information of China (English)

    WANG; RongMin

    2001-01-01

    Citric acid is an important additive in foods, cosmetics, medicine and so on, but it discharges about 10 ton of factory effluent when 1 ton of citric acid is produced. The COD of the factory effluent is near 20000 mg/L. The treatment of citric acid factory effluent is a serious problem in environmental chemistry.  It is found that molecular sieve support metal complexes have high catalytic activity in aerobic oxidation of alkene [1,2]. In this paper, a kind of molecular sieve catalyst was prepared. The catalyst was used for the treatment of citric acid factory effluent by method of catalytic oxygen oxidation.  ……

  9. Catalytic partial oxidation coupled with membrane purification to improve resource and energy efficiency in syngas production.

    Science.gov (United States)

    Iaquaniello, G; Salladini, A; Palo, E; Centi, G

    2015-02-01

    Catalytic partial oxidation coupled with membrane purification is a new process scheme to improve resource and energy efficiency in a well-established and large scale-process like syngas production. Experimentation in a semi industrial-scale unit (20 Nm(3)  h(-1) production) shows that a novel syngas production scheme based on a pre-reforming stage followed by a membrane for hydrogen separation, a catalytic partial oxidation step, and a further step of syngas purification by membrane allows the oxygen-to-carbon ratio to be decreased while maintaining levels of feed conversion. For a total feed conversion of 40 %, for example, the integrated novel architecture reduces oxygen consumption by over 50 %, with thus a corresponding improvement in resource efficiency and an improved energy efficiency and economics, these factors largely depending on the air separation stage used to produce pure oxygen. PMID:25571881

  10. Reaction pathway investigation on the selective catalytic reduction of NO with NH3 over Cu/SSZ-13 at low temperatures.

    Science.gov (United States)

    Su, Wenkang; Chang, Huazhen; Peng, Yue; Zhang, Chaozhi; Li, Junhua

    2015-01-01

    The mechanism of the selective catalytic reduction of NO with NH3 was studied using Cu/SSZ-13. The adspecies of NO and NH3 as well as the active intermediates were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy and temperature-programmed surface reaction. The results revealed that three reactions were possible between adsorbed NH3 and NOx. NO2(-) could be generated by direct formation or NO3(-) reduction via NO. In a standard selective catalytic reduction (SCR) reaction, NO3(-) was hard to form, because NO2(-) was consumed by ammonia before it could be further oxidized to nitrates. Additionally, adsorbed NH3 on the Lewis acid site was more active than NH4(+). Thus, SCR mainly followed the reaction between Lewis acid site-adsorbed NH3 and directly formed NO2(-). Higher Cu loading could favor the formation of active Cu-NH3, Cu-NO2(-), and Cu-NO3(-), improving the SCR activity at low temperature. PMID:25485842

  11. Optical and electro-catalytic studies of nanostructured thulium oxide for vitamin C detection

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Jay [Department of BIN Fusion Technology, Chonbuk National University, Jeonju, Jeonbuk 561-756 (Korea, Republic of); Department of Polymer-Nano Science and Technology, Chonbuk National University, Jeonju, Jeonbuk 561-756 (Korea, Republic of); Srivastava, Manish [Department of Physics, Dehradun Institute of Technology (DIT), School of Engineering, Greater Noida 201308 (India); Roychoudhury, Appan [Department of Biotechnology, Delhi Technological University, Shahbad Daulatpur, Main Bawana Road, Delhi 110 042 (India); Lee, Dong Won [Department of BIN Fusion Technology, Chonbuk National University, Jeonju, Jeonbuk 561-756 (Korea, Republic of); Department of Polymer-Nano Science and Technology, Chonbuk National University, Jeonju, Jeonbuk 561-756 (Korea, Republic of); Lee, Seung Hee, E-mail: lsh1@jbnu.ac.kr [Department of BIN Fusion Technology, Chonbuk National University, Jeonju, Jeonbuk 561-756 (Korea, Republic of); Department of Polymer-Nano Science and Technology, Chonbuk National University, Jeonju, Jeonbuk 561-756 (Korea, Republic of); Malhotra, B.D., E-mail: bansi.malhotra@gmail.com [Department of Biotechnology, Delhi Technological University, Shahbad Daulatpur, Main Bawana Road, Delhi 110 042 (India); Department of Science and Technology Centre on Biomolecular Electronics, Biomedical Instrumentation Section, Material Physics and Engineering Division, CSIR-National Physical Laboratory, Dr. K.S. Krishnan Marg, New Delhi 110 012 (India); Center for NanoBioengineering and Spintronics, Chungnam National University, 220 Gung-Dong, Yuseong-Gu, Daejeon 305-764 (Korea, Republic of)

    2013-11-25

    Highlights: •Nanostructured thulium oxide has been prepared using the hydrothermal process. •Thulium oxide exhibits excellent electrochemical response towards ascorbic acid. •Thulium oxide is interesting electro-optical material. •Rare earth metal oxide offers potential application biosensing and optoelectronics. -- Abstract: In this report, the nanostructured thulium oxide (Tm{sub 2}O{sub 3}) has been prepared using the hydrothermal process without using any template and further heat treatment. The crystalline structure and morphology of prepared sample have been determined by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and Fourier transform infrared (FTIR) spectroscopic techniques. The optical properties of prepared sample have been examined by ultra-violet (UV–Vis), photoluminescence (PL), Raman and X-ray photoelectron spectroscopy (XPS) studies. Furthermore, Tm{sub 2}O{sub 3} nanoparticles have been electrophoretically deposited (EPD) onto indium–tin–oxide (ITO) glass substrate and utilized for electro-oxidation of ascorbic acid (AA). The electro-catalytic behavior of Tm{sub 2}O{sub 3}/ITO and bare ITO electrodes for AA electro-oxidation has been studied by cyclic voltammetry. Catalytic oxidation peak current shows a linear dependence on the AA concentration and a linear calibration curve is obtained in the concentration range of 0.2–8 mM of AA. The obtained results indicate that the nanostructured Tm{sub 2}O{sub 3} based electrode offers an efficient strategy and a new promising platform for application of the rare earth metal oxide material in electrochemistry and bioelectronics.

  12. Gold-TiO2-Nickel catalysts for low temperature-driven CO oxidation reaction

    Science.gov (United States)

    Hinojosa-Reyes, Mariana; Zanella, Rodolfo; Maturano-Rojas, Viridiana; Rodríguez-González, Vicente

    2016-04-01

    Nickel-doped-TiO2 catalysts were prepared by the sol-gel method and surface modified with gold nanoparticles (AuNPs) by the urea-deposition-precipitation technique. The as-synthesized catalysts were characterized by X-ray diffraction, Raman and XPS spectroscopies, N2 physisorption, STEM-HAADF microscopy and TPR hydrogen consumption. The Au/TiO2-Ni catalysts were evaluated catalytically performing CO oxidation reactions. The catalyst with nickel content of 1 wt. % (Au/TiO2-Ni 1) showed the highest CO conversion with respect to the high-nickel-content or bare/commercial TiO2 at 0 °C. In situ DRIFTS showed a strong participation of both nickel due to the presence of surface-nickel-metallic nanoparticles formed during the CO adsorption process at reaction temperatures above 200 °C, and surface-bridged-nickel-CO species. A minor deactivation rate was observed for the Au/TiO2-Ni 1 catalyst in comparison with the Au/TiO2 one. The oxygen vacancies that were created on the sol-gel-doped TiO2 improved the catalytic behavior during the performance of CO oxidation reactions, and inhibited the AuNP sintering.

  13. Stability and catalytic performance of vanadia supported on nanostructured titania catalyst in oxidative dehydrogenation of propane

    International Nuclear Information System (INIS)

    Highlights: • Vanadia supported on titanate nanotube shows enhanced dispersion of vanadia. • Deactivatoin during propane ODH related to the rutile development. • Titanate nanotube transfers to anatase due to calcinations and presence of vanadia. - Abstract: Titanate nanotubes with a high specific surface area were synthesized by the simple hydrothermal method and investigated as support for V2O5 catalyst in oxidative dehydrogenation of propane (ODP). The structures of pristine nanotubes as well as the prepared catalysts were investigated by XRD, Raman, FTIR, HRTEM, SEM, EDS, BET, and XPS techniques. The characterization of the as-synthesized nanotubes showed the synthesis of hydrogen titanate nanotube. The incipient wetness impregnation method was utilized to prepare VTNT-x (x = 5, 10, and 15 wt.% vanadia supported on nanotube) together with VTi5 (5 wt.% vanadia supported on Degussa P25). The anatase phase was developed in VTNT-x catalysts upon calcination along with specific surface area loss. Higher vanadia loading resulted in the lowering of support capacity in maintaining vanadia in dispersed state such that eventually crystalline vanadia appeared. The measured catalyst activity demonstrates that in spite of major support surface area loss in VTNT-5 catalyst, the propylene yield is superior in comparison with VTi5 catalyst. The catalyst activity can be correlated with maximum reduction temperature. Deactivation of VTi5 and VTNT-5 as well as VTNT-15 were studied for 3,000 min time-on-stream. It was found that the activity of VTNT-5 catalyst remain unchanged while a decline in catalytic activity observed in VTi5 and VTNT-15 catalysts. The development of rutile was considered as being a major element in the deactivation of the investigated catalysts which is influenced by the presence of vanadium and reaction atmosphere

  14. Stability and catalytic performance of vanadia supported on nanostructured titania catalyst in oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Kootenaei, A.H. Shahbazi [Department of Chemical Engineering, College of Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran (Iran, Islamic Republic of); Towfighi, J., E-mail: towfighi@modares.ac.ir [Department of Chemical Engineering, College of Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran (Iran, Islamic Republic of); Khodadadi, A.; Mortazavi, Y. [Catalysis and Nanostructured Materials Laboratory, Oil and Gas Processing Center of Excellence, Department of Chemical Engineering, College of Engineering, University of Tehran, P.O. Box 11365-4563, Tehran (Iran, Islamic Republic of)

    2014-04-01

    Highlights: • Vanadia supported on titanate nanotube shows enhanced dispersion of vanadia. • Deactivatoin during propane ODH related to the rutile development. • Titanate nanotube transfers to anatase due to calcinations and presence of vanadia. - Abstract: Titanate nanotubes with a high specific surface area were synthesized by the simple hydrothermal method and investigated as support for V{sub 2}O{sub 5} catalyst in oxidative dehydrogenation of propane (ODP). The structures of pristine nanotubes as well as the prepared catalysts were investigated by XRD, Raman, FTIR, HRTEM, SEM, EDS, BET, and XPS techniques. The characterization of the as-synthesized nanotubes showed the synthesis of hydrogen titanate nanotube. The incipient wetness impregnation method was utilized to prepare VTNT-x (x = 5, 10, and 15 wt.% vanadia supported on nanotube) together with VTi5 (5 wt.% vanadia supported on Degussa P25). The anatase phase was developed in VTNT-x catalysts upon calcination along with specific surface area loss. Higher vanadia loading resulted in the lowering of support capacity in maintaining vanadia in dispersed state such that eventually crystalline vanadia appeared. The measured catalyst activity demonstrates that in spite of major support surface area loss in VTNT-5 catalyst, the propylene yield is superior in comparison with VTi5 catalyst. The catalyst activity can be correlated with maximum reduction temperature. Deactivation of VTi5 and VTNT-5 as well as VTNT-15 were studied for 3,000 min time-on-stream. It was found that the activity of VTNT-5 catalyst remain unchanged while a decline in catalytic activity observed in VTi5 and VTNT-15 catalysts. The development of rutile was considered as being a major element in the deactivation of the investigated catalysts which is influenced by the presence of vanadium and reaction atmosphere.

  15. Stability and catalytic performance of vanadia supported on nanostructured titania catalyst in oxidative dehydrogenation of propane

    Science.gov (United States)

    Kootenaei, A. H. Shahbazi; Towfighi, J.; Khodadadi, A.; Mortazavi, Y.

    2014-04-01

    Titanate nanotubes with a high specific surface area were synthesized by the simple hydrothermal method and investigated as support for V2O5 catalyst in oxidative dehydrogenation of propane (ODP). The structures of pristine nanotubes as well as the prepared catalysts were investigated by XRD, Raman, FTIR, HRTEM, SEM, EDS, BET, and XPS techniques. The characterization of the as-synthesized nanotubes showed the synthesis of hydrogen titanate nanotube. The incipient wetness impregnation method was utilized to prepare VTNT-x (x = 5, 10, and 15 wt.% vanadia supported on nanotube) together with VTi5 (5 wt.% vanadia supported on Degussa P25). The anatase phase was developed in VTNT-x catalysts upon calcination along with specific surface area loss. Higher vanadia loading resulted in the lowering of support capacity in maintaining vanadia in dispersed state such that eventually crystalline vanadia appeared. The measured catalyst activity demonstrates that in spite of major support surface area loss in VTNT-5 catalyst, the propylene yield is superior in comparison with VTi5 catalyst. The catalyst activity can be correlated with maximum reduction temperature. Deactivation of VTi5 and VTNT-5 as well as VTNT-15 were studied for 3,000 min time-on-stream. It was found that the activity of VTNT-5 catalyst remain unchanged while a decline in catalytic activity observed in VTi5 and VTNT-15 catalysts. The development of rutile was considered as being a major element in the deactivation of the investigated catalysts which is influenced by the presence of vanadium and reaction atmosphere.

  16. Iodine Oxide Thermite Reactions: Physical and Biological Effects

    Science.gov (United States)

    Russell, Rod; Pantoya, Michelle; Bless, Stephan; Clark, William

    2009-06-01

    We investigated the potential for some thermite-like material reactions to kill bacteria spores. Iodine oxides and silver oxides react vigorously with metals like aluminum, tantalum, and neodymium. These reactions theoretically produce temperatures as high as 8000K, leading to vaporization of the reactants, producing very hot iodine and/or silver gases. We performed a series of computations and experiments to characterize these reactions under both quasi-static and ballistic impact conditions. Criteria for impact reaction were established. Measurements of temperature and pressure changes and chemical evolution will be reported. Basic combustion characterizations of these reactions, such as thermal equilibrium analysis and reaction propagation rates as well as ignition sensitivity, will be discussed. Additionally, testing protocols were developed to characterize the biocidal effects of these reactive materials on B. subtilis spores. The evidence from these tests indicates that these reactions produce heat, pressure, and highly biocidal gases.

  17. Investigation of catalyst and solvent systems for the catalytic oxidation of Kraft lignin

    OpenAIRE

    Mora Mir, Joan

    2010-01-01

    Lignin is one of the main constituents of wood together with cellulose and hemicellulose and can be used as a renewable feedstock for the production of chemicals. Lignin is an amorphous polymer which is separated from cellulose during the pulping processes in the paper industry. The Kraft process is the most extended pulping process and the so called Kraft lignin is one of the most promising sources for the obtaining of value-added products from its degradation. The catalytic oxidation of ...

  18. Thermodynamic Study on the Catalytic Partial Oxidation of Methane to Syngas

    Institute of Scientific and Technical Information of China (English)

    XUJian; WEIWeisheng; 等

    2002-01-01

    The catalytic partial oxidation of methane to syngas (CO+H2) has been simulated thermodynamically with the advanced process simulator PRO/Ⅱ. The influences of temperature,pressure,CH4/O2 ratio and steam addition in feed gas on the conversion of CH4 selectively to syngas and heat duty required were investigated, and their effects on carbon formation were also discussed. The simulation results were in good agreement with the literature data taken from a spouted bed reactor.

  19. Catalytic production of carbon nanotubes over first row transition metal oxides supported on montmorillonite

    International Nuclear Information System (INIS)

    Clay-carbon nanotube composites were prepared by employing the catalytic chemical vapor deposition method (CCVD) over different transition metal oxides supported on montmorillonite. Various analytical techniques including SEM, TEM, XRD and DTA/TGA were used for the characterization of the final composite materials. The morphology, quality and structure of the produced nanotubes is shown to be dependent on the type of transition metals

  20. Catalytic oxidation of hydrocarbons by dinuclear iron complexes

    International Nuclear Information System (INIS)

    Our efforts during the past eight months were directed towards characterizing synthetic complexes that model the electronic and reactivity properties of the active site of methane monooxygenase (MMO), a metalloenzyme found in methanotrophic bacteria responsible for the biological oxidation of methane to methanol. We have investigated the structural/electronic and reactivity properties of a series of dinuclear model complexes that can function as oxygen atom transfer catalysts. In particular, our studies focused on [Fe2+2(H2Hbab)2(N-MeIM)], its DMF solvated form, [Fe2+2(H2Hbab)2(DMF)2(N-MeIM)], and the mixed valent species [[Fe2+2(H2Hbab)2(DMF)4]+, (H4Hbab = 1,2-bis(2-hydroxybenzamido) benzene). We have also examined [Fe3+2(H2Hbab)2(DMF)4]2, [Fe3+2(H2Hbab)2(OMe)2], and μ-oxo[Fe3+2(H2Hbab)2(DMF)2], which are unable to act as oxygen atom transfer catalysts

  1. Strategies for catalyst development: possibilities of the ``rational approach`` illustrated with partial oxidation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, W.; Schedel-Niedrig, T.; Schloegl, R. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Abt. Oberflaechenphysik

    1998-12-31

    The paper discusses two petrochemical selective oxidation reactions namely the practised formation of styrene (STY) and the desired oxidative functionalisation of propane. The present knowledge about the mode of operation of oxide catalysts is critically considered. The dehydrogenation of ethylbenzene (EB) should be described by an oxidehydration with water acting as oxidant. The potential role of the coke formed during catalytic reaction as co-catalyst will be discussed. Selective oxidation is connected with the participation of lattice oxygen mechanism which transforms unselective gas phase oxygen into selective oxygen. The atomistic description of this process is still quite unclear as well as the electron structural properties of the activated oxygen atom. The Role of solid state acidity as compared to the role of lattice oxygen is much less well investigated modern multiphase-multielement oxide (MMO) catalysts. The rationale is that the significant efforts made to improve current MMO systems by chemical modifications can be very much more fruitful when in a first step the mode of action of a catalyst is clarified on the basis of suitable experiments. Such time-consuming experiments at the beginning of a campaign for catalyst improvement pay back their investment in later stages of the project when strategies of chemical development can be derived on grounds of understanding. (orig.)

  2. Enhanced methanol electro-oxidation reaction on Pt-CoOx/MWCNTs hybrid electro-catalyst

    Science.gov (United States)

    Nouralishahi, Amideddin; Rashidi, Ali Morad; Mortazavi, Yadollah; Khodadadi, Abbas Ali; Choolaei, Mohammadmehdi

    2015-04-01

    The electro-catalytic behavior of Pt-CoOx/MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH4 as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoOx, Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of COads on Pt active sites by the participation of CoOx. Compared to Pt/MWCNTs, Pt-CoOx/MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoOx/MWCNTs, at small overpotentials. However, at higher overpotentials, the oxidation of adsorbed oxygen-containing groups controls the total rate of MOR process.

  3. Theoretical Study on the Dark Oxidation Reaction Mechanism of Ethers

    Institute of Scientific and Technical Information of China (English)

    WANG Gui-Xiu; ZHU Rong-Xiu; ZHANG Dong-Ju; LIU Cheng-Bu

    2006-01-01

    The dark oxidation reactions of ethers including aether, isopropyl ether, phenyl isopropyl ether, and benzyl isopropyl ether have been studied by using density functional theory calculations. The structures of initial contact charge transfer complexes (CCTCs), transition states and caged radical intermediates have been located at the B3LYP/6-31G (d) level. The bonding nature of ethers with triplet O2 in CCTCs has been analyzed, and the detailed mechanism of dark oxidation reactions of ether is presented clearly.

  4. Photo Catalytic Oxidation of Alcohols in Water under Natural Weathering Conditions in the Presence of Bromo Source

    Institute of Scientific and Technical Information of China (English)

    P.H.Yan; R.R.Wang; J.Q.Wang; Y.X.Yang; S.Wu; H.Zhao; Z.Q.Lei

    2007-01-01

    1 Results The oxidation of alcohols into the corresponding carbonyl compound is one of the most important functional group transformation in organic synthesis[1]. Traditionally,such transformations have been performed with stoichiometric inorganic oxidant or other high valent metal oxidant[2]. Despite a variety of systems for the catalytic oxidation of alcohols have been developed,there is ongoing interest in the search for new efficient and environmental friendly oxidation system.To the best of our kno...

  5. The Pathophysiology of Extracellular Hemoglobin Associated with Enhanced Oxidative Reactions

    Directory of Open Access Journals (Sweden)

    Joseph M Rifkind

    2015-01-01

    Full Text Available Hemoglobin (Hb continuously undergoes autoxidation producing superoxide which dismutates into hydrogen peroxide (H2O2 and is a potential source for subsequent oxidative reactions. Autoxidation is most pronounced under hypoxic conditions in the microcirculation and for unstable dimers formed at reduced Hb concentrations. In the red blood cell (RBC, oxidative reactions are inhibited by an extensive antioxidant system. For extracellular Hb, whether from hemolysis of RBCs and/or the infusion of Hb-based blood substitutes, the oxidative reactions are not completely neutralized by the available antioxidant system. Un-neutralized H2O2 oxidizes ferrous and ferric Hbs to Fe(IV-ferrylHb and oxyferrylHb, respectively. FerrylHb further reacts with H2O2 producing heme degradation products and free iron. OxyferrylHb, in addition to Fe(IV contains a free radical that can undergo additional oxidative reactions. Fe(IIIHb produced during Hb autoxidation also readily releases heme, an additional source for oxidative stress. These oxidation products are a potential source for oxidative reactions in the plasma, but to a greater extent when the lower molecular weight Hb dimers enter cells and tissues. Heme and oxyferryl have been shown to have a proinflammatory effect further increasing their potential for oxidative stress. These oxidative reactions contribute to a number of pathological situations including atherosclerosis, kidney malfunction, sickle cell disease and malaria. The toxic effects of extracellular Hb are of particular concern for increased hemolysis due to hemolytic anemia. Hemolysis is further exacerbated in various diseases and their treatments. Blood transfusions are required whenever there is an appreciable decrease in RBCs due to hemolysis or blood loss. It is, therefore, essential that transfused blood, whether stored RBCs or blood obtained by an Autologous Blood Recovery System from the patient, does not further increase extracellular Hb.

  6. Preparation, Characterization and NO-CO Redox Reaction Studies over Palladium and Rhodium Oxides Supported on Manganese Dioxide

    Directory of Open Access Journals (Sweden)

    M.S. Fal Desai

    2015-03-01

    Full Text Available The catalytic activity of PdO/MnO2 and Rh2O3/MnO2 is investigated for NO-CO redox reaction. Supported catalysts are prepared by wet impregnation method. Among the tested catalysts, PdO/MnO2 shows higher activity for this reaction. Active metal dispersion on MnO2 enhances the selectivity for N2 over N2O in this reaction. The XRD substantiate the formation of MnO2 monophasic phase. SEM images show the formation of elongated particles. TEM images indicate nano-size rod-like morphologies. An increase in the catalytic activity is observed on supported Pd and Rh oxides on MnO2. Temperature programed desorption studies with NO and CO are undertaken to investigate the catalytic surface studies. © 2015 BCREC UNDIP. All rights reservedReceived: 22nd November 2014; Revised: 31st December 2014; Accepted: 2nd January 2015How to Cite: Fal Desai, M.S., Kunkalekar, R.K., Salker, A.V. (2015. Preparation, Characterization and NO-CO Redox Reaction Studies over Palladium and Rhodium Oxides Supported on Manganese Dioxide. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 98-103. (doi:10.9767/bcrec.10.1.7802.98-103Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7802.98-103 

  7. Catalytic combustion of methane by perovskite-type oxide nanoparticles as pollution prevention strategy

    Science.gov (United States)

    Zaza, F.; Luisetto, I.; Serra, E.; Tuti, S.; Pasquali, M.

    2016-06-01

    The transition from the existing brown economy towards the desired green economy drives the research efforts to the development of advanced technologies promoting the efficient utilization of energy sources. Catalysis science offers to combustion technology significant opportunity to increase the fuel efficiency by lowering the internal temperature gradients and reduce the environmental impact by lowering local peak temperature and, consequently, thermodynamically inhibiting the nitrogen oxides formation. Alternative catalytic materials are transition metals oxide, including complex oxides with perovskite crystalline structure. The aim of this work is to synthetize lanthanum ferrite perovskites with lanthanum ions partially substituted by strontium ions in order to study the substitution effects on structural properties and redox activity of the original oxide. Lanthanum ferrite oxides partially substituted with different Strontium amount were synthesized by solution combustion method. The perovskite nanopowders obtained were characterized by XRD, SEM, TPR analyses for defining crystalline structure, morphology and redox properties. Finally, the catalytic activity for methane combustion was tested. The most performing catalysts was La0.6Sr0.4FeO3 having the highest oxygen vacancy concentration as revealed by TPR analysis.

  8. Mechanism of Catalytic Water Oxidation by the Ruthenium Blue Dimer Catalyst: Comparative Study in D2O versus H2O

    Directory of Open Access Journals (Sweden)

    Yulia Pushkar

    2013-01-01

    Full Text Available Water oxidation is critically important for the development of energy solutions based on the concept of artificial photosynthesis. In order to gain deeper insight into the mechanism of water oxidation, the catalytic cycle for the first designed water oxidation catalyst, cis,cis-[(bpy2(H2ORuIIIORuIII(OH2(bpy2]4+ (bpy is 2,2-bipyridine known as the blue dimer (BD, is monitored in D2O by combined application of stopped flow UV-Vis, electron paramagnetic resonance (EPR and resonance Raman spectroscopy on freeze quenched samples. The results of these studies show that the rate of formation of BD[4,5] by Ce(IV oxidation of BD[3,4] (numbers in square bracket denote oxidation states of the ruthenium (Ru centers in 0.1 M HNO3, as well as further oxidation of BD[4,5] are slower in D2O by 2.1–2.5. Ce(IV oxidation of BD[4,5] and reaction with H2O result in formation of an intermediate, BD[3,4]′, which builds up in reaction mixtures on the minute time scale. Combined results under the conditions of these experiments at pH 1 indicate that oxidation of BD[3,4]′ is a rate limiting step in water oxidation with the BD catalyst.

  9. Catalytic Upgrading of Biomass-Derived Compounds via C-C Coupling Reactions. Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Cong [Argonne National Lab. (ANL), Argonne, IL (United States); Evans, Tabitha J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Cheng, Lei [Argonne National Lab. (ANL), Argonne, IL (United States); Nimlos, Mark R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Mukarakate, Calvin [National Renewable Energy Lab. (NREL), Golden, CO (United States); Robichaud, David J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Assary, Rajeev S. [Argonne National Lab. (ANL), Argonne, IL (United States); Curtiss, Larry A. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2015-10-02

    These catalytic C–C coupling and deoxygenation reactions are essential for upgrading of biomass-derived oxygenates to fuel-range hydrocarbons. Detailed understanding of mechanistic and energetic aspects of these reactions is crucial to enabling and improving the catalytic upgrading of small oxygenates to useful chemicals and fuels. Using periodic density functional theory (DFT) calculations, we have investigated the reactions of furan and acetaldehyde in an HZSM-5 zeolite catalyst, a representative system associated with the catalytic upgrading of pyrolysis vapors. Comprehensive energy profiles were computed for self-reactions (i.e., acetaldehyde coupling and furan coupling) and cross-reactions (i.e., acetaldehyde + furan) of this representative mixture. Major products proposed from the computations are further confirmed using temperature controlled mass spectra measurements. Moreover, the computational results show that furan interacts with acetaldehyde in HZSM-5 via an alkylation mechanism, which is more favorable than the self-reactions, indicating that mixing furans with aldehydes could be a promising approach to maximize effective C–C coupling and dehydration while reducing the catalyst deactivation (e.g., coke formation) from aldehyde condensation.

  10. The Effect of Metal Oxide on Nanoparticles from Thermite Reactions

    Science.gov (United States)

    Moore, Lewis Ryan

    2006-01-01

    The purpose of this research was to determine how metal oxide used in a thermite reaction can impact the production of nanoparticles. The results showed the presence of nanoparticles (less than 1 micron in diameter) of at least one type produced by each metal oxide. The typical particles were metallic spheres, which ranged from 300 nanometers in…

  11. A non-acid-assisted and non-hydroxyl-radical-related catalytic ozonation with ceria supported copper oxide in efficient oxalate degradation in water

    KAUST Repository

    Zhang, Tao

    2012-06-01

    Oxalate is usually used as a refractory model compound that cannot be effectively removed by ozone and hydroxyl radical oxidation in water. In this study, we found that ceria supported CuO significantly improved oxalate degradation in reaction with ozone. The optimum CuO loading amount was 12%. The molar ratio of oxalate removed/ozone consumption reached 0.84. The catalytic ozonation was most effective in a neutral pH range (6.7-7.9) and became ineffective when the water solution was acidic or alkaline. Moreover, bicarbonate, a ubiquitous hydroxyl radical scavenger in natural waters, significantly improved the catalytic degradation of oxalate. Therefore, the degradation relies on neither hydroxyl radical oxidation nor acid assistance, two pathways usually proposed for catalytic ozonation. These special characters of the catalyst make it suitable to be potentially used for practical degradation of refractory hydrophilic organic matter and compounds in water and wastewater. With in situ characterization, the new surface Cu(II) formed from ozone oxidation of the trace Cu(I) of the catalyst was found to be an active site in coordination with oxalate forming multi-dentate surface complex. It is proposed that the complex can be further oxidized by molecular ozone and then decomposes through intra-molecular electron transfer. The ceria support enhanced the activity of the surface Cu(I)/Cu(II) in this process. © 2012 Elsevier B.V.

  12. Heterogeneous catalytic ozonation of ciprofloxacin in water with carbon nanotube supported manganese oxides as catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Sui, Minghao, E-mail: suiminghao.sui@gmail.com [State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092 (China); Xing, Sichu; Sheng, Li; Huang, Shuhang; Guo, Hongguang [State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092 (China)

    2012-08-15

    Highlights: Black-Right-Pointing-Pointer Ciprofloxacin in water was degraded by heterogeneous catalytic ozonation. Black-Right-Pointing-Pointer MnOx were supported on MWCNTs to serve as catalyst for ozonation. Black-Right-Pointing-Pointer MnOx/MWCNT exhibited highly catalytic activity on ozonation of ciprofloxacin in water. Black-Right-Pointing-Pointer MnOx/MWCNT resulted in effective antibacterial activity inhibition on ciprofloxacin. Black-Right-Pointing-Pointer MnOx/MWCNT promoted the generation of hydroxyl radicals. - Abstract: Carbon nanotube-supported manganese oxides (MnOx/MWCNT) were used as catalysts to assist ozone in degrading ciprofloxacin in water. Manganese oxides were successfully loaded on multi-walled carbon nanotube surfaces by simply impregnating the carbon nanotube with permanganate solution. The catalytic activities of MnOx/MWCNT in ciprofloxacin ozonation, including degradation, mineralization effectiveness, and antibacterial activity change, were investigated. The presence of MnOx/MWCNT significantly elevated the degradation and mineralization efficiency of ozone on ciprofloxacin. The microbiological assay with a reference Escherichia coli strain indicated that ozonation with MnOx/MWCNT results in more effective antibacterial activity inhibition of ciprofloxacin than that in ozonation alone. The effects of catalyst dose, initial ciprofloxacin concentration, and initial pH conditions on ciprofloxacin ozonation with MnOx/MWCNT were surveyed. Electron spin resonance trapping was applied to assess the role of MnOx/MWCNT in generating hydroxyl radicals (HO{center_dot}) during ozonation. Stronger 5,5-dimethyl-1-pyrroline-N-oxide-OH signals were observed in the ozonation with MnOx/MWCNT compared with those in ozonation alone, indicating that MnOx/MWCNT promoted the generation of hydroxyl radicals. The degradation of ciprofloxacin was studied in drinking water and wastewater process samples to gauge the potential effects of water background matrix on

  13. Catalytic Studies Featuring Palladium(II Benzoylthiourea Derivative as Catalyst in Sonogashira Reaction

    Directory of Open Access Journals (Sweden)

    Wan M. Khairul

    2014-10-01

    Full Text Available A benzoylthiourea derivative (LTU and its metal complexation of palladium(II chloride (MLTU has been successfully synthesized and characterized via typical spectroscopic and analytical techniques namely IR, 1H and 13C Nuclear Magnetic Resonance, UV-Visible and Gas Chromatography Flame Ionization Detector (GC-FID. The Infrared spectrum for LTU shows four significant bands of interest namely ν(N-H, ν(C=O, ν(C-N and ν(C=S and the values were observed within the range. The 1H NMR spectrum for the compound shows expected protons for N-H at δH 10.95 ppm and δH 11.15 ppm while the 13C NMR spectrum shows resonances of carbonyl (C=O carbon and thiones (C=S at δC 168.26 ppm and δC 180.56 ppm, respectively. From UV-Vis spectrum, it shows the presence of n-pi* and pi→pi*electronic transitions which are expected to be attributed from the phenyl ring, carbonyl (C=O and thiones (C=S chromophores. Complexation of LTU with palladium(II chloride was done to afford MLTU which in turn, was tested as homogeneous catalyst in Sonogashira cross-coupling reaction. The reaction was monitored by GC-FID at 6 hours reaction period. The percentage conversion of 4-bromoacetophenone to the coupled product was 75.73% indicated that MLTU can act as an ideal potential catalyst in the Sonogashira reaction. © 2014 BCREC UNDIP. All rights reservedReceived: 14th May 2014; Revised: 30th August 2014; Accepted: 3rd September 2014 How to Cite: Khairul, W.M., Faisol, S.L.M., Jasman, S.M., Shamsuddin, M. (2014. Catalytic Studies Featuring Palladium(II Benzoylthiourea Derivative as Catalyst in Sonogashira Reaction. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (3: 241-248 (doi:10.9767/bcrec.9.3.6880.241-248Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.3.6880.241-248

  14. An FTIR study on the catalytic effect of water molecules on the reaction of CO successive hydrogenation at 3 K

    International Nuclear Information System (INIS)

    Graphical abstract: This work highlights a selective catalytic action of water molecules on the reaction of CO hydrogenation at 3 K. Research highlights: → [CO/H2O] and [H/H2] are coinjected at 3 K. → H2 molecules condense rapidly at 3 K and screen the reaction mostly at the 1st step. → The observed catalytic effects on CO hydrogenation increase with water concentration. - Abstract: The reaction of successive CO hydrogenation has been performed at 3 K by coinjecting CO molecules and H atoms. The concentration of CO has been progressively reduced and replaced by water molecules to create two different environments where CO and H2O are successively the dominant species in the binary (CO/H2O) mixture. The catalytic effect of water molecules on CO hydrogenation appears clearly since the early times of the experiment and evolves with the formation of the CO/H2/H2O mixed-matrix. The process of CO hydrogenation, initially frozen at the first step of the reaction, is brought to completion through water influence. Water molecules guide the reaction toward the formation of CH3OH and promote different reaction steps depending on water concentration. Water molecules increase the probability of reactive to encounter H atoms either physically, by introducing structural changes in the matrix, or chemically, by raising the number of chemical pathways.

  15. Enhanced catalytic oxidation ability of ternary layered double hydroxides for organic pollutants degradation.

    Science.gov (United States)

    Fahel, Jean; Kim, Sanghoon; Durand, Pierrick; André, Erwan; Carteret, Cédric

    2016-05-10

    Co(2+) and Cu(2+) substituted MgAl layered double hydroxides with an M(2+)/M(3+) atomic ratio of 2.0 were synthesized by a co-precipitation method and fully characterized using various techniques including powder X-ray diffraction, ICP-AES analysis, FT-IR, DR UV-Vis spectroscopy, N2 adsorption-desorption and transmission electron microscopy. The materials revealed a good crystallinity with no phase impurity and successful substitution of cobalt and copper ions in the framework of binary LDH with the target ratio of metals in the sheet. The adsorption characteristics (kinetic and isotherm) and the catalytic oxidation of organic pollutants, methylene blue (cationic dye) and orange II (anionic) were carried out to investigate a potential use of LDH materials as catalysts. In particular, Co3Cu1Al2 LDH exhibited an excellent catalytic activity towards catalytic dye degradation, especially for orange II with good stability and reusability over several times. Furthermore, this LDH material showed good catalytic performance for several chlorophenol compounds, suggesting its practical application in wastewater treatment. Therefore, layered double hydroxides substituted with Co(2+) and Cu(2+) could be promising candidates in various applications, such as the abatement of organic pollutants. PMID:27097543

  16. Intrinsic catalytic properties of extruded clay honeycomb monolith toward complete oxidation of air pollutants.

    Science.gov (United States)

    Assebban, Mhamed; El Kasmi, Achraf; Harti, Sanae; Chafik, Tarik

    2015-12-30

    The present work highlights the intrinsic catalytic properties of extruded clay honeycomb monolith toward complete oxidation of various air pollutants namely CO, methane, propane, acetylene, propene, n-butene, methanol, ethanol, n-propanol, n-butanol, acetone, dimethyl ether, benzene, toluene, o-xylene, monochlorobenzene and 1,2-dichlorobenzene. Total catalytic conversion was achieved for all tested compounds with different behaviors depending on pollutants' structural and chemical nature. The comparison of T50 values obtained from light-off curves allowed the establishment of the following reactivity sequence: ketone>alcohol>ether>CO>alkyne>aromatic>alkene>chlorinated aromatic>alkane. The intrinsic catalytic performances of the natural clay was ascribed to the implication of a quite complex mixture constituted by OH groups (Brønsted acids) and coordinately-unsaturated cations, such as Al(3+), Fe(3+) and Fe(2+) (Lewis acids). Hence, the combination of the clay's intrinsic catalytic performances and easier extrudability suggests a promissory potential for application in air pollution control. PMID:26259164

  17. Discovery of New Oxygen Evolution Reaction Electrocatalysts by Combinatorial Investigation of the Ni–La–Co–Ce Oxide Composition Space

    OpenAIRE

    Haber, Joel A.; Guevarra, Dan; Jung, Suho; Jin, Jian; Gregoire, John M.

    2014-01-01

    We report a new family of earth-abundant electrocatalysts for the oxygen evolution reaction (OER) discovered via high-throughput screening of 1771 discrete metal oxide compositions covering the nickel–lanthanum–cobalt–cerium composition space. The catalytic performance of each of these compositions was measured under conditions applicable to distributed solar fuel generation using a three-electrode scanning-drop electrochemical cell. These high-throughput measurements show enhanced activity f...

  18. Ultrafast Dynamics of Plasmon-Exciton Interaction of Ag Nanowire- Graphene Hybrids for Surface Catalytic Reactions.

    Science.gov (United States)

    Ding, Qianqian; Shi, Ying; Chen, Maodu; Li, Hui; Yang, Xianzhong; Qu, Yingqi; Liang, Wenjie; Sun, Mengtao

    2016-01-01

    Using the ultrafast pump-probe transient absorption spectroscopy, the femtosecond-resolved plasmon-exciton interaction of graphene-Ag nanowire hybrids is experimentally investigated, in the VIS-NIR region. The plasmonic lifetime of Ag nanowire is about 150 ± 7 femtosecond (fs). For a single layer of graphene, the fast dynamic process at 275 ± 77 fs is due to the excitation of graphene excitons, and the slow process at 1.4 ± 0.3 picosecond (ps) is due to the plasmonic hot electron interaction with phonons of graphene. For the graphene-Ag nanowire hybrids, the time scale of the plasmon-induced hot electron transferring to graphene is 534 ± 108 fs, and the metal plasmon enhanced graphene plasmon is about 3.2 ± 0.8 ps in the VIS region. The graphene-Ag nanowire hybrids can be used for plasmon-driven chemical reactions. This graphene-mediated surface-enhanced Raman scattering substrate significantly increases the probability and efficiency of surface catalytic reactions co-driven by graphene-Ag nanowire hybridization, in comparison with reactions individually driven by monolayer graphene or single Ag nanowire. This implies that the graphene-Ag nanowire hybrids can not only lead to a significant accumulation of high-density hot electrons, but also significantly increase the plasmon-to-electron conversion efficiency, due to strong plasmon-exciton coupling. PMID:27601199

  19. Classical Keggin Intercalated into Layered Double Hydroxides: Facile Preparation and Catalytic Efficiency in Knoevenagel Condensation Reactions.

    Science.gov (United States)

    Jia, Yueqing; Fang, Yanjun; Zhang, Yingkui; Miras, Haralampos N; Song, Yu-Fei

    2015-10-12

    The family of polyoxometalate (POM) intercalated layered double hydroxide (LDH) composite materials has shown great promise for the design of functional materials with numerous applications. It is known that intercalation of the classical Keggin polyoxometalate (POM) of [PW12 O40 ](3-) (PW12 ) into layered double hydroxides (LDHs) is very unlikely to take place by conventional ion exchange methods due to spatial and geometrical restrictions. In this paper, such an intercalated compound of Mg0.73 Al0.22 (OH)2 [PW12 O40 ]0.04 ⋅0.98 H2 O (Mg3 Al-PW12 ) has been successfully obtained by applying a spontaneous flocculation method. The Mg3 Al-PW12 has been fully characterized by using a wide range of methods (XRD, SEM, TEM, XPS, EDX, XPS, FT-IR, NMR, BET). XRD patterns of Mg3 Al-PW12 exhibit no impurity phase usually observed next to the (003) diffraction peak. Subsequent application of the Mg3 Al-PW12 as catalyst in Knoevenagel condensation reactions of various aldehydes and ketones with Z-CH2 -Z' type substrates (ethyl cyanoacetate and malononitrile) at 60 °C in mixed solvents (V2-propanol :Vwater =2:1) demonstrated highly efficient catalytic activity. The synergistic effect between the acidic and basic sites of the Mg3 Al-PW12 composite proved to be crucial for the efficiency of the condensation reactions. Additionally, the Mg3 Al-PW12 -catalyzed Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate demonstrated the highest turnover number (TON) of 47 980 reported so far for this reaction. PMID:26337902

  20. Positive patch test reactions to oxidized limonene

    DEFF Research Database (Denmark)

    Bråred Christensson, Johanna; Andersen, Klaus E; Bruze, Magnus;

    2014-01-01

    BACKGROUND: R-Limonene is a common fragrance terpene found in domestic and industrial products. R-Limonene autoxidizes on air exposure, and the oxidation products can cause contact allergy. In a recent multicentre study, 5.2% (range 2.3-12.1%) of 2900 patients showed a positive patch test reactio...

  1. CO-H2-O2 reaction on a catalytic surface: A computer simulation study

    International Nuclear Information System (INIS)

    The oxidation of carbon monoxide to form carbon dioxide and the oxidation of hydrogen to form water are the reactions of environmental and industrial importance. These two reactions have been studied independently by Monte Carlo computer simulation using Langmuir-Hinshelwood mechanism but no effort has been made to study the combined CO-H2-O2 reaction on these lines. Keeping in view the importance of this 3-component system, the surface coverages and production rates are studied as a function of CO partial pressure for different ratios of H2 and O2. The diffusion of reacting species on the surface as well as their desorption from the surface is also introduced to include temperature effects. The phase diagrams of the system are drawn to observe the behavior of these atoms/molecules on the surface and the production of CO2 and H2O are determined at different concentrations of H2. The results are compared with 2-component systems.

  2. Principles of water oxidation and O2-based hydrocarbon transformation by multinuclear catalytic sites

    Energy Technology Data Exchange (ETDEWEB)

    Musaev, Djamaladdin G [Chemistry, Emory University; Hill, Craig L [Chemistry, Emory University; Morokuma, Keiji [Chemistry, Emory University

    2014-10-28

    Abstract The central thrust of this integrated experimental and computational research program was to obtain an atomistic-level understanding of the structural and dynamic factors underlying the design of catalysts for water oxidation and selective reductant-free O2-based transformations. The focus was on oxidatively robust polyoxometalate (POM) complexes in which a catalytic active site interacts with proximal metal centers in a synergistic manner. Thirty five publications in high-impact journals arose from this grant. I. Developing an oxidatively and hydrolytically stable and fast water oxidation catalyst (WOC), a central need in the production of green fuels using water as a reductant, has proven particularly challenging. During this grant period we have designed and investigated several carbon-free, molecular (homogenous), oxidatively and hydrolytically stable WOCs, including the Rb8K2[{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2]·25H2O (1) and [Co4(H2O)2(α-PW9O34)2]10- (2). Although complex 1 is fast, oxidatively and hydrolytically stable WOC, Ru is neither abundant nor inexpensive. Therefore, development of a stable and fast carbon-free homogenous WOC, based on earth-abundant elements became our highest priority. In 2010, we reported the first such catalyst, complex 2. This complex is substantially faster than 1 and stable under homogeneous conditions. Recently, we have extended our efforts and reported a V2-analog of the complex 2, i.e. [Co4(H2O)2(α-VW9O34)2]10- (3), which shows an even greater stability and reactivity. We succeeded in: (a) immobilizing catalysts 1 and 2 on the surface of various electrodes, and (b) elucidating the mechanism of O2 formation and release from complex 1, as well as the Mn4O4L6 “cubane” cluster. We have shown that the direct O-O bond formation is the most likely pathway for O2 formation during water oxidation catalyzed by 1. II. Oxo transfer catalysts that contain two proximal and synergistically interacting redox active metal

  3. β-Alanine-DBU" A Highly Efficient Catalytic System forKnoevenageI-Doebner Reaction under Mild Conditionsβ-Alanine-DBU" A Highly Efficient Catalytic System forKnoevenageI-Doebner Reaction under Mild Conditions

    Institute of Scientific and Technical Information of China (English)

    祝令建; 雷宁; 缪震元; 盛春泉; 庄春林; 姚建忠; 张万年

    2012-01-01

    A mild and efficient Knoevenagel-Doebner reaction from malonic acid and a wide range of aldehydes was catalyzed by a catalytic system consisting offlalanine and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), affording the corresponding (E)-a,fl-unsaturated carboxylic acids in good to excellent yields and with high stereoselectivity. The advantage of the method is that the reaction could proceed smoothly at ambient temperature so that it can tolerate a variety of functional groups and avoid unnecessary side reactions.

  4. Catalytic Formation of Propylene Carbonate from Supercritical Carbon Dioxide/Propylene Oxide Mixture

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Propylene carbonate was synthesized from supercritical carbon dioxide (SC-CO2)/ propylene oxide mixture with phthalocyaninatoaluminium chloride (ClAlPc)/ tetrabutylammon-ium bromide (n-Bu4NBr) as catalyst. The high rate of reaction was attributed to rapid diffusion and the high miscibility of propylene oxide in SC-CO2 under employed conditions. Various reaction periods present different formation rate of propylene carbonate, mainly due to the existence of phase change during the reaction. The experimental results demonstrate that SC-CO2 could be used as not only an environmentally benign solvent but also a carbon precursor in synthesis.

  5. Catalytic activities enhanced by abundant structural defects and balanced N distribution of N-doped graphene in oxygen reduction reaction

    Science.gov (United States)

    Bai, Xiaogong; Shi, Yantao; Guo, Jiahao; Gao, Liguo; Wang, Kai; Du, Yi; Ma, Tingli

    2016-02-01

    N-doped graphene (NG) is a promising candidate for oxygen reduction reaction (ORR) in the cathode of fuel cells. However, the catalytic activity of NG is lower than that of commercial Pt/C in alkaline and acidic media. In this study, NG samples were obtained using urea as N source. The structural defects and N distribution in the samples were adjusted by regulating the pyrolysis temperature. The new NG type exhibited remarkable catalytic activities for ORR in both alkaline and acidic media.

  6. Facile preparation of β-Ni(OH)2-NiCo2O4 hybrid nanostructure and its application in the electro-catalytic oxidation of methanol

    International Nuclear Information System (INIS)

    Highlights: • Surfactant-free synthetic methodology is reported for hybrid nanostructures. • The electrochemical oxidation of methanol was investigated. • β-Ni(OH)2-NiCo2O4 modified CPE exhibited the highest activity in methanol oxidation. - Abstract: A surfactant-free synthetic methodology is reported for the preparation of β-Ni(OH)2-NiCo2O4 hybrid nanostructure. For comparative study, β-Ni(OH)2-NiO, β-Ni(OH)2-Co3O4, NiCo2O4, NiO, Co3O4, and β-Ni(OH)2 were also synthesized. Materials were characterized by X-ray diffraction, nitrogen sorption, scanning electron microscopy, and transmission electron microscopy. The electrochemical oxidation of methanol is investigated at β-Ni(OH)2-NiCo2O4 modified electrode in the alkaline medium using cyclic voltammetry (CV) and chronoamperometry methods. A detailed investigation is made for the electro-catalytic oxidation of methanol by varying several reaction parameters such as potential scan rate, methanol concentration, etc. Mechanism of methanol oxidation is proposed based on the CV and double steps chronoamperometry studies. β-Ni(OH)2-NiCo2O4 modified electrode exhibited comparatively higher electro-catalytic activity in the methanol oxidation when compared to other modified electrodes investigated in this study

  7. Selective catalytic reduction of nitrogen oxides from industrial gases by hydrogen or methane

    International Nuclear Information System (INIS)

    This work deals with the selective catalytic reduction of nitrogen oxides (NOx), contained in the effluents of industrial plants, by hydrogen or methane. The aim is to replace ammonia, used as reducing agent, in the conventional process. The use of others reducing agents such as hydrogen or methane is interesting for different reasons: practical, economical and ecological. The catalyst has to convert selectively NO into N2, in presence of an excess of oxygen, steam and sulfur dioxide. The developed catalyst is constituted by a support such as perovskites, particularly LaCoO3, on which are dispersed noble metals (palladium, platinum). The interaction between the noble metal and the support, generated during the activation of the catalyst, allows to minimize the water and sulfur dioxide inhibitor phenomena on the catalytic performances, particularly in the reduction of NO by hydrogen. (O.M.)

  8. Catalytic oxidative treatment of diluted black liquor at mild conditions using copper oxide/cerium oxide catalyst.

    Science.gov (United States)

    Garg, Anurag; Mishra, Indra M; Chand, Shri

    2008-02-01

    Wet-air oxidation of diluted black liquor (chemical oxygen demand [COD] approximately 3250 to 14 500 mg/L) was performed at mild operating conditions (temperature = 388 to 423 K and total pressure = 0.6 MPa) in the presence of heterogeneous 60% copper oxide (CuO)/ 40% cerium oxide (CeO2) catalyst. Maximum COD reduction of 77.3% was obtained at 423 K at pH 3.0, which was marginally higher than that obtained at 413 K temperature (77.1%). In the acidic environment (pH < or = 3), most of the COD was removed in the form of settleable solids during the transient heating of the wastewater from room temperature to the desired one. The solid residue obtained after the reaction has a heating value of 20.1 MJ/kg, which is comparable with that of Indian coal. Thermal degradation kinetic determination suggested that thermal characteristics of the solid residue are well represented by a power law model with Agarwal and Sivasubramanian approximation (Safi et al., 2004). PMID:18330223

  9. A Bioorthogonal Reaction of N-Oxide and Boron Reagents.

    Science.gov (United States)

    Kim, Justin; Bertozzi, Carolyn R

    2015-12-21

    The development of bioorthogonal reactions has classically focused on bond-forming ligation reactions. In this report, we seek to expand the functional repertoire of such transformations by introducing a new bond-cleaving reaction between N-oxide and boron reagents. The reaction features a large dynamic range of reactivity, showcasing second-order rate constants as high as 2.3×10(3)  M(-1)  s(-1) using diboron reaction partners. Diboron reagents display minimal cell toxicity at millimolar concentrations, penetrate cell membranes, and effectively reduce N-oxides inside mammalian cells. This new bioorthogonal process based on miniscule components is thus well-suited for activating molecules within cells under chemical control. Furthermore, we demonstrate that the metabolic diversity of nature enables the use of naturally occurring functional groups that display inherent biocompatibility alongside abiotic components for organism-specific applications. PMID:26568479

  10. Laccase-Functionalized Graphene Oxide Assemblies as Efficient Nanobiocatalysts for Oxidation Reactions

    OpenAIRE

    Patila, Michaela; Kouloumpis, Antonios; Gournis, Dimitrios; Rudolf, Petra; Stamatis, Haralambos

    2016-01-01

    Multi-layer graphene oxide-enzyme nanoassemblies were prepared through the multi-point covalent immobilization of laccase from Trametes versicolor (TvL) on functionalized graphene oxide (fGO). The catalytic properties of the fGO-TvL nanoassemblies were found to depend on the number of the graphene oxide-enzyme layers present in the nanostructure. The fGO-TvL nanoassemblies exhibit an enhanced thermal stability at 60 °C, as demonstrated by a 4.7-fold higher activity as compared to the free enz...

  11. Catalytic NO reduction with ammonia at low temperatures on V2O5/AC catalysts. Effect of metal oxides addition and SO2

    International Nuclear Information System (INIS)

    The catalytic behavior of the V-M/AC (M=W, Mo, Zr, and Sn) catalysts were studied for the NO reduction with ammonia at low temperatures, especially in the presence of SO2. The presence of the metal oxides does not increase the V2O5/AC activity but decreases it. Except V-Mo/AC, the other catalysts are promoted by SO2 at 250C, especially for V-Sn/AC. However, the promoting effect of SO2 is gradually depressed by catalyst deactivation. Changes in catalyst preparation method can improve the catalyst stability in short-term but cannot completely prevent the catalyst from a long-term deactivation. Mechanisms of the promoting effect and the deactivation of V-Sn/AC catalyst by SO2 were studied using Fourier transform infrared spectroscopy (FT-IR) spectra and measurement of catalyst surface area and pore volume. The results showed that both the SO2 promotion and deactivation are associated with the formation of sulfate species on the catalyst surface. In the initial period of the selective catalytic reduction (SCR) reaction in the presence of SO2, the formed sulfate species provide new acid sites to enhance ammonia adsorption and thus the catalytic activity. However, as the SCR reaction proceeds, excess amount of sulfate species and then ammonium-sulfate salts are formed which is stabilized by the presence of tin oxide, resulting in gradual plugging of the pore structures and the catalyst deactivation

  12. The catalytic behavior of La-Mn-O nanoparticle perovskite-type oxide catalysts for the combustion of the soot particle from the diesel engine

    Institute of Scientific and Technical Information of China (English)

    WANG Hong; ZHAO Zhen; XU Chunming; LIU Jian; LU Zhixiao

    2005-01-01

    The La1-xMx MnO3(M=Li, Na, K, Rb, x=0, 0.10, 0.25) perovskite-type oxides whose sizes are nanoparticle have been prepared by the citric acid-ligated method. The characters of the catalysts were characterized by means of XRD, IR, SEM and BET surface area measurement. The catalytic activity for the combustion of soot particulate was evaluated by a technique of the temperature-programmed reaction. In the LaMnO3 catalyst, the partial substitution of alkali metal (Li, Na, K, Rb) into A-site enhanced the catalytic activity for the combustion of soot particle. The La0.75K0.25MnO3 oxides are good candidate catalysts for the soot particle removal reaction, and the combustion temperatures of soot particle are between 285℃ and 430℃ when the contact of catalysts and soot is loose, and their catalytic activities for the combustion of soot particle are as good as supported Pt catalysts, which is the best catalyst system so far reported for soot combustion under loose contact conditions.

  13. Selective catalytic reduction of nitric oxide by ammonia over Cu-exchanged Cuban natural zeolites

    International Nuclear Information System (INIS)

    The catalytic selective reduction of NO over Cu-exchanged natural zeolites (mordenite (MP) and clinoptilolite (HC)) from Cuba using NH3 as reducing agent and in the presence of excess oxygen was studied. Cu(II)-exchanged zeolites are very active catalysts, with conversions of NO of 95%, a high selectivity to N2 at low temperatures, and exhibiting good water tolerance. The chemical state of the Cu(II) in exchanged zeolites was characterized by H2-TPR and XPS. Cu(II)-exchanged clinoptilolite underwent a severe deactivation in the presence of SO2. However, Cu(II)-exchanged mordenite not only maintained its catalytic activity, but even showed a slight improvement after 20h of reaction in the presence of 100ppm of SO2

  14. Heterogeneous catalytic ozonation of ciprofloxacin in water with carbon nanotube supported manganese oxides as catalyst

    International Nuclear Information System (INIS)

    Highlights: ► Ciprofloxacin in water was degraded by heterogeneous catalytic ozonation. ► MnOx were supported on MWCNTs to serve as catalyst for ozonation. ► MnOx/MWCNT exhibited highly catalytic activity on ozonation of ciprofloxacin in water. ► MnOx/MWCNT resulted in effective antibacterial activity inhibition on ciprofloxacin. ► MnOx/MWCNT promoted the generation of hydroxyl radicals. - Abstract: Carbon nanotube-supported manganese oxides (MnOx/MWCNT) were used as catalysts to assist ozone in degrading ciprofloxacin in water. Manganese oxides were successfully loaded on multi-walled carbon nanotube surfaces by simply impregnating the carbon nanotube with permanganate solution. The catalytic activities of MnOx/MWCNT in ciprofloxacin ozonation, including degradation, mineralization effectiveness, and antibacterial activity change, were investigated. The presence of MnOx/MWCNT significantly elevated the degradation and mineralization efficiency of ozone on ciprofloxacin. The microbiological assay with a reference Escherichia coli strain indicated that ozonation with MnOx/MWCNT results in more effective antibacterial activity inhibition of ciprofloxacin than that in ozonation alone. The effects of catalyst dose, initial ciprofloxacin concentration, and initial pH conditions on ciprofloxacin ozonation with MnOx/MWCNT were surveyed. Electron spin resonance trapping was applied to assess the role of MnOx/MWCNT in generating hydroxyl radicals (HO·) during ozonation. Stronger 5,5-dimethyl-1-pyrroline-N-oxide–OH signals were observed in the ozonation with MnOx/MWCNT compared with those in ozonation alone, indicating that MnOx/MWCNT promoted the generation of hydroxyl radicals. The degradation of ciprofloxacin was studied in drinking water and wastewater process samples to gauge the potential effects of water background matrix on MnOx/MWCNT catalytic ozonation.

  15. Influence of fuel properties, nitrogen oxides, and exhaust treatment by an oxidation catalytic converter on the mutagenicity of diesel engine emissions

    Energy Technology Data Exchange (ETDEWEB)

    Buenger, Juergen; Bruening, Thomas [Ruhr University Bochum, Research Institute for Occupational Medicine of the Institutions for Statutory Accident Insurance and Prevention (BGFA), Bochum (Germany); Krahl, Juergen; Schroeder, Olaf [Federal Agricultural Research Centre, Institute of Biosystems Engineering, Braunschweig (Germany); Weigel, Andreas; Mueller, Michael; Hallier, Ernst; Westphal, Goetz [University of Goettingen, Department of Occupational and Social Medicine, Gottingen (Germany)

    2006-08-15

    Particle emissions of diesel engines (DEP) content polycyclic aromatic hydrocarbons (PAH) these compounds cause a strong mutagenicity of solvent extracts of DEP. We investigated the influence of fuel properties, nitrogen oxides (NO{sub x}), and an oxidation catalytic converter (OCC) on the mutagenic effects of DEP. The engine was fuelled with common diesel fuel (DF), low-sulphur diesel fuel (LSDF), rapeseed oil methyl ester (RME), and soybean oil methyl ester (SME) and run at five different load modes in two series with and without installation of an OCC in the exhaust pipe. Particles from the cooled and diluted exhaust were sampled onto glass fibre filters and extracted with dichloromethane in a soxhlet apparatus. The mutagenicity of the extracts was tested using the Salmonella typhimurium/mammalian microsome assay with tester strains TA98 and TA100. Without OCC the number of revertant colonies was lower in extracts of LSDF than in extracts of DF. The lowest numbers of revertant colonies were induced by the plant oil derived fuels. In three load modes, operation with the OCC led to a reduction of the mutagenicity. However, direct mutagenic effects under heavy duty conditions (load mode A) were significantly increased for RME (TA98, TA100) and SME (TA98). A consistent but not significant increase in direct mutagenicity was observed for DF and LSDF at load mode A, and for DF at idling (load mode E) when emissions were treated with the OCC. These results raise concern over the use of oxidation catalytic converters with diesel engines. We hypothesise that the OCC increases formation of direct acting mutagens under certain conditions by the reaction of NO{sub x} with PAH resulting in the formation of nitrated-PAH. Most of these compounds are powerful direct acting mutagens. (orig.)

  16. Influence of fuel properties, nitrogen oxides, and exhaust treatment by an oxidation catalytic converter on the mutagenicity of diesel engine emissions.

    Science.gov (United States)

    Bünger, Jürgen; Krahl, Jürgen; Weigel, Andreas; Schröder, Olaf; Brüning, Thomas; Müller, Michael; Hallier, Ernst; Westphal, Götz

    2006-08-01

    Particle emissions of diesel engines (DEP) content polycyclic aromatic hydrocarbons (PAH) these compounds cause a strong mutagenicity of solvent extracts of DEP. We investigated the influence of fuel properties, nitrogen oxides (NO( x )), and an oxidation catalytic converter (OCC) on the mutagenic effects of DEP. The engine was fuelled with common diesel fuel (DF), low-sulphur diesel fuel (LSDF), rapeseed oil methyl ester (RME), and soybean oil methyl ester (SME) and run at five different load modes in two series with and without installation of an OCC in the exhaust pipe. Particles from the cooled and diluted exhaust were sampled onto glass fibre filters and extracted with dichloromethane in a soxhlet apparatus. The mutagenicity of the extracts was tested using the Salmonella typhimurium/mammalian microsome assay with tester strains TA98 and TA100. Without OCC the number of revertant colonies was lower in extracts of LSDF than in extracts of DF. The lowest numbers of revertant colonies were induced by the plant oil derived fuels. In three load modes, operation with the OCC led to a reduction of the mutagenicity. However, direct mutagenic effects under heavy duty conditions (load mode A) were significantly increased for RME (TA98, TA100) and SME (TA98). A consistent but not significant increase in direct mutagenicity was observed for DF and LSDF at load mode A, and for DF at idling (load mode E) when emissions were treated with the OCC. These results raise concern over the use of oxidation catalytic converters with diesel engines. We hypothesise that the OCC increases formation of direct acting mutagens under certain conditions by the reaction of NO( x ) with PAH resulting in the formation of nitrated-PAH. Most of these compounds are powerful direct acting mutagens. PMID:16555046

  17. Catalytic selective oxidation or oxidative functionalization of methane and ethane to organic oxygenates

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Selective oxidation or oxidative functionalization of methane and ethane by both homogeneous and heterogeneous catalysis is presented concerning: (1) selective oxidation of methane and ethane to organic oxygenates by hydrogen peroxide in a water medium in the presence of homogeneous osmium catalysts, (2) selective oxidation of methane to formaldehyde over highly dispersed iron and copper heterogeneous catalysts, (3) selective oxidation of ethane to acetaldehyde and formaldehyde over supported molybdenum catalysts, and (4) oxidative carbonylation of methane to methyl acetate over heterogeneous catalysts containing dual sites of rhodium and iron.

  18. NO-CO-O2 Reaction on a Metal Catalytic Surface using Eley-Rideal Mechanism

    Institute of Scientific and Technical Information of China (English)

    Waqar Ahmad

    2008-01-01

    Interactions among the reacting species NO, CO and O2 on metal catalytic surfaces are studied by means of Monte Carlo simulation using the Eley-Rideal (ER) mechanism. The study of this three-component system is important for understanding of the reaction kinetics by varying the relative ratios of the reactants. It is found that contrary to the conventional Langmuir-Hinshelwood (LH) thermal mechanism in which two irreversible phase transitions are obtained between active states and poisoned states, a single phase transition is observed when the ER mechanism is combined with the LH mechanism. The phase diagrams of the surface coverage and the steady state production of CO2, N2 and N2O are evaluated as a function of the partial pressures of the reactants in the gas phase. The continuous production of CO2 starts as soon as the CO pressure is switched on and the second order phase transition at the first critical point is eliminated, which is in agreement with the experimental findings.

  19. Novel plasma catalytic reaction for structural-controlled growth of graphene and graphene nanoribbon

    Science.gov (United States)

    Kato, Toshiaki

    2013-09-01

    An advanced plasma chemical vapor deposition (CVD) method has outstanding advantages for the structural-controlled growth and functionalization of carbon nanotubes (CNTs) and graphene. Graphene nanoribbons combine the unique electronic and spin properties of graphene with a transport gap. This makes them an attractive candidate material for the channels of next-generation transistors. However, the reliable site and alignment control of nanoribbons with high on/off current ratios remains a challenge. We have developed a new, simple, scalable method based on novel plasma catalytic reaction for directly fabricating narrow (23 nm) graphene nanoribbon devices with a clear transport gap (58.5 meV) and a high on/off ratio (10000). Indeed, graphene nanoribbons can be grown at any desired position on an insulating substrate without any post-growth treatment, and large-scale, two- and three dimensional integration of graphene nanoribbon devices should be realizable, thereby accelerating the practical evolution of graphene nanoribbon-based electrical applications.

  20. Tuning the catalytic activity of graphene nanosheets for oxygen reduction reaction via size and thickness reduction.

    Science.gov (United States)

    Benson, John; Xu, Qian; Wang, Peng; Shen, Yuting; Sun, Litao; Wang, Tanyuan; Li, Meixian; Papakonstantinou, Pagona

    2014-11-26

    Currently, the fundamental factors that control the oxygen reduction reaction (ORR) activity of graphene itself, in particular, the dependence of the ORR activity on the number of exposed edge sites remain elusive, mainly due to limited synthesis routes of achieving small size graphene. In this work, the synthesis of low oxygen content (graphene nanosheets with lateral dimensions smaller than a few hundred nanometers were achieved using a combination of ionic liquid assisted grinding of high purity graphite coupled with sequential centrifugation. We show for the first time that the graphene nanosheets possessing a plethora of edges exhibited considerably higher electron transfer numbers compared to the thicker graphene nanoplatelets. This enhanced ORR activity was accomplished by successfully exploiting the plethora of edges of the nanosized graphene as well as the efficient electron communication between the active edge sites and the electrode substrate. The graphene nanosheets were characterized by an onset potential of -0.13 V vs Ag/AgCl and a current density of -3.85 mA/cm2 at -1 V, which represent the best ORR performance ever achieved from an undoped carbon based catalyst. This work demonstrates how low oxygen content nanosized graphene synthesized by a simple route can considerably impact the ORR catalytic activity and hence it is of significance in designing and optimizing advanced metal-free ORR electrocatalysts.

  1. Catalytic oxidation of anionic surfactants by electrochemical oxidation with CuO-Co2O3-PO43- modified kaolin

    International Nuclear Information System (INIS)

    A new catalytic oxidation of anionic surfactants by electrochemistry method was designed and used to investigate the removal of anionic surfactant from simulated wastewater. Synergetic effect on COD removal was studied when integrating the electrochemical reactor, using porous graphite as anode and cathode, with the effective CuO-Co2O3-PO43- modified kaolin catalyst in a single undivided cell. The result showed that this combined process could effectively remove anionic surfactant. Its COD removal efficiency was much higher than those individual processes and could reach up to 90% in 60 min. The operating parameters such as initial pH, cell voltage, and current intensity were also investigated. Possible theory for COD removal was also proposed to predict the role of modified kaolin, electro-catalysis and oxidation in the combined process. The pollutants in wastewater could be decreased by the high reactive OH· that produced on the surface of catalyst by the decomposition of electrochemical generated H2O2. The result indicates that the catalytic oxidation by electrochemistry method is a promising wastewater treatment technique

  2. Catalytic effects on methanol oxidation produced by cathodization of platinum electrodes.

    Science.gov (United States)

    Díaz, Verónica; Zinola, Carlos F

    2007-09-01

    A catalytic effect is found for methanol oxidation after new active surface states are produced on polycrystalline platinum by potentiostatic cathodization in acid media at room temperature. This procedure originates surface states not available on the original polycrystalline electrodes with unexpected cyclic voltammetric responses; i.e., at least four new peaks below 0.9 V are observed. The cathodization process also induces a rearrangement of the bulk platinum oxide, showing a defined peak at 1.2 V. The appearance of these new states is also proven by open-circuit potential decays. The electrocatalytic activity of these new surfaces in methanol oxidation is compared with that of the untreated electrodes by electrochemical impedance spectroscopy, chronoamperometry, and cyclic voltammetry. The cathodic procedure enhances the methanol oxidation voltammetric current peaks with charge density values higher than those on untreated platinum. The integration of chronoamperometric plots over 10 min in methanol acid media presents the largest difference between 0.6 and 0.7 V with respect to the original surface. Analysis of the impedance data shows that the values of polarization resistance for methanol oxidation on the cathodically treated platinum are lower than those of the original surface. According to the time constant values for methanol oxidation, the original surface can be considered less tolerant of the formation of catalytic poisons. A discussion of the most likely mechanism for the formation of the new active sites on platinum is presented here, assuming the presence of hydrogen subsurface states, ordered water clusters, and low-coordinated platinum atoms. PMID:17543323

  3. Size-Dependent Electrocatalytic Activity of Free Gold Nanoparticles for the Glucose Oxidation Reaction.

    Science.gov (United States)

    Hebié, Seydou; Napporn, Teko W; Morais, Cláudia; Kokoh, K Boniface

    2016-05-18

    Understanding the fundamental relationship between the size and the structure of electrode materials is essential to design catalysts and enhance their activity. Therefore, spherical gold nanoparticles (GNSs) with a mean diameter from 4 to 15 nm were synthesized. UV/Vis spectroscopy, transmission electron microscopy, and under-potential deposition of lead (UPDPb ) were used to determine the morphology, size, and surface crystallographic structure of the GNSs. The UPDPb revealed that their crystallographic facets are affected by their size and the growth process. The catalytic properties of these GNSs toward glucose electrooxidation were studied by cyclic voltammetry, taking into account the scan rate and temperature effects. The results clearly show the size-dependent electrocatalytic activity for glucose oxidation reactions that are controlled by diffusion. Small GNSs with an average size of 4.2 nm exhibited high catalytic activity. This drastic increase in activity results from the high specific area and reactivity of the surface electrons induced by their small size. The reaction mechanism was investigated by in situ Fourier transform infrared reflectance spectroscopy. Gluconolactone and gluconate were identified as the intermediate and the final reaction product, respectively, of the glucose electrooxidation.

  4. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab

    2015-09-24

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation. © 2015 American Chemical Society.

  5. Catalytic Role of Manganese Oxides in Prebiotic Nucleobases Synthesis from Formamide

    Science.gov (United States)

    Bhushan, Brij; Nayak, Arunima; Kamaluddin

    2016-06-01

    Origin of life processes might have begun with the formation of important biomonomers, such as amino acids and nucleotides, from simple molecules present in the prebiotic environment and their subsequent condensation to biopolymers. While studying the prebiotic synthesis of naturally occurring purine and pyrimidine derivatives from formamide, the manganese oxides demonstrated not only good binding for formamide but demonstrated novel catalytic activity. A novel one pot manganese oxide catalyzed synthesis of pyrimidine nucleobases like thymine is reported along with the formation of other nucleobases like purine, 9-(hydroxyacetyl) purine, cytosine, 4(3 H)-pyrimidinone and adenine in acceptable amounts. The work reported is significant in the sense that the synthesis of thymine has exhibited difficulties especially under one pot conditions and also such has been reported only under the catalytic activity of TiO2. The lower oxides of manganese were reported to show higher potential as catalysts and their existence were favored by the reducing atmospheric conditions prevalent on early Earth; thereby confirming the hypothesis that mineral having metals in reduced form might have been more active during the course of chemical evolution. Our results further confirm the role of formamide as a probable precursor for the formation of purine and pyrimidine bases during the course of chemical evolution and origin of life.

  6. Catalytic partial oxidation of methane over porous silica supported VO{sub x} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Pirovano, C.; Schoenborn, E.; Kalevaru, V.N.; Wohlrab, S.; Luecke, B.; Martin, A. [University Rostock e.V., Rostock (Germany). Leibniz Inst. for Catalysis

    2011-07-01

    High surface area mesoporous siliceous MCM-41 and SBA-15 materials have been used as supports to disperse vanadium oxide species using wet impregnation and incipient wetness impregnation methods. These materials were used as catalysts for the partial oxidation of methane (POM) to formaldehyde. The physico-chemical properties of the solids were studied by means of BET, DR-UV/Vis spectroscopy, Py-FTIR and TEM. The influence of support and the preparation method on the dispersion of VOx is also investigated. The catalytic properties of the catalysts were examined in a fixed bed stainless steel reactor at 923 K. So far a maximum production of formaldehyde can be detected on SBA-15 supported VOx-catalysts prepared by incipient wetness impregnation. On this V/SBA-15 material a covalent attachment of catalytic active molecular vanadium species dominates, which in turn leads to a lower activation temperature and thereby reduced over-oxidation. From the best case, the space time yield of HCHO could be reached close to 775 g{sub HCHO} Kg{sub cat}{sup -1} h{sup -1}. (orig.)

  7. Catalytic Role of Manganese Oxides in Prebiotic Nucleobases Synthesis from Formamide.

    Science.gov (United States)

    Bhushan, Brij; Nayak, Arunima; Kamaluddin

    2016-06-01

    Origin of life processes might have begun with the formation of important biomonomers, such as amino acids and nucleotides, from simple molecules present in the prebiotic environment and their subsequent condensation to biopolymers. While studying the prebiotic synthesis of naturally occurring purine and pyrimidine derivatives from formamide, the manganese oxides demonstrated not only good binding for formamide but demonstrated novel catalytic activity. A novel one pot manganese oxide catalyzed synthesis of pyrimidine nucleobases like thymine is reported along with the formation of other nucleobases like purine, 9-(hydroxyacetyl) purine, cytosine, 4(3 H)-pyrimidinone and adenine in acceptable amounts. The work reported is significant in the sense that the synthesis of thymine has exhibited difficulties especially under one pot conditions and also such has been reported only under the catalytic activity of TiO2. The lower oxides of manganese were reported to show higher potential as catalysts and their existence were favored by the reducing atmospheric conditions prevalent on early Earth; thereby confirming the hypothesis that mineral having metals in reduced form might have been more active during the course of chemical evolution. Our results further confirm the role of formamide as a probable precursor for the formation of purine and pyrimidine bases during the course of chemical evolution and origin of life. PMID:26758444

  8. Mechanistic exploration of the catalytic cycles for the CO oxidation by O2 over FeO(1-3) application of the energetic span model.

    Science.gov (United States)

    Wang, Huan-Jiang; Wang, Yong-Cheng

    2014-06-01

    Carbon monoxide (CO) and oxygen (O2) catalyzed by small neutral iron oxide clusters (FeO(1-3)) was investigated at the density functional level of theory using the Becke-Perdew-Wang functional (BPW91). Three reaction pathways along with singlet, triplet and quintet states were calculated for ascertaining the presence of some spin inversion during the catalytic cycle. The catalytic cycle was found to be "two state reactivity" resulting from the crossing among the multistate energetic profiles. The Landau-Zener equation was used to calculate the thermally-averaged spin transition probabilities for the non-adiabatic surface crossing reaction. In order to predict the efficiency of catalyst the energetic span model developed by Kozuch was implemented, whereas this model is not suitable for handling the diabatic reaction, this feature we must take into consideration. To this end, a kinetic assessment is carried out with an expansion of the energetic span model, including the spin-crossing effects. This approximation enables one to measure the efficiency of catalytic cycle including spin-crossing effects by quantum mechanical computation.

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

    Institute of Scientific and Technical Information of China (English)

    何润霞; 姜浩强; 武芳; 智科端; 王娜; 周晨亮; 刘全生

    2014-01-01

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

  10. Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

    DEFF Research Database (Denmark)

    Beier, Matthias Josef

    . Compared to alcohol oxidation the epoxidation of olefins with molecular oxygen is more difficult. Using N,N-dimethylformamide (DMF) as a solvent the Co-based metal-organic framework (MOF) STA-12(Co) catalyzed the epoxidation of styrene, (E)- and (Z)-stilbene. While the stilbene isomers were converted....... XAS revealed that silver was in the metallic state. Silver particle sizes estimated from XAS were significantly smaller (2- 3 nm) than from transmission electron microscopy (TEM) and X-ray diffraction (XRD; ca. 30 nm). It was proposed that silver-oxygen species might cause local disorder which would...... of silver was observed with the impregnated silver catalyst. By using silver supported on CeO2-SiO2 prepared by flame spray pyrolysis, leaching could be limited significantly. XAS investigation revealed that the active catalyst is most likely metallic silver. Compared to silver on silica calcined at 500 °C...

  11. Co-Al Mixed Oxides Prepared via LDH Route Using Microwaves or Ultrasound: Application for Catalytic Toluene Total Oxidation

    Directory of Open Access Journals (Sweden)

    Eric Genty

    2015-05-01

    Full Text Available Co6Al2HT hydrotalcite-like compounds were synthesized by three different methods: co-precipitation, microwaves-assisted and ultrasound-assisted methods. The mixed oxides obtained after calcination were studied by several techniques: XRD, TEM, H2-TPR and XPS. They were also tested as catalysts in the reaction of total oxidation of toluene. The physico-chemical studies revealed a modification of the structural characteristics (surface area, morphology as well as of the reducibility of the formed mixed oxides. The solid prepared by microwaves-assisted synthesis was the most active. Furthermore, a relationship between the ratio of Co2+ on the surface, the reducibility of the Co-Al mixed oxide and the T50 in toluene oxidation was demonstrated. This suggests a Mars Van Krevelen mechanism for toluene total oxidation on these catalysts.

  12. Chloride ions promoted the catalytic wet peroxide oxidation of phenol over clay-based catalysts.

    Science.gov (United States)

    Zhou, Shiwei; Zhang, Changbo; Xu, Rui; Gu, Chuantao; Song, Zhengguo; Xu, Minggang

    2016-01-01

    Catalytic wet peroxide oxidation (CWPO) of phenol over clay-based catalysts in the presence and absence of NaCl was investigated. Changes in the H2O2, Cl(-), and dissolved metal ion concentration, as well as solution pH during phenol oxidation, were also studied. Additionally, the intermediates formed during phenol oxidation were detected by liquid chromatography-mass spectroscopy and the chemical bonding information of the catalyst surfaces was analyzed by X-ray photoelectron spectroscopy (XPS). The results showed that the presence of Cl(-) increased the oxidation rate of phenol to 155%, and this phenomenon was ubiquitous during the oxidation of phenolic compounds by H2O2 over clay-based catalysts. Cl(-)-assisted oxidation of phenol was evidenced by several analytical techniques such as mass spectroscopy (MS) and XPS, and it was hypothesized that the rate-limiting step was accelerated in the presence of Cl(-). Based on the results of this study, the CWPO technology appears to be promising for applications in actual saline phenolic wastewater treatment. PMID:26942523

  13. Catalytic oxidation of 4-tert-butyltoluene over Ti-MCM-41

    Institute of Scientific and Technical Information of China (English)

    Wei Hua Yu; Chun Hui Zhou; Xiang Sheng Xu; Zhong Hua Ge

    2007-01-01

    The surface-grafted titanium MCM-41 materials were prepared by anchoring titanocene onto the inner walls of MCM-41. The materials were characterized by powder X-ray diffraction (XRD), N2 adsorption-desorption isotherm and diffuse reflectance UV-visible (UV-vis) spectroscopies. The catalytic properties of Ti-MCM-41 were tested in oxidation of 4-tert-butyltoluene with tert-butylhydroperoxide (TBHP) in liquid phase. MCM-41 with loading 4.8 mol% Ti gave the maximal conversions of 23.6% of 4-tert-butyltoluene with a complete selectivity to 4-tert-butylbenzaldehyde.

  14. MWW-type titanosilicate synthesis, structural modification and catalytic applications to green oxidations

    CERN Document Server

    Wu, Peng; Xu, Le; Liu, Yueming; He, Mingyuan

    2013-01-01

    This book provides a comprehensive review of a new generation of selective oxidation titanosilicate catalysts with the MWW topology (Ti-MWW) based on the research achievements of the past 12 years. It gives an overview of the synthesis, structure modification and catalytic properties of Ti-MWW. Ti-MWW can readily be prepared by means of direct hydrothermal synthesis with crystallization-supporting agents, using dual-structure-directing agents and a dry-gel conversion technique. It also can be post-synthesized through unique reversible structure transformation and liquid-phase isomorphous subst

  15. Influence of heme-thiolate in shaping the catalytic properties of a bacterial nitric-oxide synthase.

    Science.gov (United States)

    Hannibal, Luciana; Somasundaram, Ramasamy; Tejero, Jesús; Wilson, Adjele; Stuehr, Dennis J

    2011-11-11

    Nitric-oxide synthases (NOS) are heme-thiolate enzymes that generate nitric oxide (NO) from L-arginine. Mammalian and bacterial NOSs contain a conserved tryptophan (Trp) that hydrogen bonds with the heme-thiolate ligand. We mutated Trp(66) to His and Phe (W66H, W66F) in B. subtilis NOS to investigate how heme-thiolate electronic properties control enzyme catalysis. The mutations had opposite effects on heme midpoint potential (-302, -361, and -427 mV for W66H, wild-type (WT), and W66F, respectively). These changes were associated with rank order (W66H < WT < W66F) changes in the rates of oxygen activation and product formation in Arg hydroxylation and N-hydroxyarginine (NOHA) oxidation single turnover reactions, and in the O(2) reactivity of the ferrous heme-NO product complex. However, enzyme ferrous heme-O(2) autoxidation showed an opposite rank order. Tetrahydrofolate supported NO synthesis by WT and the mutant NOS. All three proteins showed similar extents of product formation (L-Arg → NOHA or NOHA → citrulline) in single turnover studies, but the W66F mutant showed a 2.5 times lower activity when the reactions were supported by flavoproteins and NADPH. We conclude that Trp(66) controls several catalytic parameters by tuning the electron density of the heme-thiolate bond. A greater electron density (as in W66F) improves oxygen activation and reactivity toward substrate, but decreases heme-dioxy stability and lowers the driving force for heme reduction. In the WT enzyme the Trp(66) residue balances these opposing effects for optimal catalysis.

  16. Ship-in-bottle synthesis of NaY zeolite encapsulated Cosalen complex and its catalytic performance for cyclohexane oxidation

    Institute of Scientific and Technical Information of China (English)

    YUAN Xia; LI Fang; LUO He'an

    2007-01-01

    N,N'-bis(salicylidene)ethylenediiminocobalt (Cosalen) was encapsulated into microporous NaY zeolite via the technique of "ship-in-bottle".The encapsulated complex (Cosalen-NaY) was characterized by Fourier-transform infrared spectrum,ultraviolet-visible spectrum, Bmnauer-Emmett-Teller surface areas, X-ray diffraction,thermogravimetry-differential thermal analysis and scanning electron microscope.The reaction of cyclohexane oxidation using oxygen was chosen to investigate the catalytic performance of Cosalen-NaY, and the effects of oxygen pressure. temperature and reaction time were also studied.The results show that Cosalen complex is encapsulated into the supercage of the zeolite and the structure of NaY zeolite remains integrity and the thermal stabilitv of Cosalen is greatly enhanced after encapsulation.Cosalen-NaY shows the better activity in the oxidation of eyclohexane without reductant and solvent.The conversion of cyclohexane is up to 13.4%at 150 ℃ for 3 h under oxygen pressure of 0.85 MPa, with the higher total selectivity to cyclohexanol, cyclohexanone, cyclohexyl hydroperoxide(CHHP)and acid (79.2%)than the neat complex(55.5%). NaY zeolite carrier maybe contributes to the results. There is no obviPUS induction period to initiate the reaction;furthermore. the amount of CHHP among the products is small, which indicates that the Cosalen-NaY has the strong abilitv to accelerate the decomposition of CHHP. Recycling tests show that the hybrid material can be used repeatedly with a negligible loss of active sites.

  17. Dramatically different kinetics and mechanism at solid/liquid and solid/gas interfaces for catalytic isopropanol oxidation over size-controlled platinum nanoparticles.

    Science.gov (United States)

    Wang, Hailiang; Sapi, Andras; Thompson, Christopher M; Liu, Fudong; Zherebetskyy, Danylo; Krier, James M; Carl, Lindsay M; Cai, Xiaojun; Wang, Lin-Wang; Somorjai, Gabor A

    2014-07-23

    We synthesize platinum nanoparticles with controlled average sizes of 2, 4, 6, and 8 nm and use them as model catalysts to study isopropanol oxidation to acetone in both the liquid and gas phases at 60 °C. The reaction at the solid/liquid interface is 2 orders of magnitude slower than that at the solid/gas interface, while catalytic activity increases with the size of platinum nanoparticles for both the liquid-phase and gas-phase reactions. The activation energy of the gas-phase reaction decreases with the platinum nanoparticle size and is in general much higher than that of the liquid-phase reaction which is largely insensitive to the size of catalyst nanoparticles. Water substantially promotes isopropanol oxidation in the liquid phase. However, it inhibits the reaction in the gas phase. The kinetic results suggest different mechanisms between the liquid-phase and gas-phase reactions, correlating well with different orientations of IPA species at the solid/liquid interface vs the solid/gas interface as probed by sum frequency generation vibrational spectroscopy under reaction conditions and simulated by computational calculations.

  18. Activity and Stability of Rare Earth-Based Hydride Alloys as Catalysts of Hydrogen Absorption-Oxidation Reactions

    Institute of Scientific and Technical Information of China (English)

    Ying Taokai(应桃开); Gao Xueping(高学平); Hu Weikang(胡伟康); Noréus Dag

    2004-01-01

    Rare earth-based AB5-type hydrogen storage alloys as catalysts of hydrogen-diffusion electrodes for hydrogen absorption and oxidation reactions in alkaline fuel cells were investigated. It is demonstrated that the meta-hydride hydrogen-diffusion electrodes could be charged by hydrogen gas and electrochemically discharged at the same time to retain a stable oxidation potential for a long period. The catalytic activities and stability are almost comparable with a Pt catalyst on the active carbon. Further improvement of performances is expected via reduction of catalyst size into nanometers.

  19. Free-radical production and oxidative reactions of hemoglobin.

    OpenAIRE

    Winterbourn, C C

    1985-01-01

    Mechanisms of autoxidation of hemoglobin, and its reactions with H2O2, O2-, and oxidizing or reducing xenobiotics are discussed. Reactive intermediates of such reactions can include drug free radicals, H2O2, and O2-, as well as peroxidatively active ferrylhemoglobin and methemoglobin-H2O2. The contributions of these species to hemoglobin denaturation and drug-induced hemolysis, and the actions of various protective agents, are considered.

  20. Carbon and nitrogen removal from glucose-glycine melanoidins solution as a model of distillery wastewater by catalytic wet air oxidation.

    Science.gov (United States)

    Phuong Thu, Le; Michèle, Besson

    2016-06-01

    Sugarcane molasses distillery wastewater contains melanoidins, which are dark brown recalcitrant nitrogenous polymer compounds. Studies were carried out in batch mode to evaluate Pt and Ru supported catalysts in the Catalytic Wet Air Oxidation (CWAO) process of a synthetic melanoidins solution, prepared by stoichiometric reaction of glucose with glycine. The addition of a catalyst slightly improved TOC removal compared with the non-catalytic reaction, and especially promoted the conversion of ammonium produced from organically-bound nitrogen in melanoidins to molecular nitrogen and nitrate. The selectivity to N2 attained 89% in the presence of the Pt catalysts in the reaction conditions used (TOC=2200mgL(-1), TN=280mgL(-1), 0.5g catalyst loaded with 3% metal, 210°C, 70bar total air pressure). To avoid leaching of the active metal by organically-bound nitrogen, the reaction was very efficiently performed in a two-step reaction consisting in WAO to convert nitrogen into ammonium, before the introduction of a catalyst. PMID:26900982