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Sample records for catalytic ozonation-biological coupled

  1. Direct catalytic cross-coupling of organolithium compounds

    NARCIS (Netherlands)

    Giannerini, Massimo; Fananas Mastral, Martin; Feringa, Ben L.

    2013-01-01

    Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern sy

  2. Direct catalytic cross-coupling of alkenyllithium compounds

    NARCIS (Netherlands)

    Hornillos, Valentin; Giannerini, Massimo; Vila, Carlos; Fananas-Mastral, Martin; Feringa, Ben L.

    2015-01-01

    A catalytic method for the direct cross-coupling of alkenyllithium reagents with aryl and alkenyl halides is described. The use of a catalyst comprising Pd-2(dba)(3)/XPhos allows for the stereoselective preparation of a wide variety of substituted alkenes in high yields under mild conditions. In add

  3. 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.

  4. 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-.

  5. 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.

  6. Studies of coupled chemical and catalytic coal conversion methods

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.; Chatterjee, K.; Cheng, C.; Ettinger, M.; Flores, F.; Jiralerspong, S.; Miyake, M.; Muntean, J.

    1991-12-01

    The objective of this research was to convert coal into a soluble substance under mild conditions. The strategy involved two steps, first to breakdown the macromolecular network of coal, and second to add hydrogen catalytically. We investigated different basic reagents that could, in priciple, break down coal's structure and alkylation strategies that might enhance its solubility. We examined O- and C-alkylation, the importance of the strength of the base, the character of the added alkyl groups and other reaction parameters. This work provided new information concerning the way in which hydrogen bonding, polarization interactions between aromatic structures and covalent bonding could be disrupted and solubility enhanced. The objective of our research was to explore new organochromium chemistry that might be feasible for the hydrogenation of coal under mild conditions.

  7. Studies of coupled chemical and catalytic coal conversion methods

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.; Chatterjee, K.; Cheng, C.; Ettinger, M.; Flores, F.; Jiralerspong, S.; Miyake, M.; Muntean, J.

    1991-12-01

    The objective of this research was to convert coal into a soluble substance under mild conditions. The strategy involved two steps, first to breakdown the macromolecular network of coal, and second to add hydrogen catalytically. We investigated different basic reagents that could, in priciple, break down coal`s structure and alkylation strategies that might enhance its solubility. We examined O- and C-alkylation, the importance of the strength of the base, the character of the added alkyl groups and other reaction parameters. This work provided new information concerning the way in which hydrogen bonding, polarization interactions between aromatic structures and covalent bonding could be disrupted and solubility enhanced. The objective of our research was to explore new organochromium chemistry that might be feasible for the hydrogenation of coal under mild conditions.

  8. Preparation of Pd-Diimine@SBA-15 and Its Catalytic Performance for the Suzuki Coupling Reaction

    Directory of Open Access Journals (Sweden)

    Jiahuan Yu

    2016-11-01

    Full Text Available A highly efficient and stable Pd-diimine@SBA-15 catalyst was successfully prepared by immobilizing Pd onto diimine-functionalized mesoporous silica SBA-15. With the help of diimine functional groups grafted onto the SBA-15, Pd could be anchored on a support with high dispersion. Pd-diimine@SBA-15 catalyst exhibited excellent catalytic performance for the Suzuki coupling reaction of electronically diverse aryl halides and phenylboronic acid under mild conditions with an ultralow amount of Pd (0.05 mol % Pd. When the catalyst amount was increased, it could catalyze the coupling reaction of chlorinated aromatics with phenylboronic acid. Compared with the catalytic performances of Pd/SBA-15 and Pd-diimine@SiO2 catalysts, the Pd-diimine@SBA-15 catalyst exhibited higher hydrothermal stability and could be repeatedly used four times without a significant decrease of its catalytic activity.

  9. 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.

  10. Catalytic Olefin Hydroamidation Enabled by Proton-Coupled Electron Transfer.

    Science.gov (United States)

    Miller, David C; Choi, Gilbert J; Orbe, Hudson S; Knowles, Robert R

    2015-10-28

    Here we report a ternary catalyst system for the intramolecular hydroamidation of unactivated olefins using simple N-aryl amide derivatives. Amide activation in these reactions occurs via concerted proton-coupled electron transfer (PCET) mediated by an excited state iridium complex and weak phosphate base to furnish a reactive amidyl radical that readily adds to pendant alkenes. A series of H-atom, electron, and proton transfer events with a thiophenol cocatalyst furnish the product and regenerate the active forms of the photocatalyst and base. Mechanistic studies indicate that the amide substrate can be selectively homolyzed via PCET in the presence of the thiophenol, despite a large difference in bond dissociation free energies between these functional groups.

  11. 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.

  12. Enzyme as catalytic wheel powered by a Markovian engine: conformational coupling and barrier surfing models

    Science.gov (United States)

    Tsong, Tian Yow; Chang, Cheng-Hung

    2005-05-01

    We examine a typical Michaelis-Menten Enzyme (MME) and redress it to form a transducer of free energy, and electric, acoustic, or other types of energy. This amendment and extension is necessary in lieu of recent experiments in which enzymes are shown to perform pump, motor, and locomotion functions resembling their macroscopic counterparts. Classical textbook depicts enzyme, or an MME, as biocatalyst which can enhance the rate of a chemical reaction by lowering the activation barrier but cannot shift the thermodynamic equilibrium of the biochemical reaction. An energy transducer, on the other hand, must also be able to harvest, store, or divert energy and in doing so alter the chemical equilibrium, change the energy form, fuel an energy consuming process, or perform all these functions stepwise in one catalytic turnover. The catalytic wheel presented in this communication is both a catalyst and an energy transducer and can perform all these tasks with ease. A Conformational Coupling Model for the rotary motors and a Barrier Surfing Model for the track-guided stepping motors and transporters, are presented and compared. It is shown that the core engine of the catalytic wheel, or a Brownian motor, is a Markovian engine. It remains to be seen if this core engine is the basic mechanism for a wide variety of bio-molecular energy transducers, as well as certain other dynamic systems, for example, the Parrondo's Games.

  13. 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.

  14. Coupling thermogravimetric and acoustic emission measurements: its application to study the inhibition of catalytic coke deposition

    Energy Technology Data Exchange (ETDEWEB)

    Ropital, Francois; Dascotte, Philippe; Marchand, Pierre [Institut Francais du Petrole, 1 Avenue Bois Preau, 92952 Rueil-Malmaison (France); Faure, Thierry; Lenain, Jean-Claude; Proust, Alain [Euro Physical Acoustics, 27 Rue Magellan, 94373 Sucy-en-Brie Cedex (France)

    2004-07-01

    In order to improve the knowledge on the high temperature behaviour of metallic materials, the coupling of several in situ physical analysis methods is a promising way. For this purpose a thermogravimetric balance has been equipped with a specific acoustic emission device in order to continuously measure the mass variation of the corrosion sample and the acoustic emission transient under experimental conditions of temperature and gas phase compositions that are representative of the industrial environments. The catalytic coke deposition condition that is a major problem for the refinery and petrochemical industries, has been studied with such a device. The carbon deposition on reactor walls can induce localised disruption in the process such as heat-transfer reduction and pressure drops. To prevent these perturbations, proper selections of the metallurgical or internal coating compositions of the equipment, or the injection of accurate amount of inhibitors have to be decided. The feasibility of the coupling at high temperature of thermogravimetric and acoustic emission has been demonstrated. This new technique has been applied to study the inhibition of the catalytic coke deposition on pure iron by sulphur additives in the temperature range of 650 deg. C and under different mixed atmospheres of hydrocarbon and hydrogen contents. Good correlation has been obtained between the coking rates measured by thermogravimetric measurements and the intensities of the acoustic emission parameters. (authors)

  15. Parkin mitochondrial translocation is achieved through a novel catalytic activity coupled mechanism

    Institute of Scientific and Technical Information of China (English)

    Xinde Zheng; Tony Hunter

    2013-01-01

    Pink1,a mitochondrial kinase,and Parkin,an E3 ubiquitin ligase,function in mitochondrial maintenance.Pink1 accumulates on depolarized mitochondria,where it recruits Parkin to mainly induce K63-1inked chain ubiquitination of outer membrane proteins and eventually mitophagy.Parkin belongs to the RBR E3 iigase family.Recently,it has been proposed that the RBR domain transfers ubiquitin to targets via a cysteine-ubiquitin enzyme intermediate,in a manner similar to HECT domain E3 ligases.However,direct evidence for a ubiquitin transfer mechanism and its importance for Parkin's in vivo function is still missing.Here,we report that Parkin E3 activity relies on cysteinemediated ubiquitin transfer during mitophagy.Mutating the putative catalytic cysteine to serine (Parkin C431S)traps ubiquitin,and surprisingly,also abrogates Parkin mitochondrial translocation,indicating that E3 activity is essential for Parkin translocation.We found that Parkin can bind to K63-1inked ubiquitin chains,and that targeting K63-mimicking ubiquitin chains to mitochondria restores Parkin C431S localization.We propose that Parkin translocation is achieved through a novel catalytic activity coupled mechanism.

  16. Parkin mitochondrial translocation is achieved through a novel catalytic activity coupled mechanism

    Science.gov (United States)

    Zheng, Xinde; Hunter, Tony

    2013-01-01

    Pink1, a mitochondrial kinase, and Parkin, an E3 ubiquitin ligase, function in mitochondrial maintenance. Pink1 accumulates on depolarized mitochondria, where it recruits Parkin to mainly induce K63-linked chain ubiquitination of outer membrane proteins and eventually mitophagy. Parkin belongs to the RBR E3 ligase family. Recently, it has been proposed that the RBR domain transfers ubiquitin to targets via a cysteine∼ubiquitin enzyme intermediate, in a manner similar to HECT domain E3 ligases. However, direct evidence for a ubiquitin transfer mechanism and its importance for Parkin's in vivo function is still missing. Here, we report that Parkin E3 activity relies on cysteine-mediated ubiquitin transfer during mitophagy. Mutating the putative catalytic cysteine to serine (Parkin C431S) traps ubiquitin, and surprisingly, also abrogates Parkin mitochondrial translocation, indicating that E3 activity is essential for Parkin translocation. We found that Parkin can bind to K63-linked ubiquitin chains, and that targeting K63-mimicking ubiquitin chains to mitochondria restores Parkin C431S localization. We propose that Parkin translocation is achieved through a novel catalytic activity coupled mechanism. PMID:23670163

  17. 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.

  18. In situ generated hypoiodous acid in an efficient and heterogeneous catalytic system for the homo-oxidative coupling of thiols

    Directory of Open Access Journals (Sweden)

    Ghorbani-Choghamarani Arash

    2013-01-01

    Full Text Available Supported hydrogen peroxide on polyvinylpolypyrrolidone (PVPH2O2, silica sulfuric acid (SiO2-OSO3H and catalytic amounts of potassium iodide (KI has been developed as a heterogeneous medium for the rapid oxidative coupling of thiols into symmetrical homodisulfides. This oxidizing system proceeds under extremely mild conditions and gives no other oxidized side products.

  19. Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer

    Science.gov (United States)

    Choi, Gilbert J.; Zhu, Qilei; Miller, David C.; Gu, Carol J.; Knowles, Robert R.

    2016-11-01

    Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process—a subset of the classical Hofmann-Löffler-Freytag reaction—amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using

  20. High catalytic efficiency of palladium nanoparticles immobilized in a polymer membrane containing poly(ionic liquid) in Suzuki–Miyaura cross-coupling reaction

    OpenAIRE

    Gu, Yingying; Favier, Isabelle; Pradel, Christian; Gin, Douglas L.; Lahitte, Jean-Francois; Noble, Richard D.; Gómez, Montserrat; Remigy, Jean-Christophe

    2015-01-01

    International audience; The elaboration of a polymeric catalytic membrane containing palladium nanoparticles is presented. The membrane was prepared using a photo-grafting process with imidazolium-based ionic liquid monomers as modifying agent and microPES® as support membrane. Ionic liquid serves as a stabilizer and immobilizer for the catalytic species, i.e. palladium nanoparticles. The Suzuki–Miyaura cross-coupling reaction was carried out on the catalytic membrane in flow-through configur...

  1. Application of integrated ozone biological aerated filters and membrane filtration in water reuse of textile effluents.

    Science.gov (United States)

    He, Yaozhong; Wang, Xiaojun; Xu, Jinling; Yan, Jinli; Ge, Qilong; Gu, Xiaoyang; Jian, Lei

    2013-04-01

    A combined process including integrated ozone-BAFs (ozone biological aerated filters) and membrane filtration was first applied for recycling textile effluents in a cotton textile mill with capacity of 5000 m(3)/d. Influent COD (chemical oxygen demand) in the range of 82-120 mg/L, BOD5 (5-day biochemical oxygen demand) of 12.6-23.1 mg/L, suspended solids (SSs) of 38-52 mg/L and color of 32-64° were observed during operation. Outflows with COD≤45 mg/L, BOD5≤7.6 mg/L, SS≤15 mg/L, color≤8° were obtained after being decontaminated by ozone-BAF with ozone dosage of 20-25 mg/L. Besides, the average removal rates of PVA (polyvinyl alcohol) and UV254 were 100% and 73.4% respectively. Permeate water produced by RO (reverse osmosis) could be reused in dyeing and finishing processes, while the RO concentrates could be discharged directly under local regulations with COD≤100 mg/L, BOD5≤21 mg/L, SS≤52 mg/L, color≤32°. Results showed that the combined process could guarantee water reuse with high quality, and solve the problem of RO concentrate disposal.

  2. Ozone-biological activated carbon as a pretreatment process for reverse osmosis brine treatment and recovery.

    Science.gov (United States)

    Lee, Lai Yoke; Ng, How Yong; Ong, Say Leong; Hu, Jiang Yong; Tao, Guihe; Kekre, Kiran; Viswanath, Balakrishnan; Lay, Winson; Seah, Harry

    2009-09-01

    Ozonation was used in this study to improve biodegradability of RO brine from water reclamation facilities. An ozone dosage ranging from 3 to 10 mg O(3)/L and contact times of 10 and 20 min in batch studies were found to increase the biodegradability (BOD(5)/TOC ratio) of the RO brine by 1.8-3.5 times. At the same time, total organic carbon (TOC) removal was in the range of 5.3-24.5%. The lab-scale ozone-biological activated carbon (BAC) at an ozone dosage of 6.0mg O(3)/L with 20-min contact time was able to achieve 3 times higher TOC removal compared to using BAC alone. Further processing with Capacitive Deionization (CDI) process was able to generate a product water with better water quality than the RO feed water, i.e., with more than 80% ions removal and a lower TOC concentration. The ozone-BAC pretreatment has the potential of reducing fouling in the CDI process.

  3. 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

  4. 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.

  5. Biogenic synthesis of palladium nanoparticles using Pulicaria glutinosa extract and their catalytic activity towards the Suzuki coupling reaction.

    Science.gov (United States)

    Khan, Mujeeb; Khan, Merajuddin; Kuniyil, Mufsir; Adil, Syed Farooq; Al-Warthan, Abdulrahman; Alkhathlan, Hamad Z; Tremel, Wolfgang; Tahir, Muhammad Nawaz; Siddiqui, Mohammed Rafiq H

    2014-06-28

    Green synthesis of nanomaterials finds the edge over chemical methods due to its environmental compatibility. Herein, we report a facile and eco-friendly method for the synthesis of palladium (Pd) nanoparticles (NPs) using an aqueous solution of Pulicaria glutinosa, a plant widely found in a large region of Saudi Arabia, as a bioreductant. The as-prepared Pd NPs were characterized using ultraviolet-visible (UV-vis) spectroscopy, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier transform-infrared spectroscopy (FT-IR). The hydroxyl groups of the plant extract (PE) molecules were found mainly responsible for the reduction and growth of Pd NPs. FT-IR analysis confirmed the dual role of the PE, both as a bioreductant as well as a capping ligand, which stabilizes the surface of Pd NPs. The crystalline nature of the Pd NPs was identified using XRD analysis which confirmed the formation of a face-centered cubic structure (JCPDS: 87-0641, space group: Fm3m (225)). Furthermore, the as-synthesized Pd NPs demonstrated excellent catalytic activity towards the Suzuki coupling reaction under aqueous and aerobic conditions. Kinetic studies of the catalytic reaction monitored using GC confirmed that the reaction completes in less than 5 minutes.

  6. Promotion and Suppression of Centriole Duplication Are Catalytically Coupled through PLK4 to Ensure Centriole Homeostasis

    Directory of Open Access Journals (Sweden)

    Minhee Kim

    2016-08-01

    Full Text Available PLK4 is the major kinase driving centriole duplication. Duplication occurs only once per cell cycle, forming one new (or daughter centriole that is tightly engaged to the preexisting (or mother centriole. Centriole engagement is known to block the reduplication of mother centrioles, but the molecular identity responsible for the block remains unclear. Here, we show that the centriolar cartwheel, the geometric scaffold for centriole assembly, forms the identity of daughter centrioles essential for the block, ceasing further duplication of the mother centriole to which it is engaged. To ensure a steady block, we found that the cartwheel requires constant maintenance by PLK4 through phosphorylation of the same substrate that drives centriole assembly, revealing a parsimonious control in which “assembly” and “block for new assembly” are linked through the same catalytic reaction to achieve homeostasis. Our results support a recently deduced model that the cartwheel-bound PLK4 directly suppresses centriole reduplication.

  7. Tetrahedral DNA nanostructure-based microRNA biosensor coupled with catalytic recycling of the analyte.

    Science.gov (United States)

    Miao, Peng; Wang, Bidou; Chen, Xifeng; Li, Xiaoxi; Tang, Yuguo

    2015-03-25

    MicroRNAs are not only important regulators of a wide range of cellular processes but are also identified as promising disease biomarkers. Due to the low contents in serum, microRNAs are always difficult to detect accurately . In this study, an electrochemical biosensor for ultrasensitive detection of microRNA based on tetrahedral DNA nanostructure is developed. Four DNA single strands are engineered to form a tetrahedral nanostructure with a pendant stem-loop and modified on a gold electrode surface, which largely enhances the molecular recognition efficiency. Moreover, taking advantage of strand displacement polymerization, catalytic recycling of microRNA, and silver nanoparticle-based solid-state Ag/AgCl reaction, the proposed biosensor exhibits high sensitivity with the limit of detection down to 0.4 fM. This biosensor shows great clinical value and may have practical utility in early diagnosis and prognosis of certain diseases.

  8. Redox-coupled structural changes of the catalytic a' domain of protein disulfide isomerase.

    Science.gov (United States)

    Inagaki, Koya; Satoh, Tadashi; Yagi-Utsumi, Maho; Le Gulluche, Anne-Charlotte; Anzai, Takahiro; Uekusa, Yoshinori; Kamiya, Yukiko; Kato, Koichi

    2015-09-14

    Protein disulfide isomerase functions as a folding catalyst in the endoplasmic reticulum. Its b' and a' domains provide substrate-binding sites and undergo a redox-dependent domain rearrangement coupled to an open-closed structural change. Here we determined the first solution structure of the a' domain in its oxidized form and thereby demonstrate that oxidation of the a' domain induces significant conformational changes not only in the vicinity of the active site but also in the distal b'-interfacial segment. Based on these findings, we propose that this conformational transition triggers the domain segregation coupled with the exposure of the hydrophobic surface.

  9. Environmentally benign synthesis of amides and ureas via catalytic dehydrogenation coupling of volatile alcohols and amines in a Pd-Ag membrane reactor

    KAUST Repository

    Chen, Tao

    2016-05-31

    In this study, we report the direct synthesis of amides and ureas via the catalytic dehydrogenation of volatile alcohols and amines using the Milstein catalyst in a Pd-Ag/ceramic membrane reactor. A series of amides and ureas, which could not be synthesized in an open system by catalytic dehydrogenation coupling, were obtained in moderate to high yields via catalytic dehydrogenation of volatile alcohols and amines. This process could be monitored by the hydrogen produced. Compared to the traditional method of condensation, this catalytic system avoids the stoichiometric pre-activation or in situ activation of reagents, and is a much cleaner process with high atom economy. This methodology, only possible by employing the Pd-Ag/ceramic membrane reactor, not only provides a new environmentally benign synthetic approach of amides and ureas, but is also a potential method for hydrogen storage.

  10. Catalytic Asymmetric Coupling of 2-Naphthols by Chiral Tridentate Oxovanadium(IV) Complexes

    Institute of Scientific and Technical Information of China (English)

    HON; Sang-Wen

    2001-01-01

    A series of chiral oxovanadium(IV) complexes derived from tridentate N-3,5-substituted-, N-3,4-benzo-and N-5,6-benzo-salicylidene-α-amino acids can serve as efficient catalysts for the enantioselective oxidative couplings of various 3-, 6-, and 7-substituted 2-naphthols under O2. The best scenario involves the use of a vanadyl complex arising from 2-hydroxy-l-naphthaldehyde and valine (or phenylalanine) in CCl4, leading to BINOLs in good yields (75-100%) and with enantioselectivities of up to 68%.……

  11. Catalytic Asymmetric Coupling of 2-Naphthols by Chiral Tridentate Oxovanadium(IV) Complexes

    Institute of Scientific and Technical Information of China (English)

    HON Sang-Wen; LI Chun-Hsin; KUO Jen-Huang; BARHATE N. B.; LIU Yi-Hung; WANG Yu; CHEN Chien-Tien

    2001-01-01

    @@ A series of chiral oxovanadium(IV) complexes derived from tridentate N-3,5-substituted-, N-3,4-benzo-and N-5,6-benzo-salicylidene-α-amino acids can serve as efficient catalysts for the enantioselective oxidative couplings of various 3-, 6-, and 7-substituted 2-naphthols under O2. The best scenario involves the use of a vanadyl complex arising from 2-hydroxy-l-naphthaldehyde and valine (or phenylalanine) in CCl4, leading to BINOLs in good yields (75-100%) and with enantioselectivities of up to 68%.

  12. Characterization and catalytic behavior of Na-W-Mn-Zr-S-P/SiO2 prepared by different methods in oxidative coupling of methane

    Institute of Scientific and Technical Information of China (English)

    Wen Zheng; Dangguo Cheng; Fengqiu Chen; Xiaoli Zhan

    2010-01-01

    Na-W-Mn-Zr-S-P/SiO2 catalysts for oxidative coupling of methane(OCM)were prepared by incipient wetness impregnation,sol-gel and mixture slurry methods.The catalyst prepared by mixture slurry method showed the best catalytic performance among all samples.In addition,the effects of different addition sequences of Na,W,Mn,Zr,S and P on the catalytic performance were studied.The absence of Na before the addition of Mn and Zr in the catalysts preparation depressed the formation of the active phases of Mn203 and ZrO2 and decreased the activities of the catalysts significantly.

  13. Copper(I) complexes with trispyrazolylmethane ligands: synthesis, characterization, and catalytic activity in cross-coupling reactions.

    Science.gov (United States)

    Haldón, Estela; Álvarez, Eleuterio; Nicasio, M Carmen; Pérez, Pedro J

    2012-08-01

    Three novel Cu(I) complexes bearing tris(pyrazolyl)methane ligands, Tpm(x), have been prepared from reactions of equimolar amounts of CuI and the ligands Tpm, (HC(pz)(3)), Tpm*, (HC(3,5-Me(2)-pz)(3)), and Tpm(Ms), (HC(3-Ms-pz)(3)). X-ray diffraction studies have shown that the Tpm and Tpm(Ms) derivatives exhibit a 2:1 Cu:ligand ratio, whereas the Tpm* complex is a mononuclear species in nature. The latter has been employed as a precatalyst in the arylation of amides and aromatic thiols with good activity. The synthesis of a Tpm*Cu(I)-phthalimidate, a feasible intermediate in this catalytic process, has also been performed. Low temperature (1)H NMR studies in CDCl(3) have indicated that this complex exists in solution as a mixture of two, neutral and ionic forms. Conductivity measurements have reinforced this proposal, the ionic form predominating in a very polar solvent such as DMSO. The reaction of Tpm*Cu(I)-phthalimidate with iodobenzene afforded the expected C-N coupling product in 76% yield accounting for its role as an intermediate in this transformation.

  14. 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.

  15. Catalytic Performance of CeO2/ZnO Nanocatalysts on the Oxidative Coupling of Methane with Carbon Dioxide and their Fractal Features

    Institute of Scientific and Technical Information of China (English)

    Yongjun He; Blun Yang; Haimin Pan; Guozhi Li

    2004-01-01

    CeO2/ZnO nanocatalysts were prepared from the coupling route of homogeneous precipitation with microemulsion and the impregnation method. The catalytic performance of these two kinds of catalysts on the oxidative coupling of methane with carbon dioxide was tested and compared; the fractal behavior of the nanocatalysts was analyzed using fractal theory. The CeO2/ZnO nanocatalysts had much higher activity than the catalysts prepared by impregnation method. There was no regular relationship between the average size of CeO2/ZnO nanocatalysts and their catalytic performance; however, the conversion of methane increased with the increase of the fractal dimension of CeO2/ZnO nanocatalysts.

  16. 2D/2D nano-hybrids of γ-MnO₂ on reduced graphene oxide for catalytic ozonation and coupling peroxymonosulfate activation.

    Science.gov (United States)

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

    2016-01-15

    Two-dimensional reduced graphene oxide (2D rGO) was employed as both a shape-directing medium and support to fabricate 2D γ-MnO2/2D rGO nano-hybrids (MnO2/rGO) via a facile hydrothermal route. For the first time, the 2D/2D hybrid materials were used for catalytic ozonation of 4-nitrophenol. The catalytic efficiency of MnO2/rGO was much higher than either MnO2 or rGO only, and rGO was suggested to play the role for promoting electron transfers. Quenching tests using tert-butanol, p-benzoquinone, and sodium azide suggested that the major radicals responsible for 4-nitrophenol degradation and mineralization are O2(-) and (1)O2, but not ·OH. Reusability tests demonstrated a high stability of the materials in catalytic ozonation with minor Mn leaching below 0.5 ppm. Degradation mechanism, reaction kinetics, reusability and a synergistic effect between catalytic ozonation and coupling peroxymonosulfate (PMS) activation were also discussed.

  17. Immobilized Pd nanoparticles on Tris-modified SiO2:Synthesis, characterization, and catalytic activity in Heck cross-coupling reactions

    Institute of Scientific and Technical Information of China (English)

    Abdol R.Hajipour; Ghobad Azizi

    2014-01-01

    The preparation of supported Pd nanoparticles on Tris (tris(hydroxymethyl)aminomethane)-modi-fied SiO2 gel and their catalytic application in Heck coupling are investigated. The catalyst was char-acterized using a combination of X-ray diffraction, transmission electron microscopy, field-emission scanning electron microscopy, and scanning electron microscopy/energy-dispersive X-ray spec-troscopy. The supported Pd nanoparticles were found to be a highly active and reusable catalyst for the Heck reaction at a low Pd loading (0.02 mol%) because of stabilization by the Tris moieties. Several reaction parameters, including the type and amount of solvent, base, and temperature, were evaluated. The heterogeneity of the catalytic system was investigated using different approaches, and showed that slight Pd leaching into the reaction solution occurred under the reaction condi-tions. Despite this metal leaching, the catalyst can be reused seven times without significant loss of its activity.

  18. Nickel(II) complexes containing ONS donor ligands: Synthesis, characterization, crystal structure and catalytic application towards C-C cross-coupling reactions

    Indian Academy of Sciences (India)

    Panneerselvam Anitha; Rajendran Manikandan; Paranthaman Vijayan; Govindan Prakash; Periasamy Viswanathamurthi; Ray Jay Butcher

    2015-04-01

    Nickel(II) complexes containing thiosemicarbazone ligands [Ni(L)2] (1-3) (L = 9,10-phenanthrenequinonethiosemicarbazone (HL1), 9,10-phenanthrenequinone-N-methylthio semicarbazone (HL2) and 9, 10-phenanthrenequinone-N-phenylthiosemicarbazone (HL3)) have been synthesized and characterized by elemental analysis and spectroscopic (IR, UV-Vis, 1H, 13C-NMR and ESI mass) methods. The molecular structures of complexes 1 and 2 were identified by means of single-crystal X-ray diffraction analysis. The analysis revealed that the complexes possess a distorted octahedral geometry with the ligand coordinating in a uni-negative tridentate ONS fashion. The catalytic activity of complexes towards some C–C coupling reactions (viz., Kumada-Corriu, Suzuki-Miyaura and Sonogashira) has been examined. The complexes behave as efficient catalysts in the Kumada-Corriu and Sonogashira coupling reactions rather than Suzuki-Miyaura coupling.

  19. Construction of new biopolymer (chitosan)-based pincer-type Pd(II) complex and its catalytic application in Suzuki cross coupling reactions

    Science.gov (United States)

    Baran, Talat; Menteş, Ayfer

    2017-04-01

    In this paper we described the fabrication, characterization and application of a new biopolymer (chitosan)-based pincer-type Pd(II) catalyst in Suzuki cross coupling reactions using a non-toxic, cheap, eco-friendly and practical method. The catalytic activity tests showed remarkable product yields as well as TON (19800) and TOF (330000) values with a small catalyst loading. In addition, the catalyst indicated good recyclability in the Suzuki C-C reaction. This biopolymer supported catalyst can be used with various catalyst systems due to its unique properties, such as being inert, green in nature, low cost and chemically durable.

  20. Development of catalytic systems for selective hydrogenation and hydrogenolysis based on statistical planning methods coupled with kinetic studies

    Energy Technology Data Exchange (ETDEWEB)

    Zhorov, Yu.M.; Morozova, E.V.; Panchenkov, G.M.

    1979-01-01

    An efficient catalyst design methodology is described, which was used in developing an active and stable mixed oxide catalytic composition for selective hydrogenation of m-bonds under conditions excluding hydrogenolysis of C-C bonds. Catalysts of optimum composition, i.e., 40-50Vertical Bar3< CuO/25-30Vertical Bar3< NiO/20-35Vertical Bar3< SiO/sub 2/, and structure (20-30 A. average pore radius) can be prepared by coprecipitation of copper and nickel salts with silica gel powder in a sodium silicate solution at 90/sup 0/C. By using these catalysts, crotonaldehyde (CA) was hydrogenated to n-butanol in one stage with over 99Vertical Bar3< yields at 180/sup 0/C. The same catalyst was efficient in selective hydrogenation of acetylene (contained in relatively high concentrations in pyrolysis gases) to ethylene at 130/sup 0/C, hydrogenation of piperylene (a by-product in isoprene manufacture) to n-pentenes at 160/sup 0/C, with almost 100Vertical Bar3< selectivity, and in hydrogenolysis of C-S and C-N bonds at 290/sup 0/-370/sup 0/C. Catalytic hydrorefining of a gasoline fraction (105/sup 0/-180/sup 0/C bp) at 350/sup 0/C and 40 atm, reduced its sulfur content from 0.03Vertical Bar3< to 0.00001Vertical Bar3<, and completely removed nitrogen.

  1. Influence of alkali metal doping on surface properties and catalytic activity/selectivity of CaO catalysts in oxidative coupling of methane

    Institute of Scientific and Technical Information of China (English)

    V.H.Rane; S.T.Chaudhari; V.R.Choudhary

    2008-01-01

    Surface properties (viz. surface area, basicity/base strength distribution, and crystal phases) of alkali metal doped CaO (alkali metal/Ca = 0.1 and 0.4) catalysts and their catalytic activity/selectivity in oxidative coupling of methane (OCM) to higher hydrocarbons at different reaction conditions (viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm3·g-1·h-1) have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties (viz. surface area, basicity/base strength distribution) and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity (strong basic sites) and the C2+ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO (Na/Ca = 0.1, before calcination) catalyst (calcined at 750 ℃), showed best performance (C2+selectivity of 68.8% with 24.7% methane conversion), whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.

  2. Dinuclear NHC-palladium complexes containing phosphine spacers: synthesis, X-ray structures and their catalytic activities towards the Hiyama coupling reaction.

    Science.gov (United States)

    Yang, Jin; Li, Pinhua; Zhang, Yicheng; Wang, Lei

    2014-05-21

    Six dinuclear N-heterocyclic carbene (NHC) palladium complexes, [PdCl2(IMes)]2(μ-dppe) (1), [PdCl2(IPr)]2(μ-dppe) (2), [PdCl2(IMes)]2(μ-dppb) (3), [PdCl2(IPr)]2(μ-dppb) (4), [PdCl2(IMes)]2(μ-dpph) (5), and [PdCl2(IPr)]2(μ-dpph) (6) [IMes = N,N'-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene; IPr = N,N'-bis-(2,6-di(iso-propyl)phenyl)imidazol-2-ylidene; dppe = 1,2-bis(diphenylphosphino)ethane, dppb = 1,4-bis(diphenylphosphino)butane; and dpph = 1,6-bis(diphenylphosphino)hexane], have been synthesized through bridge-cleavage reactions of chloro-bridged dimeric compounds, [Pd(μ-Cl)(Cl)(NHC)]2, with the corresponding diphosphine ligands. The obtained compounds were fully characterized by (1)H NMR, (13)C NMR and (31)P NMR spectroscopy, FT-IR, elemental analysis and single-crystal X-ray crystallography. Moreover, further explorations of the catalytic potential of the dinuclear carbene palladium complexes as catalysts for the Pd-catalyzed transformations have been performed under microwave irradiation conditions, and the complexes exhibited moderate to good catalytic activity in the Hiyama coupling reaction of trimethoxyphenylsilane with aryl chlorides.

  3. Determination of trace uranium by resonance fluorescence method coupled with photo-catalytic technology and dual cloud point extraction.

    Science.gov (United States)

    Li, Jiekang; Li, Guirong; Han, Qian

    2016-12-01

    In this paper, two kinds of salophens (Sal) with different solubilities, Sal1 and Sal2, have been respectively synthesized, and they all can combine with uranyl to form stable complexes: [UO2(2+)-Sal1] and [UO2(2+)-Sal2]. Among them, [UO2(2+)-Sal1] was used as ligand to extract uranium in complex samples by dual cloud point extraction (dCPE), and [UO2(2+)-Sal2] was used as catalyst for the determination of uranium by photocatalytic resonance fluorescence (RF) method. The photocatalytic characteristic of [UO2(2+)-Sal2] on the oxidized pyronine Y (PRY) by potassium bromate which leads to the decrease of RF intensity of PRY were studied. The reduced value of RF intensity of reaction system (ΔF) is in proportional to the concentration of uranium (c), and a novel photo-catalytic RF method was developed for the determination of trace uranium (VI) after dCPE. The combination of photo-catalytic RF techniques and dCPE procedure endows the presented methods with enhanced sensitivity and selectivity. Under optimal conditions, the linear calibration curves range for 0.067 to 6.57ngmL(-1), the linear regression equation was ΔF=438.0 c (ngmL(-1))+175.6 with the correlation coefficient r=0.9981. The limit of detection was 0.066ngmL(-1). The proposed method was successfully applied for the separation and determination of uranium in real samples with the recoveries of 95.0-103.5%. The mechanisms of the indicator reaction and dCPE are discussed.

  4. Determination of trace uranium by resonance fluorescence method coupled with photo-catalytic technology and dual cloud point extraction

    Science.gov (United States)

    Li, Jiekang; Li, Guirong; Han, Qian

    2016-12-01

    In this paper, two kinds of salophens (Sal) with different solubilities, Sal1 and Sal2, have been respectively synthesized, and they all can combine with uranyl to form stable complexes: [UO22 +-Sal1] and [UO22 +-Sal2]. Among them, [UO22 +-Sal1] was used as ligand to extract uranium in complex samples by dual cloud point extraction (dCPE), and [UO22 +-Sal2] was used as catalyst for the determination of uranium by photocatalytic resonance fluorescence (RF) method. The photocatalytic characteristic of [UO22 +-Sal2] on the oxidized pyronine Y (PRY) by potassium bromate which leads to the decrease of RF intensity of PRY were studied. The reduced value of RF intensity of reaction system (ΔF) is in proportional to the concentration of uranium (c), and a novel photo-catalytic RF method was developed for the determination of trace uranium (VI) after dCPE. The combination of photo-catalytic RF techniques and dCPE procedure endows the presented methods with enhanced sensitivity and selectivity. Under optimal conditions, the linear calibration curves range for 0.067 to 6.57 ng mL- 1, the linear regression equation was ΔF = 438.0 c (ng mL- 1) + 175.6 with the correlation coefficient r = 0.9981. The limit of detection was 0.066 ng mL- 1. The proposed method was successfully applied for the separation and determination of uranium in real samples with the recoveries of 95.0-103.5%. The mechanisms of the indicator reaction and dCPE are discussed.

  5. Synthesis, characterization, and catalytic activity in Suzuki coupling and catalase-like reactions of new chitosan supported Pd catalyst.

    Science.gov (United States)

    Baran, Talat; Inanan, Tülden; Menteş, Ayfer

    2016-07-10

    The aim of this study is to analyze the synthesis of a new chitosan supported Pd catalyst and examination of its catalytic activity in: Pd catalyst was synthesized using chitosan as a biomaterial and characterized with FTIR, TG/DTG, XRD, (1)H NMR, (13)C NMR, SEM-EDAX, ICP-OES, Uv-vis spectroscopies, and magnetic moment, along with molar conductivity analysis. Biomaterial supported Pd catalyst indicated high activity and long life time as well as excellent turnover number (TON) and turnover frequency (TOF) values in Suzuki reaction. Biomaterial supported Pd catalyst catalyzed H2O2 decomposition reaction with considerable high activity using comparatively small loading catalyst (10mg). Redox potential of biomaterial supported Pd catalyst was still high without negligible loss (13% decrease) after 10 cycles in reusability tests. As a consequence, eco-friendly biomaterial supported Pd catalyst has superior properties such as high thermal stability, long life time, easy removal from reaction mixture and durability to air, moisture and high temperature.

  6. Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction

    Directory of Open Access Journals (Sweden)

    Ruth Gomes

    2014-11-01

    Full Text Available A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state 13C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N2 sorption, HR-TEM, and NH3 temperature programmed desorption-thermal conductivity detector (TPD-TCD analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, β-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

  7. Cooperative activation of cyclobutanones and olefins leads to bridged ring systems by a catalytic [4 + 2] coupling

    Science.gov (United States)

    Ko, Haye Min; Dong, Guangbin

    2014-08-01

    Bridged ring systems are widely found in natural products, and successful syntheses of them frequently feature intramolecular Diels-Alder reactions. These reactions are subclassified as either type I or type II depending on how the diene motif is tethered to the rest of the substrate (type I are tethered at the 1-position of the diene and type II at the 2-position). Although the type I reaction has been used with great success, the molecular scaffolds accessible by the type II reactions are limited by the strain inherent in the formation of an sp2 carbon at a bridgehead position. Here, we describe a complementary approach that provides access to these structures through the C-C activation of cyclobutanones and their coupling with olefins. Various alkenes have been coupled with cyclobutanones to provide a range of bridged skeletons. The ketone group of the products serves as a convenient handle for downstream functionalization.

  8. Catalytic Proton Coupled Electron Transfer from Metal Hydrides to Titanocene Amides, Hydrazides and Imides: Determination of Thermodynamic Parameters Relevant to Nitrogen Fixation.

    Science.gov (United States)

    Pappas, Iraklis; Chirik, Paul J

    2016-10-03

    The hydrogenolysis of titanium-nitrogen bonds in a series of bis(cyclopentadienyl) titanium amides, hydrazides and imides by proton coupled electron transfer (PCET) is described. Twelve different N-H bond dissociation free energies (BDFEs) among the various nitrogen-containing ligands were measured or calculated, and effects of metal oxidation state and N-ligand substituent were determined. Two metal hydride complexes, (η(5)-C5Me5)(py-Ph)Rh-H (py-Ph = 2-pyridylphenyl, [Rh]-H) and (η(5)-C5R5)(CO)3Cr-H ([Cr](R)-H, R= H, Me) were evaluated for formal H atom transfer reactivity and were selected due to their relatively weak M-H bond strengths yet ability to activate and cleave molecular hydrogen. Despite comparable M-H BDFEs, disparate reactivity between the two compounds was observed and was traced to the vastly different acidities of the M-H bonds and overall redox potentials of the molecules. With [Rh]-H, catalytic syntheses of ammonia, silylamine and N,N-dimethylhydrazine have been accomplished from the corresponding titanium(IV) complex using H2 as the stoichiometric H atom source. The data presented in this study provides the thermochemical foundation for the synthesis of NH3 by proton coupled electron transfer at a well-defined transition metal center.

  9. 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.

  10. Palladium-phosphorus/sulfur nanoparticles (NPs) decorated on graphene oxide: synthesis using the same precursor for NPs and catalytic applications in Suzuki-Miyaura coupling

    Science.gov (United States)

    Joshi, Hemant; Sharma, Kamal Nayan; Sharma, Alpesh K.; Singh, Ajai Kumar

    2014-04-01

    PdP2 and Pd4S nanoparticles (NPs) (size: ~2-6 and 9-15 nm respectively) have been prepared for the first time from a single source precursor complex [Pd(L)Cl2] (1) by its one pot thermolysis at 200 °C in TOP and OA/ODE (1 : 1) respectively. These NPs were stirred with graphene oxide (GO) at room temperature to prepare NP composites, GO-PdP2 and GO-Pd4S. The GO-PdP2 NPs have been synthesized for the first time. The thioether ligand L prepared by reaction of 1,3-dibromo-2-propanol with the in situ generated PhSNa reacts with [PdCl2(CH3CN)2] in CH3CN at 70 °C resulting in 1. The L and 1 have been characterized by 1H and 13C{1H} NMR and HR-MS. The single crystal structure of 1 determined by X-ray diffraction reveals nearly square planar geometry around the Pd metal centre. The catalytic activities of two palladium nano-phases having phosphorus and sulphur respectively as a co-constituent for Suzuki-Miyaura coupling have been found to be exceptionally different, as PdP2 nanoparticles (NPs) grafted on graphene oxide (GO-PdP2) are significantly more efficient than Pd4S NPs grafted on GO. Without grafting PdP2 and Pd4S both have low efficiency. This is the first report comparing the influence of P and S on the catalytic activity of Pd NPs. TEM, SEM-EDX and powder-XRD have been used to authenticate all NPs. The GO-PdP2 NPs have been found to be efficient catalysts for Suzuki-Miyaura coupling reactions (yield up to 96% in 30 min) at room temperature to 80 °C. Their recyclability has been found up to 6 cycles. In contrast, GO-Pd4S NPs are little active in comparison with GO-PdP2 NPs. The size of NPs and their distribution on GO appear to be key factors affecting the catalytic efficiency of the composite NPs. Leaching of Pd from GO-PdP2 NPs contributes significantly to the catalysis as evidenced by the three phase test, hot-filtration and recycling experiments. The catalysis is almost homogeneous.PdP2 and Pd4S nanoparticles (NPs) (size: ~2-6 and 9-15 nm respectively) have

  11. Catalytically Enhanced Hydrogen Sorption in Mg-MgH2 by Coupling Vanadium-Based Catalyst and Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Atikah Kadri

    2015-06-01

    Full Text Available Mg (MgH2-based composites, using carbon nanotubes (CNTs and pre-synthesized vanadium-based complex (VCat as the catalysts, were prepared by high-energy ball milling technique. The synergistic effect of coupling CNTs and VCat in MgH2 was observed for an ultra-fast absorption rate of 6.50 wt. % of hydrogen per minute and 6.50 wt. % of hydrogen release in 10 min at 200 °C and 300 °C, respectively. The temperature programmed desorption (TPD results reveal that coupling VCat and CNTs reduces both peak and onset temperatures by more than 60 °C and 114 °C, respectively. In addition, the presence of both VCat and CNTs reduces the enthalpy and entropy of desorption of about 7 kJ/mol H2 and 11 J/mol H2·K, respectively, as compared to those of the commercial MgH2, which ascribe to the decrease of desorption temperature. From the study of the effect of CNTs milling time, it is shown that partially destroyed CNTs (shorter milling time are better to enhance the hydrogen sorption performance.

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

    OpenAIRE

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

    2016-01-01

    We examined oxidative coupling of methane (OCM) over various Ce–W–O catalysts at 423 K in an electric field. Ce2(WO4)3/CeO2 catalyst showed high OCM activity. In a periodic operation test over Ce2(WO4)3/CeO2 catalyst, C2 selectivity exceeded 60% during three redox cycles. However, Ce2(WO4)3/CeO2 catalyst without the electric field showed low activity, even at 1073 K: CH4 Conv., 6.0%; C2 Sel., 2.1%. A synergetic effect between the Ce2(WO4)3 structure and electric field created the reactive oxy...

  13. Catalytic conversion of sugarcane bagasse to cellulosic ethanol: TiO2 coupled nanocellulose as an effective hydrolysis enhancer.

    Science.gov (United States)

    Jabasingh, S Anuradha; Lalith, D; Prabhu, M Arun; Yimam, Abubekker; Zewdu, Taye

    2016-01-20

    The present study deals with the production of cellulosic ethanol from bagasse using the synthesized TiO2 coupled nanocellulose (NC-TiO2) as catalyst. Aspergillus nidulans AJSU04 cellulase was used for the hydrolysis of bagasse. NC-TiO2 at various concentrations was added to bagasse in order to enhance the yield of reducing sugars. Complex interaction between cellulase, bagasse, NC-TiO2 and the reaction environment is thoroughly studied. A mathematical model was developed to describe the hydrolysis reaction. Ethanol production from enzymatically hydrolyzed sugarcane bagasse catalyzed with NC-TiO2 was carried out using Saccharomyces cerevisiae ATCC 20602. The glucose release rates and ethanol concentrations were determined. Ethanol produced was found to be strongly dependent on pretreatment given, hydrolysis and fermentation conditions. The study confirmed the promising accessibility of NC-TiO2, for enhanced glucose production rates and improved ethanol yield.

  14. Green synthesis of Pd/CuO nanoparticles by Theobroma cacao L. seeds extract and their catalytic performance for the reduction of 4-nitrophenol and phosphine-free Heck coupling reaction under aerobic conditions.

    Science.gov (United States)

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Bagherzadeh, Mojtaba

    2015-06-15

    We report the green synthesis of palladium/CuO nanoparticles (Pd/CuO NPs) using Theobroma cacao L. seeds extract and their catalytic activity for the reduction of 4-nitrophenol and Heck coupling reaction under aerobic conditions. The catalyst was characterized using the powder XRD, TEM, EDS, UV-vis and FT-IR. This method has the advantages of high yields, elimination of surfactant, ligand and homogeneous catalysts, simple methodology and easy work up. The catalyst can be recovered from the reaction mixture and reused several times without any significant loss of catalytic activity.

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

    Science.gov (United States)

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

    2016-04-01

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

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

    Science.gov (United States)

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

    2016-04-27

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

  17. Close-coupled Catalytic Two-Stage Liquefaction (CTSL{trademark}) process bench studies. Final report, [October 1, 1988--July 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Comolli, A.G.; Johanson, E.S.; Karolkiewicz, W.F.; Lee, L.K.; Popper, G.A.; Stalzer, R.H.; Smith, T.O.

    1993-06-01

    This is the final report of a four year and ten month contract starting on October 1, 1988 to July 31, 1993 with the US Department of Energy to study and improve Close-Coupled Catalytic Two-Stage Direct Liquefaction of coal by producing high yields of distillate with improved quality at lower capital and production costs in comparison to existing technologies. Laboratory, Bench and PDU scale studies on sub-bituminous and bituminous coals are summarized and referenced in this volume. Details are presented in the three topical reports of this contract; CTSL Process Bench Studies and PDU Scale-Up with Sub-Bituminous Coal-DE-88818-TOP-1, CTSL Process Bench Studies with Bituminous Coal-DE-88818-TOP-2, and CTSL Process Laboratory Scale Studies, Modelling and Technical Assessment-DE-88818-TOP-3. Results are summarized on experiments and studies covering several process configurations, cleaned coals, solid separation methods, additives and catalysts both dispersed and supported. Laboratory microautoclave scale experiments, economic analysis and modelling studies are also included along with the PDU-Scale-Up of the CTSL processing of sub-bituminous Black Thunder Mine Wyoming coal. During this DOE/HRI effort, high distillate yields were maintained at higher throughput rates while quality was markedly improved using on-line hydrotreating and cleaned coals. Solid separations options of filtration and delayed coking were evaluated on a Bench-Scale with filtration successfully scaled to a PDU demonstration. Directions for future direct coal liquefaction related work are outlined herein based on the results from this and previous programs.

  18. Nickel-doped zinc aluminate oxides: starch-assisted synthesis, structural, optical properties, and their catalytic activity in oxidative coupling of methane

    Science.gov (United States)

    Visinescu, Diana; Papa, Florica; Ianculescu, Adelina C.; Balint, Ioan; Carp, Oana

    2013-03-01

    Nanosized nickel-substituted zinc aluminate oxides were obtained by the gradual insertion of nickel cations within the zinc aluminate lattice, using starch as active ingredient. The obtained (Ni x Zn1- x Al2)-starch ( x = 0.1, 0.2, 0.4, 0.6, 0.8, 1) gel precursors were characterized through infrared spectroscopy and thermal analysis. The thermal behavior of the precursors are influenced by the nickel content, the DTA curves for the richer nickel samples revealing stronger, faster and overlapping exothermic reactions, that can be completed at lower temperatures. The corresponding spinelic oxides were obtained after calcination treatments at 800 °C and analyzed by means of NIR-UV-Vis spectroscopy, XRD measurements, SEM, TEM, and HRTEM investigations. The spinelic structure for all oxide samples is confirmed by XRD analysis, although small amounts of NiO cannot be neglected. TEM/HRTEM analysis revealed mesopores embedded in plate-like large (68.8 nm) particles of Ni0.2Zn0.8Al2O4 sample and smaller (15.7 nm) uniform equiaxial particles, with a more pronounced tendency of agglomeration for Ni0.8Zn0.2Al2O4 oxide. A formation mechanism for Ni0.2Zn0.8Al2O4 oxides was proposed based on DTA/TG, XRD, and SEM analyses. NIR-UV-Vis spectra for Ni x Zn1- x Al2O4 showed a significant presence of tetrahedral nickel cations that augments with nickel concentration increase. CIE- L * a * b * color parameters shown a variation of the lightness and also of the green and blue color components with x, the best color characteristics being obtained for x = 0.6. The oxides with a substitution degree x = 0.2 and 0.8 tested in the oxidative coupled of methane reaction (OCM) showed positive catalytic activity and selectivity due to an interesting synergetic effect of Zn(II) and Ni(II) ions.

  19. Oxidative photoredox-catalytic activation of aliphatic nucleophiles for C(sp(3))-C(sp(2)) cross-coupling reactions.

    Science.gov (United States)

    Jahn, Emanuela; Jahn, Ullrich

    2014-12-01

    In the light you will find the road (Led Zeppelin): Visible-light photoredox catalysis leads the way in overcoming the reactivity limitations of alkyl nucleophiles in cross-coupling reactions. Iridium-triggered oxidative photoredox activation of alkyltrifluoroborate or carboxylic acids affords alkyl radicals, which undergo nickel-catalyzed cross-coupling reactions.

  20. A surface enhanced Raman scattering quantitative analytical platform for detection of trace Cu coupled the catalytic reaction and gold nanoparticle aggregation with label-free Victoria blue B molecular probe.

    Science.gov (United States)

    Li, Chongning; Ouyang, Huixiang; Tang, Xueping; Wen, Guiqing; Liang, Aihui; Jiang, Zhiliang

    2017-01-15

    With development of economy and society, there is an urgent need to develop convenient and sensitive methods for detection of Cu(2+) pollution in water. In this article, a simple and sensitive SERS sensor was proposed to quantitative analysis of trace Cu(2+) in water. The SERS sensor platform was prepared a common gold nanoparticle (AuNP)-SiO2 sol substrate platform by adsorbing HSA, coupling with the catalytic reaction of Cu(2+)-ascorbic acid (H2A)-dissolved oxygen, and using label-free Victoria blue B (VBB) as SERS molecular probes. The SERS sensor platform response to the AuNP aggregations by hydroxyl radicals (•OH) oxidizing from the Cu(2+) catalytic reaction, which caused the SERS signal enhancement. Therefore, by monitoring the increase of SERS signal, Cu(2+) in water can be determined accurately. The results show that the SERS sensor platforms owns a linear response with a range from 0.025 to 25μmol/L Cu(2+), and with a detection limit of 0.008μmol/L. In addition, the SERS method demonstrated good specificity for Cu(2+), which can determined accurately trace Cu(2+) in water samples, and good recovery and accuracy are obtained for the water samples. With its high selectivity and good accuracy, the sensitive SERS quantitative analysis method is expected to be a promising candidate for determining copper ions in environmental monitoring and food safety.

  1. EFFECTS OF SOLVENT, BASE, AND TEMPERATURE IN THE OPTIMISATION OF A NEW CATALYTIC SYSTEM FOR SONOGASHIRA CROSS-COUPLING USING NCP PINCER PALLADACYCLE

    Directory of Open Access Journals (Sweden)

    Diego S. Rosa

    2015-05-01

    Full Text Available The optimisation of a new catalyst system using NCP pincer palladacycle 1 was investigated using the experimental design technique. NCP pincer palladacycle 1 was previously investigated in Suzuki-Miyaura and Heck-Mizoroki cross-couplings and found to be a highly efficient catalyst precursor. In this study, the effects of the type of base (K3PO4 or DABCO, solvent (DMF or dioxane and reaction temperature (130 or 150 ºC in the second step on the reactional yield in Sonogashira cross-coupling were assessed using the two-factor design. The results showed that temperature is statistically significant in relation to the reaction yield.

  2. Role of Ag2S coupling on enhancing the visible-light-induced catalytic property of TiO2 nanorod arrays

    Science.gov (United States)

    Li, Zhengcao; Xiong, Shan; Wang, Guojing; Xie, Zheng; Zhang, Zhengjun

    2016-01-01

    In order to obtain a better photocatalytic performance under visible light, Ag2S-coupled TiO2 nanorod arrays (NRAs) were prepared through the electron beam deposition with glancing angle deposition (GLAD) technique, annealing in air, followed by the successive ionic layer absorption and reaction (SILAR) method. The properties of the photoelectrochemical and photocatalytic degradation of methyl orange (MO) were thus conducted. The presence of Ag2S on TiO2 NRAs was observed to have a significant improvement on the response to visible light. It’s resulted from that Ag2S coupling can improve the short circuit photocurrent density and enhance the photocatalytic activity remarkably.

  3. Experimental Study on Ozone-biological Activated Carbon for Advanced Treatment of Petrochemical Wastewater%臭氧-生物活性炭深度处理石化废水的试验研究

    Institute of Scientific and Technical Information of China (English)

    王亚轩; 赵慧

    2012-01-01

    In this experiment, the technology combination including Bio-SAC bioreactor, effecient fibre filter, ozone-biological activated carbon filter was used to deep treat wastewater after secondary biological treatment of petrochemical plant in Daqing city. The results indicated that the wastewater after treatment could meet the demands of water quality standard of circulating cooling water, Bio-SAC reactor had still high degradation capacity for residual refractory organism of water after secondary biological treatment, ozone-biological activated carbon was superior to normal biology carbon in the aspect of removal of organism, chroma, turbidity and saturated cycle.%试验通过Bio-SAC生物反应器、高效纤维过滤器、臭氧滑性炭过滤器等工艺组合将大庆某石化公司二级生物处理后的废水进行深度处理。试验结果表明经该系统处理后的污水完全满足循环冷却水的水质要求,Bio-SAC生物反应器对二级生物处理后水中残留难降解有机物仍有较强的降解能力,臭氧化生物活性炭在去除有机物、色度、浊度、饱和周期方面均优于普通生物活性炭。

  4. Selective extraction and release using (EDTA-Ni)-layered double hydroxide coupled with catalytic oxidation of 3,3',5,5'-tetramethylbenzidine for sensitive detection of copper ion.

    Science.gov (United States)

    Tang, Sheng; Chang, Yuepeng; Chia, Guo Hui; Lee, Hian Kee

    2015-07-23

    Copper is an important heavy metal in various biological processes. Many methods have been developed for detecting of copper ions (Cu(2+)) in aqueous samples. However, an easy, cheap, selective and sensitive method is still desired. In this study, a selective extraction-release-catalysis approach has been developed for sensitive detection of copper ion. Ethylenediaminetetraacetic acid (EDTA) chelated with nickel ion (Ni(2+)) were intercalated in a layered double hydroxide via a co-precipitation reaction. The product was subsequently applied as sorbent in dispersive solid-phase extraction for the enrichment of Cu(2+) at pH 6. Since Cu(2+) has a stronger complex formation constant with EDTA, Ni(2+) exchanged with Cu(2+) selectively. The resulting sorbent containing Cu(2+) was transferred to catalyze the 3,3',5,5'-tetramethylbenzidine oxidation reaction, since Cu(2+) could be released by the sorbent effectively and has high catalytic ability for the reaction. Blue light emitted from the oxidation product was measured by ultraviolet-visible spectrophotometry for the determination of Cu(2+). The extraction temperature, extraction time, and catalysis time were optimized. The results showed that this method provided a low limit of detection of 10nM, a wide linear range (0.05-100μM) and good linearity (r(2)=0.9977). The optimized conditions were applied to environmental water samples. Using Cu(2+) as an example, this work provided a new and interesting approach for the convenient and efficient detection of metal cations in aqueous samples.

  5. Reductive removal of nitrate by electrochemistry/catalytic hydrogenation coupling process: kinetics and mechanism%电化学/催化加氢工艺去除硝酸盐的动力学及机理

    Institute of Scientific and Technical Information of China (English)

    张志强; 徐勇鹏; 时文歆; 张瑞君; 鲍现; 崔福义

    2016-01-01

    为解决地下水硝酸盐(NO3--N)污染问题,采用电化学/催化加氢耦合工艺对其进行去除,重点考察该工艺对NO3--N的降解动力学及反应机理.结果表明,电化学/催化加氢耦合工艺在厌氧条件下能够在短时间内将NO3--N完全去除,去除速率(以N计)可达72.6 mg.L-1.h-1 ,反应符合二级反应动力学规律,常数k=0.005 5 cm2.mA-1.min-1 . 水中NO3--N一部分由电化学反硝化降解去除,另一部分由催化加氢还原去除,两种反应通过电解水产H2反应耦联成为一个整体,宏观上符合电化学反硝化机理.%The kinetics and mechanism in the electrochemistry/catalytic hydrogenation ( E/C ) coupling process, which was employed to remove nitrate ( NO3--N ) from groundwater, was investigated in this paper. The results demonstrated that the NO3--N could be rapidly removed by E/C under anoxic conditions, and the degradation efficiency of NO3--N followed the increasing current density(ID) with observed second order reaction rate and the constant( k ) value of 0. 005 5 cm2·mA-1·min-1 . The NO3--N reductive by E/C with two kinds of reactions, electrochemistry denitrification and catalytic reduction, both of which aggregated by the reaction of brine electrolysis.

  6. 光催化内循环耦合MBR处理垃圾渗滤液%Study on the treatments of landfill leachate by the internal photo-catalytic circulation coupled with MBR process

    Institute of Scientific and Technical Information of China (English)

    冯斐; 胡兆吉; 赖劲虎; 吴婷

    2016-01-01

    The novel integrative equipment of internal photo-catalytic circulation coupled with MBR was used to treat landfill leachate in this study.When the inflow CODcr concentration,internal photo-catalytic hydraulic retention time,dosing of H2 O2 ,hydraulic retention time of MBR unit were controlled at 250 mg· L-1 ,3 hour,106 mg·L-1 and 25 hour,respectively.The system could obtain the average CODcr removal ratio of 67.3%.During the tests,the evolution of EPS concentration and transverse membrane pressure were detected under different dosing of H2 O2 .In conclusion,the novel equipment could be easily controlled and operated.%采用自行设计一体化光催化内循环耦合 MBR工艺对垃圾渗滤液进行深度处理。当垃圾渗滤液进水 COD为250 mg·L-1,催化循环段水力停留时间为3 h、双氧水投加量为106 mg·L-1;MBR段水力停留时间为25 h,系统对COD的平均去除率可以达到67.3%。试验过程中检测不同双氧水投加条件下 MBR体系中 EPS的变化及跨膜压差的变化。系统操作灵活,易于控制。

  7. 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.

  8. Catalytic mechanisms of direct pyrrole synthesis via dehydrogenative coupling mediated by PNP-Ir or PNN-Ru pincer complexes: Crucial role of proton-transfer shuttles in the PNP-Ir system

    KAUST Repository

    Qu, Shuanglin

    2014-04-02

    Kempe et al. and Milstein et al. have recently advanced the dehydrogenative coupling methodology to synthesize pyrroles from secondary alcohols (e.g., 3) and β-amino alcohols (e.g., 4), using PNP-Ir (1) and PNN-Ru (2) pincer complexes, respectively. We herein present a DFT study to characterize the catalytic mechanism of these reactions. After precatalyst activation to give active 1A/2A, the transformation proceeds via four stages: 1A/2A-catalyzed alcohol (3) dehydrogenation to give ketone (11), base-facilitated C-N coupling of 11 and 4 to form an imine-alcohol intermediate (18), base-promoted cyclization of 18, and catalyst regeneration via H2 release from 1R/2R. For alcohol dehydrogenations, the bifunctional double hydrogen-transfer pathway is more favorable than that via β-hydride elimination. Generally, proton-transfer (H-transfer) shuttles facilitate various H-transfer processes in both systems. Notwithstanding, H-transfer shuttles play a much more crucial role in the PNP-Ir system than in the PNN-Ru system. Without H-transfer shuttles, the key barriers up to 45.9 kcal/mol in PNP-Ir system are too high to be accessible, while the corresponding barriers (<32.0 kcal/mol) in PNN-Ru system are not unreachable. Another significant difference between the two systems is that the addition of alcohol to 1A giving an alkoxo complex is endergonic by 8.1 kcal/mol, whereas the addition to 2A is exergonic by 8.9 kcal/mol. The thermodynamic difference could be the main reason for PNP-Ir system requiring lower catalyst loading than the PNN-Ru system. We discuss how the differences are resulted in terms of electronic and geometric structures of the catalysts and how to use the features in catalyst development. © 2014 American Chemical Society.

  9. The catalytic effect of sodium and lithium ions on coupled sorption-reduction of chromate at the biotite edge-fluid interface

    Science.gov (United States)

    Ilton, Eugene S.; Veblen, David R.; Moses, Carl O.; Raeburn, Stuart P.

    1997-09-01

    Large single crystals of biotite and near-endmember phlogopite were reacted with aqueous solutions bearing 20 μM Cr(VI) and different concentrations of NaCl, LiCl, RbCl, CsCl, NaClO 4, and Na 2SO 4. Solutions were maintained at 25 ± 0.5°C, 1 atm, and pH = 4.00 ± 0.02. Samples were extracted from the reaction chamber at 1, 3, 5, 10, and 20 h. The edges and basal planes of the reacted micas were analyzed by X-ray photoelectron spectroscopy (XPS) for major elements and Cr. XPS analyses of biotite show trivalent chromium on edge surfaces but no detectable chromium on the basal plane. XPS analyses of near-endmember phlogopites that were reacted in the same experiments as biotite showed no detectable Cr on either the basal plane or edge surfaces. Increasing Na and Li salt concentrations increased the rate of coupled sorption-reduction of chromate at the biotite edge-fluid interface, where the order of effectiveness was NaCl ˜ NaClO 4 > Na 2SO 4 > LiCl. In contrast, no Cr was detected on mica edges after reaction in RbCl and CsCl solutions. Comparison of equimolar NaCl and LiCl experiments indicate that the active agent is Na and Li, not ionic strength or the anion. Sulfate tends to block the reaction more so than chloride. We conclude that it is the substitution of hydrated cations for interlayer K in biotite that enhances the heterogeneous reduction of chromate at the biotite edge-fluid interface.

  10. 歧管式催化转化器流固耦合与热应力分析%Solid-fluid coupling and thermal-stress analysis for catalytic converter of manifold type

    Institute of Scientific and Technical Information of China (English)

    安伟; 万婷婷

    2011-01-01

    It will cost a lot of time,manpower and financial resources through experiments to understand the flow characteristics of catalytic converter.With the development of CAE technology, testing effort and the design cycle can be reduced greatly,besides it can provide structural optimization foundation for early product design and development.Based on one type catalytic converter of manifold type, a finite element analytical model is established,through which heat transfer boundary conditions are obtained by analyzing and calculating with method of solid-fluid coupling, the temperature field of the converter is got as well,under which thermal stress analysis is carried out.Thus the thermal-stress distribute status can be got about this type converterAnd optimization and modification for structure where the stress is concentrated and reach maximum are advised to avoid structural damage caused by the stress concentration effectively%通过实验来了解歧管式催化转化器流动特性、热变形状况,既费时又费了力.通过CAE技术可以大大减少试验工作量,缩短设计周期,为产品前期设计开发提供了结构优化依据.针对某型号歧管式催化转化器建立了有限元分析模型,采用流固耦合方法分析计算得到传热分析的边界条件,再经过传热分析得到转化器的温度场,并在此温度场下对催化转化器进行热应力分析.得到了该型号歧管结构热应力分布状况,对应力集中与应力最大处结构提出了相应的优化与修改意见,有效的避免了因应力集中造成的结构破坏.

  11. 臭氧-生物活性炭技术在水处理中的应用与研究%Study on the application of ozone-biological activated carbon process to water treatment

    Institute of Scientific and Technical Information of China (English)

    郭锋; 王潇; 肖强; 肖禾

    2011-01-01

    Ozone-biological activated carbon (O3-BAC) is a new type of efficient micro-polluted water treatment process. Its application to drinking water (surface water, ground water, domestic water, municipal water supply, etc. ) and industrial wastewater(membrane treatment discharge ,oilfield wastewater,oil refining wastewater, petrochemical wastewater, pharmaceutical wastewater, dyestuff wastewater, food processing wastewater, aquaculture wastewater, etc. ) and their research situations are introduced. The future development directions of the application of O3-BAC to water treatment are pointed out.%臭氧-生物活性炭(O-BAC)技术是一种新型高效的微污染水处理工艺.介绍了O-BAC技术在饮用水(地表水、地下水、生活污水、市政供水等制饮用水)及工业废水(膜处理排水、油田废水、炼油废水、石化废水、制药废水、焦化废水、印染废水、食品加工废水、水产养殖废水)等领域的应用和研究情况,指出了未来O-BAC技术在水处理中的发展研究方向.

  12. Si-H bond activation at {(NHC)₂Ni⁰} leading to hydrido silyl and bis(silyl) complexes: a versatile tool for catalytic Si-H/D exchange, acceptorless dehydrogenative coupling of hydrosilanes, and hydrogenation of disilanes to hydrosilanes.

    Science.gov (United States)

    Schmidt, David; Zell, Thomas; Schaub, Thomas; Radius, Udo

    2014-07-28

    The unique reactivity of the nickel(0) complex [Ni2(iPr2Im)4(COD)] (1) (iPr2Im = 1,3-di-isopropyl-imidazolin-2-ylidene) towards hydrosilanes in stoichiometric and catalytic reactions is reported. A series of nickel hydrido silyl complexes cis-[Ni(iPr2Im)2(H)(SiH(n-1)R(4-n))] (n = 1, 2) and nickel bis(silyl) complexes cis-[Ni(iPr2Im)2(SiH(n-1)R(4-n))2] (n = 1, 2, 3) were synthesized by stoichiometric reactions of 1 with hydrosilanes H(n)SiR(4-n), and fully characterized by X-ray diffraction and spectroscopic methods. These hydrido silyl complexes are examples where the full oxidative addition step is hindered. They have, as a result of the remaining Si-H interactions, remarkably short Si-H distances and feature a unique dynamic behavior in solution. Cis-[Ni(iPr2Im)2(H)(SiMePh2)] (cis-5) shows in solution at room temperature a dynamic site exchange of the NHC ligands, H-D exchange with C6D6 to give the deuteride complex cis-[Ni(iPr2Im)2(D)(SiMePh2)] (cis-5-D), and at elevated temperatures an irreversible isomerization to trans-[Ni(iPr2Im)2(D)(SiMePh2)] (trans-5-D). Reactions with sterically less demanding silanes give cis-configured bis(silyl) complexes accompanied by the release of dihydrogen. These complexes display, similarly to the hydrido silyl complexes, interestingly short Si-Si distances. Complex 1 reacts with 4 eq. HSi(OEt)3, in contrast to all the other silanes used in this study, to give the trans-configured bis(silyl) complex trans-[Ni(iPr2Im)2Ni(Si(OEt)3)2] (trans-12). The addition of two equivalents of Ph2SiH2 to 1 results, at elevated temperatures, in the formation of the dinuclear complex [{(iPr2Im)Ni-μ(2)-(HSiPh2)}2] (6). This diamagnetic, formal Ni(I) complex exhibits a long Ni-Ni bond in the solid state, as established by X-ray diffraction. The capability of the electron rich {Ni(iPr2Im)2} complex fragment to activate Si-H bonds was applied catalytically in the deuteration of Et3Si-H to Et3Si-D employing C6D6 as a convenient deuterium source

  13. Topological entropy of catalytic sets: Hypercycles revisited

    Science.gov (United States)

    Sardanyés, Josep; Duarte, Jorge; Januário, Cristina; Martins, Nuno

    2012-02-01

    The dynamics of catalytic networks have been widely studied over the last decades because of their implications in several fields like prebiotic evolution, virology, neural networks, immunology or ecology. One of the most studied mathematical bodies for catalytic networks was initially formulated in the context of prebiotic evolution, by means of the hypercycle theory. The hypercycle is a set of self-replicating species able to catalyze other replicator species within a cyclic architecture. Hypercyclic organization might arise from a quasispecies as a way to increase the informational containt surpassing the so-called error threshold. The catalytic coupling between replicators makes all the species to behave like a single and coherent evolutionary multimolecular unit. The inherent nonlinearities of catalytic interactions are responsible for the emergence of several types of dynamics, among them, chaos. In this article we begin with a brief review of the hypercycle theory focusing on its evolutionary implications as well as on different dynamics associated to different types of small catalytic networks. Then we study the properties of chaotic hypercycles with error-prone replication with symbolic dynamics theory, characterizing, by means of the theory of topological Markov chains, the topological entropy and the periods of the orbits of unimodal-like iterated maps obtained from the strange attractor. We will focus our study on some key parameters responsible for the structure of the catalytic network: mutation rates, autocatalytic and cross-catalytic interactions.

  14. Catalytic combustor for hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Mercea, J.; Grecu, E.; Fodor, T.; Kreibik, S.

    1982-01-01

    The performance of catalytic combustors for hydrogen using platinum-supported catalysts is described. Catalytic plates of different sizes were constructed using fibrous and ceramic supports. The temperature distribution as well as the reaction efficiency as a function of the fuel input rate was determined, and a comparison between the performances of different plates is discussed.

  15. 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.

  16. Catalytic Functions of Standards

    NARCIS (Netherlands)

    K. Blind (Knut)

    2009-01-01

    textabstractThe three different areas and the examples have illustrated several catalytic functions of standards for innovation. First, the standardisation process reduces the time to market of inventions, research results and innovative technologies. Second, standards themselves promote the diffusi

  17. Catalytic Synthesis Lactobionic Acid

    Directory of Open Access Journals (Sweden)

    V.G. Borodina

    2014-07-01

    Full Text Available Gold nanoparticles are obtained, characterized and deposited on the carrier. Conducted catalytic synthesis of lactobionic acid from lactose. Received lactobionic acid identify on the IR spectrum.

  18. Catalytic distillation process

    Science.gov (United States)

    Smith, Jr., Lawrence A.

    1982-01-01

    A method for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C.sub.4 feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  19. Catalytic distillation process

    Science.gov (United States)

    Smith, L.A. Jr.

    1982-06-22

    A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  20. Catalytic distillation structure

    Science.gov (United States)

    Smith, L.A. Jr.

    1984-04-17

    Catalytic distillation structure is described for use in reaction distillation columns, and provides reaction sites and distillation structure consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and is present with the catalyst component in an amount such that the catalytic distillation structure consists of at least 10 volume % open space. 10 figs.

  1. Pd Close Coupled Catalyst

    Institute of Scientific and Technical Information of China (English)

    Zhong Hua SHI; Mao Chu GONG; Yao Qiang CHEN

    2006-01-01

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

  2. Catalytic hydrotreating process

    Science.gov (United States)

    Karr, Jr., Clarence; McCaskill, Kenneth B.

    1978-01-01

    Carbonaceous liquids boiling above about 300.degree. C such as tars, petroleum residuals, shale oils and coal-derived liquids are catalytically hydrotreated by introducing the carbonaceous liquid into a reaction zone at a temperature in the range of 300.degree. to 450.degree. C and a pressure in the range of 300 to 4000 psig for effecting contact between the carbonaceous liquid and a catalytic transition metal sulfide in the reaction zone as a layer on a hydrogen permeable transition metal substrate and then introducing hydrogen into the reaction zone by diffusing the hydrogen through the substrate to effect the hydrogenation of the carbonaceous liquid in the presence of the catalytic sulfide layer.

  3. Catalytic efficiency of designed catalytic proteins.

    Science.gov (United States)

    Korendovych, Ivan V; DeGrado, William F

    2014-08-01

    The de novo design of catalysts that mimic the affinity and specificity of natural enzymes remains one of the Holy Grails of chemistry. Despite decades of concerted effort we are still unable to design catalysts as efficient as enzymes. Here we critically evaluate approaches to (re)design of novel catalytic function in proteins using two test cases: Kemp elimination and ester hydrolysis. We show that the degree of success thus far has been modest when the rate enhancements seen for the designed proteins are compared with the rate enhancements by small molecule catalysts in solvents with properties similar to the active site. Nevertheless, there are reasons for optimism: the design methods are ever improving and the resulting catalyst can be efficiently improved using directed evolution.

  4. Catalytic Phosphination and Arsination

    Institute of Scientific and Technical Information of China (English)

    Kwong Fuk Yee; Chan Kin Shing

    2004-01-01

    The catalytic, user-friendly phosphination and arsination of aryl halides and triflates by triphenylphosphine and triphenylarsine using palladium catalysts have provided a facile synthesis of functionalized aryl phosphines and arsines in neutral media. Modification of the cynaoarisne yielded optically active N, As ligands which will be screened in various asymmetric catalysis.

  5. Degradation of phenol in wastewater using high gravity coupled with electro-catalytic method%超重力-电催化耦合法降解含酚废水

    Institute of Scientific and Technical Information of China (English)

    刘引娣; 刘有智; 高璟; 李皓月

    2015-01-01

    将自制的超重力多级同心圆筒电解装置应用于电催化降解含酚废水的过程中,解决电化学法处理废水存在“气泡效应”和“传质受限”导致的废水处理效率降低的难题。考察了超重力因子、电流密度、电解时间、电解质浓度、液体循环流量、苯酚初始浓度对废水降解效果的影响,确定了超重力-电催化耦合法处理含酚废水的最佳工艺条件。结果表明:超重力因子为30、电流密度为200A/m2、电解质浓度为3g/L、液体循环流量为80L/h、电解时间为7h 时,处理初始浓度100mg/L 的含酚废水,苯酚去除率可达99.1%,COD 去除率可达24.7%。超重力电催化法强化了离子传质过程,实现了废水中苯酚的高效去除,为含酚废水的处理研究探索了一种新途径。%In order to improve processing efficiency by minimizing the impact of bubbles and mass transfer limitations in wastewater treatment,a novel high gravity electro-catalytic reactor was used in the electro-catalytic degradation of phenol in wastewater. The influences of high gravity factor,current density , electrolysis time , electrolyte concentration , liquid circulation flow rate and initial concentration of phenol on degradation efficiency were investigated and the high gravity electro-catalytic method optimum operating conditions were determined. The results showed that under the optimal conditions of high gravity factor 30,current density 200A/m2,electrolyte concentration 3g/L,liquid circulation flow rate 80L/h and electrolysis time 7h,the phenol wastewater initial mass concentration of 100 mg/L,the removal rate of phenol and COD reached 99.1% and 24.6% respectively. High gravity electro-catalytic method enhanced the mass transfer process of the ions in solution, resulting higher removal efficiency phenol in waste water.

  6. Mitsunobu Reactions Catalytic in Phosphine and a Fully Catalytic System.

    Science.gov (United States)

    Buonomo, Joseph A; Aldrich, Courtney C

    2015-10-26

    The Mitsunobu reaction is renowned for its mild reaction conditions and broad substrate tolerance, but has limited utility in process chemistry and industrial applications due to poor atom economy and the generation of stoichiometric phosphine oxide and hydrazine by-products that complicate purification. A catalytic Mitsunobu reaction using innocuous reagents to recycle these by-products would overcome both of these shortcomings. Herein we report a protocol that is catalytic in phosphine (1-phenylphospholane) employing phenylsilane to recycle the catalyst. Integration of this phosphine catalytic cycle with Taniguchi's azocarboxylate catalytic system provided the first fully catalytic Mitsunobu reaction.

  7. Catalytic membrane-installed microchannel reactors for one-second allylic arylation.

    Science.gov (United States)

    Yamada, Yoichi M A; Watanabe, Toshihiro; Torii, Kaoru; Uozumi, Yasuhiro

    2009-10-07

    A variety of catalytic membranes of palladium-complexes with linear polymer ligands were prepared inside a microchannel reactor via coordinative and ionic molecular convolution to provide catalytic membrane-installed microdevices, which were applied to the instantaneous allylic arylation reaction of allylic esters and aryl boron reagents under microflow conditions to afford the corresponding coupling products within 1 second of residence time.

  8. Novel Catalytic Membrane Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Stuart Nemser, PhD

    2010-10-01

    There are many industrial catalytic organic reversible reactions with amines or alcohols that have water as one of the products. Many of these reactions are homogeneously catalyzed. In all cases removal of water facilitates the reaction and produces more of the desired chemical product. By shifting the reaction to right we produce more chemical product with little or no additional capital investment. Many of these reactions can also relate to bioprocesses. Given the large number of water-organic compound separations achievable and the ability of the Compact Membrane Systems, Inc. (CMS) perfluoro membranes to withstand these harsh operating conditions, this is an ideal demonstration system for the water-of-reaction removal using a membrane reactor. Enhanced reaction synthesis is consistent with the DOE objective to lower the energy intensity of U.S. industry 25% by 2017 in accord with the Energy Policy Act of 2005 and to improve the United States manufacturing competitiveness. The objective of this program is to develop the platform technology for enhancing homogeneous catalytic chemical syntheses.

  9. N, N′-Olefin functionalized Bis-Imidazolium Pd(II) chloride N-Heterocyclic carbene complex builds a supramolecular framework and shows catalytic efficacy for `C–C' coupling reactions

    Indian Academy of Sciences (India)

    Gourisankar Roymahapatra; Tapastaru Samanta; Saikat Kumar Seth; Ambikesh Mahapatra; Shyamal Kumar Chattopadhyay; Joydev Dinda

    2015-06-01

    The ligand 3,3′-(-phenylenedimethylene)bis{1-(2-methylallyl)} imidazolium bromide (1) and its Palladium(II) N-heterocyclic carbene (NHC) complex (3) has been synthesized and characterized by several spectroscopic techniques and the solid-state structure of 3 has been determined by single crystal X-ray diffraction studies. The Pd(II) complex possesses ring head to tail – stacking interactions (3.767 A°) through imidazole rings. Complex 3 catalyzes Suzuki-Miyaura `C–C' coupling reaction. DFT calculations have been used to understand the HOMO/LUMO energy and hence the stability and reactivity of Pd(II) complex in syn and anti-configuration.

  10. Numerical Simulation of Fixed-Bed Catalytic Reforming Reactors: Hydrodynamics / Chemical Kinetics Coupling Simulation numérique des réacteurs de reformage catalytique en lit fixe : couplage hydrodynamique-cinétique chimique

    Directory of Open Access Journals (Sweden)

    Ferschneider G.

    2006-11-01

    Full Text Available Fixed bed reactors with a single fluid phase are widely used in the refining or petrochemical industries for reaction processes catalysed by a solid phase. The design criteria for industrial reactors are relatively well known. However, they rely on a one-dimensional writing and on the separate resolution of the equation of conservation of mass and energy, and of momentum. Thus, with complex geometries, the influence of hydrodynamics on the effectiveness of the catalyst bed cannot be taken into account. The calculation method proposed is based on the multi-dimensional writing and the simultaneous resolution of the local conservation equations. The example discussed concerns fixed-bed catalytic reactors. These reactors are distinguished by their annular geometry and the radial circulation of the feedstock. The flow is assumed to be axisymmetric. The reaction process is reflected by a simplified kinetic mechanism involving ten chemical species. Calculation of the hydrodynamic (mean velocities, pressure, thermal and mass fields (concentration of each species serves to identify the influence of internal components in two industrial reactor geometries. The map of the quantity of coke formed and deposited on the catalyst, calculated by the model, reveals potential areas of poor operation. Les réacteurs à lit fixe avec une seule phase fluide sont largement utilisés dans l'industrie du raffinage et de la pétrochimie, pour mettre en oeuvre un processus réactionnel catalysé par une phase solide. Les règles de conception des réacteurs industriels sont relativement bien connues. Cependant, elles reposent sur l'écriture monodimensionnelle et la résolution séparée, d'une part, des équations de conservation de la masse et de l'énergie et d'autre part, de la quantité de mouvement. Ainsi dans le cas de géométries complexes, l'influence de l'hydrodynamique sur l'efficacité du lit catalytique ne peut être prise en compte. La méthode de calcul

  11. HYDROGEN TRANSFER IN CATALYTIC CRACKING

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Hydrogen transfer is an important secondary reaction of catalytic cracking reactions, which affects product yield distribution and product quality. It is an exothermic reaction with low activation energy around 43.3 kJ/mol. Catalyst properties and operation parameters in catalytic cracking greatly influence the hydrogen transfer reaction. Satisfactory results are expected through careful selection of proper catalysts and operation conditions.

  12. Catalytic quantum error correction

    CERN Document Server

    Brun, T; Hsieh, M H; Brun, Todd; Devetak, Igor; Hsieh, Min-Hsiu

    2006-01-01

    We develop the theory of entanglement-assisted quantum error correcting (EAQEC) codes, a generalization of the stabilizer formalism to the setting in which the sender and receiver have access to pre-shared entanglement. Conventional stabilizer codes are equivalent to dual-containing symplectic codes. In contrast, EAQEC codes do not require the dual-containing condition, which greatly simplifies their construction. We show how any quaternary classical code can be made into a EAQEC code. In particular, efficient modern codes, like LDPC codes, which attain the Shannon capacity, can be made into EAQEC codes attaining the hashing bound. In a quantum computation setting, EAQEC codes give rise to catalytic quantum codes which maintain a region of inherited noiseless qubits. We also give an alternative construction of EAQEC codes by making classical entanglement assisted codes coherent.

  13. Catalytic Combustion of Gasified Waste

    Energy Technology Data Exchange (ETDEWEB)

    Kusar, Henrik

    2003-09-01

    This thesis concerns catalytic combustion for gas turbine application using a low heating-value (LHV) gas, derived from gasified waste. The main research in catalytic combustion focuses on methane as fuel, but an increasing interest is directed towards catalytic combustion of LHV fuels. This thesis shows that it is possible to catalytically combust a LHV gas and to oxidize fuel-bound nitrogen (NH{sub 3}) directly into N{sub 2} without forming NO{sub x} The first part of the thesis gives a background to the system. It defines waste, shortly describes gasification and more thoroughly catalytic combustion. The second part of the present thesis, paper I, concerns the development and testing of potential catalysts for catalytic combustion of LHV gases. The objective of this work was to investigate the possibility to use a stable metal oxide instead of noble metals as ignition catalyst and at the same time reduce the formation of NO{sub x} In paper II pilot-scale tests were carried out to prove the potential of catalytic combustion using real gasified waste and to compare with the results obtained in laboratory scale using a synthetic gas simulating gasified waste. In paper III, selective catalytic oxidation for decreasing the NO{sub x} formation from fuel-bound nitrogen was examined using two different approaches: fuel-lean and fuel-rich conditions. Finally, the last part of the thesis deals with deactivation of catalysts. The various deactivation processes which may affect high-temperature catalytic combustion are reviewed in paper IV. In paper V the poisoning effect of low amounts of sulfur was studied; various metal oxides as well as supported palladium and platinum catalysts were used as catalysts for combustion of a synthetic gas. In conclusion, with the results obtained in this thesis it would be possible to compose a working catalytic system for gas turbine application using a LHV gas.

  14. Unsteady catalytic processes and sorption-catalytic technologies

    Energy Technology Data Exchange (ETDEWEB)

    Zagoruiko, A N [G.K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Novosibirsk (Russian Federation)

    2007-07-31

    Catalytic processes that occur under conditions of the targeted unsteady state of the catalyst are considered. The highest efficiency of catalytic processes was found to be ensured by a controlled combination of thermal non-stationarity and unsteady composition of the catalyst surface. The processes based on this principle are analysed, in particular, catalytic selective reduction of nitrogen oxides, deep oxidation of volatile organic impurities, production of sulfur by the Claus process and by hydrogen sulfide decomposition, oxidation of sulfur dioxide, methane steam reforming and anaerobic combustion, selective oxidation of hydrocarbons, etc.

  15. Catalytic production of biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Theilgaard Madsen, A.

    2011-07-01

    The focus of this thesis is the catalytic production of diesel from biomass, especially emphasising catalytic conversion of waste vegetable oils and fats. In chapter 1 an introduction to biofuels and a review on different catalytic methods for diesel production from biomass is given. Two of these methods have been used industrially for a number of years already, namely the transesterification (and esterification) of oils and fats with methanol to form fatty acid methyl esters (FAME), and the hydrodeoxygenation (HDO) of fats and oils to form straight-chain alkanes. Other possible routes to diesel include upgrading and deoxygenation of pyrolysis oils or aqueous sludge wastes, condensations and reductions of sugars in aqueous phase (aqueous-phase reforming, APR) for monofunctional hydrocarbons, and gasification of any type of biomass followed by Fischer-Tropsch-synthesis for alkane biofuels. These methods have not yet been industrialised, but may be more promising due to the larger abundance of their potential feedstocks, especially waste feedstocks. Chapter 2 deals with formation of FAME from waste fats and oils. A range of acidic catalysts were tested in a model fat mixture of methanol, lauric acid and trioctanoin. Sulphonic acid-functionalised ionic liquids showed extremely fast convertion of lauric acid to methyl laurate, and trioctanoate was converted to methyl octanoate within 24 h. A catalyst based on a sulphonated carbon-matrix made by pyrolysing (or carbonising) carbohydrates, so-called sulphonated pyrolysed sucrose (SPS), was optimised further. No systematic dependency on pyrolysis and sulphonation conditions could be obtained, however, with respect to esterification activity, but high activity was obtained in the model fat mixture. SPS impregnated on opel-cell Al{sub 2}O{sub 3} and microporous SiO{sub 2} (ISPS) was much less active in the esterification than the original SPS powder due to low loading and thereby low number of strongly acidic sites on the

  16. Chemically-Modified Cellulose Paper as a Microstructured Catalytic Reactor

    Directory of Open Access Journals (Sweden)

    Hirotaka Koga

    2015-01-01

    Full Text Available We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

  17. Catalytic Polymer Multilayer Shell Motors for Separation of Organics.

    Science.gov (United States)

    Lin, Zhihua; Wu, Zhiguang; Lin, Xiankun; He, Qiang

    2016-01-26

    A catalytic polymer multilayer shell motor has been developed, which effects fast motion-based separation of charged organics in water. The shell motors are fabricated by sputtering platinum onto the exposed surface of silica templates embedded in Parafilm, followed by layer-by-layer assembly of polyelectrolyte multilayers to the templates. The catalytic shell motors display high bubble propulsion with speeds of up to 260 μm s(-1) (13 body lengths per second). Moreover, the polyelectrolyte multilayers assembled at high pH (pH>9.0) adsorb approximately 89% of dye molecules from water, owing to the electrostatic interaction between the positively charged polymers and the anionic dye molecules, and subsequently release them at neutral pH in a microfluidic device. The efficient propulsion coupled with the effective adsorption behavior of the catalytic shell motors in a microfluidic device results in accelerated separation of organics in water and thus holds considerable promise for water analysis.

  18. Catalytic Membrane Sensors

    Energy Technology Data Exchange (ETDEWEB)

    Boyle, T.J.; Brinker, C.J.; Gardner, T.J.; Hughes, R.C.; Sault, A.G.

    1998-12-01

    The proposed "catalytic membrane sensor" (CMS) was developed to generate a device which would selectively identify a specific reagent in a complex mixture of gases. This was to be accomplished by modifying an existing Hz sensor with a series of thin films. Through selectively sieving the desired component from a complex mixture and identifying it by decomposing it into Hz (and other by-products), a Hz sensor could then be used to detect the presence of the select component. The proposed "sandwich-type" modifications involved the deposition of a catalyst layered between two size selective sol-gel layers on a Pd/Ni resistive Hz sensor. The role of the catalyst was to convert organic materials to Hz and organic by-products. The role of the membraneo was to impart both chemical specificity by molecukir sieving of the analyte and converted product streams, as well as controlling access to the underlying Pd/Ni sensor. Ultimately, an array of these CMS elements encompassing different catalysts and membranes were to be developed which would enable improved selectivity and specificity from a compiex mixture of organic gases via pattern recognition methodologies. We have successfully generated a CMS device by a series of spin-coat deposited methods; however, it was determined that the high temperature required to activate the catalyst, destroys the sensor.

  19. Catalytic gasification of biomass

    Science.gov (United States)

    Robertus, R. J.; Mudge, L. K.; Sealock, L. J., Jr.; Mitchell, D. H.; Weber, S. L.

    1981-12-01

    Methane and methanol synthesis gas can be produced by steam gasification of biomass in the presence of appropriate catalysts. This concept is to use catalysts in a fluidized bed reactor which is heated indirectly. The objective is to determine the technical and economic feasibility of the concept. Technically the concept has been demonstrated on a 50 lb per hr scale. Potential advantages over conventional processes include: no oxygen plant is needed, little tar is produced so gas and water treatment are simplified, and yields and efficiencies are greater than obtained by conventional gasification. Economic studies for a plant processing 2000 T/per day dry wood show that the cost of methanol from wood by catalytic gasification is competitive with the current price of methanol. Similar studies show the cost of methane from wood is competitive with projected future costs of synthetic natural gas. When the plant capacity is decreased to 200 T per day dry wood, neither product is very attractive in today's market.

  20. Catalytic cracking of lignites

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, M.; Nowak, S.; Naegler, T.; Zimmermann, J. [Hochschule Merseburg (Germany); Welscher, J.; Schwieger, W. [Erlangen-Nuernberg Univ. (Germany); Hahn, T. [Halle-Wittenberg Univ., Halle (Germany)

    2013-11-01

    A most important factor for the chemical industry is the availability of cheap raw materials. As the oil price of crude oil is rising alternative feedstocks like coal are coming into focus. This work, the catalytic cracking of lignite is part of the alliance ibi (innovative Braunkohlenintegration) to use lignite as a raw material to produce chemicals. With this new one step process without an input of external hydrogen, mostly propylene, butenes and aromatics and char are formed. The product yield depends on manifold process parameters. The use of acid catalysts (zeolites like MFI) shows the highest amount of the desired products. Hydrogen rich lignites with a molar H/C ratio of > 1 are to be favoured. Due to primary cracking and secondary reactions the ratio between catalyst and lignite, temperature and residence time are the most important parameter to control the product distribution. Experiments at 500 C in a discontinuous rotary kiln reactor show yields up to 32 wt-% of hydrocarbons per lignite (maf - moisture and ash free) and 43 wt-% char, which can be gasified. Particularly, the yields of propylene and butenes as main products can be enhanced four times to about 8 wt-% by the use of catalysts while the tar yield decreases. In order to develop this innovative process catalyst systems fixed on beads were developed for an easy separation and regeneration of the used catalyst from the formed char. (orig.)

  1. Immigration process in catalytic medium

    Institute of Scientific and Technical Information of China (English)

    洪文明; 王梓坤

    2000-01-01

    The longtime behavior of the immigration process associated with a catalytic super-Brown-ian motion is studied. A large number law is proved in dimension d≤3 and a central limit theorem is proved for dimension d = 3.

  2. Immigration process in catalytic medium

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The longtime behavior of the immigration process associated with a catalytic super-Brownian motion is studied. A large number law is proved in dimension d≤3 and a central limit theorem is proved for dimension d=3.

  3. Complex Wall Boundary Conditions for Modeling Combustion in Catalytic Channels

    Science.gov (United States)

    Zhu, Huayang; Jackson, Gregory

    2000-11-01

    Monolith catalytic reactors for exothermic oxidation are being used in automobile exhaust clean-up and ultra-low emissions combustion systems. The reactors present a unique coupling between mass, heat, and momentum transport in a channel flow configuration. The use of porous catalytic coatings along the channel wall presents a complex boundary condition when modeled with the two-dimensional channel flow. This current work presents a 2-D transient model for predicting the performance of catalytic combustion systems for methane oxidation on Pd catalysts. The model solves the 2-D compressible transport equations for momentum, species, and energy, which are solved with a porous washcoat model for the wall boundary conditions. A time-splitting algorithm is used to separate the stiff chemical reactions from the convective/diffusive equations for the channel flow. A detailed surface chemistry mechanism is incorporated for the catalytic wall model and is used to predict transient ignition and steady-state conversion of CH4-air flows in the catalytic reactor.

  4. Studies on catalytic reduction of nitrate in groundwater

    Institute of Scientific and Technical Information of China (English)

    GENG Bing; ZHU Yanfang; JIN Zhaohui; LI Tielong; KANG Haiyan; WANG Shuaima

    2007-01-01

    Catalytic reduction of nitrate in groundwater by sodium formate over the catalyst was investigated.Pd-Cu/γ-Al2O3 catalyst was prepared by impregnation and characterized by brunauer-emmett-teller (BET),inductive coupled plasma (ICP),X-ray diffraction (XRD),transmission electron microscopy (TEM) and energy dispersive X-ray (EDX).It was found that total nitrogen was effectively removed from the nitrate solution (100 mg/L) and the removal efficiency was 87%.The catalytic activity was affected by pH,catalyst amount used,concentration of sodium formate,and initial concentration of nitrate.As sodium formate was used as reductant,precise control in the initial pH was needed.Excessively high or low initial pH (7.0 or 3.0) reduced catalytic activity.At initial pH of 4.5,catalytic activity was enhanced by reducing the amount of catalyst,while concentrations of sodium formate increased with a considerable decrease in N2 selectivity.In which case,catalytic reduction followed the first order kinetics.

  5. Studies on the Catalytic Activities of Cyclopalladated Ferrocenylimine in the Suzuki Reaction of Pyridylboronic Acid Derivative with Arylhalides

    Institute of Scientific and Technical Information of China (English)

    ZHANG Jin-Li; YANG Liang-Ru; ZHAO Liang; GUI Xiu-Ling; GONG Jun-Fang; WU Yang-Jie

    2003-01-01

    @@ Heterobiaryls have important biologicalproperties. [1] The use of catalytic cross-coupling methodologies forpreparing aryl functionalized heterocycles with pharmaceutical, agrochemical, materials, and supermolecular appli-cations is a burgeoning field of study. [2

  6. Coupled transfers; Transferts couples

    Energy Technology Data Exchange (ETDEWEB)

    Nicolas, X.; Lauriat, G.; Jimenez-Rondan, J. [Universite de Marne-la-Vallee, Lab. d' Etudes des Transferts d' Energie et de Matiere (LETEM), 77 (France); Bouali, H.; Mezrhab, A. [Faculte des Sciences, Dept. de Physique, Lab. de Mecanique et Energetique, Oujda (Morocco); Abid, C. [Ecole Polytechnique Universitaire de Marseille, IUSTI UMR 6595, 13 Marseille (France); Stoian, M.; Rebay, M.; Lachi, M.; Padet, J. [Faculte des Sciences, Lab. de Thermomecanique, UTAP, 51 - Reims (France); Mladin, E.C. [Universitaire Polytechnique Bucarest, Faculte de Genie Mecanique, Bucarest (Romania); Mezrhab, A. [Faculte des Sciences, Lab. de Mecanique et Energetique, Dept. de Physique, Oujda (Morocco); Abid, C.; Papini, F. [Ecole Polytechnique, IUSTI, 13 - Marseille (France); Lorrette, C.; Goyheneche, J.M.; Boechat, C.; Pailler, R. [Laboratoire des Composites ThermoStructuraux, UMR 5801, 33 - Pessac (France); Ben Salah, M.; Askri, F.; Jemni, A.; Ben Nasrallah, S. [Ecole Nationale d' Ingenieurs de Monastir, Lab. d' Etudes des Systemes Thermiques et Energetiques (Tunisia); Grine, A.; Desmons, J.Y.; Harmand, S. [Laboratoire de Mecanique et d' Energetique, 59 - Valenciennes (France); Radenac, E.; Gressier, J.; Millan, P. [ONERA, 31 - Toulouse (France); Giovannini, A. [Institut de Mecanique des Fluides de Toulouse, 31 (France)

    2005-07-01

    This session about coupled transfers gathers 30 articles dealing with: numerical study of coupled heat transfers inside an alveolar wall; natural convection/radiant heat transfer coupling inside a plugged and ventilated chimney; finite-volume modeling of the convection-conduction coupling in non-stationary regime; numerical study of the natural convection/radiant heat transfer coupling inside a partitioned cavity; modeling of the thermal conductivity of textile reinforced composites: finite element homogenization on a full periodical pattern; application of the control volume method based on non-structured finite elements to the problems of axisymmetrical radiant heat transfers in any geometries; modeling of convective transfers in transient regime on a flat plate; a conservative method for the non-stationary coupling of aero-thermal engineering codes; measurement of coupled heat transfers (forced convection/radiant transfer) inside an horizontal duct; numerical simulation of the combustion of a water-oil emulsion droplet; numerical simulation study of heat and mass transfers inside a reactor for nano-powders synthesis; reduction of a combustion and heat transfer model of a direct injection diesel engine; modeling of heat transfers inside a knocking operated spark ignition engine; heat loss inside an internal combustion engine, thermodynamical and flamelet model, composition effects of CH{sub 4}H{sub 2} mixtures; experimental study and modeling of the evolution of a flame on a solid fuel; heat transfer for laminar subsonic jet of oxygen plasma impacting an obstacle; hydrogen transport through a A-Si:H layer submitted to an hydrogen plasma: temperature effects; thermal modeling of the CO{sub 2} laser welding of a magnesium alloy; radiant heat transfer inside a 3-D environment: application of the finite volume method in association with the CK model; optimization of the infrared baking of two types of powder paints; optimization of the emission power of an infrared

  7. Catalytic arylation methods from the academic lab to industrial processes

    CERN Document Server

    Burke, Anthony J

    2014-01-01

    A current view of the challenging field of catalytic arylation reactions. Clearly structured, the chapters in this one-stop resource are arranged according to the reaction type, and focus on novel, efficient and sustainable processes, rather than the well-known and established cross-coupling methods.The entire contents are written by two authors with academic and industrial expertise to ensure consistent coverage of the latest developments in the field, as well as industrial applications, such as C-H activation, iron and gold-catalyzed coupling reactions, cycloadditions or novel methodologies

  8. Advanced treatment of port cabin washing wastewater by integrated process ozonization-biological aerated filter-biological aerated filter%一体化O3-BAF—BAF组合工艺深度处理港口洗舱废水

    Institute of Scientific and Technical Information of China (English)

    葛启龙; 汪晓军

    2013-01-01

    采用一体化臭氧曝气生物滤池(O3-BAF)—曝气生物滤池(BAF)组合工艺对二级生化处理后的港口码头洗舱化学品废水进行深度处理,进水COD约为200~240 mg/L,色度为16~32倍时,经该工艺处理后出水COD<30mg/L,去除率>91%,色度降到4倍以下,出水水质达到《生活杂用水水质标准》(CJ/T48-1999)要求.工程运行实践表明,该深度处理系统运行稳定,处理效率高,具有良好的经济效益与环境效益.%The integrated ozonization-biological aerated filter-biological aerated filter combined process has been applied to the advanced treatment of port cabin washing wastewater after secondary biochemical treatment.When the COD of the influent is 200-240 mg/L,and chroma is 16-32 times,COD of effluent is reduced to less than 30 mg/L after treatment,the removing rate is more than 91%,and chroma is reduced to less than 4 times,reaching the specified Miscellaneous Domestic Water Quality Standard(CJ/T 48-1999).The result shows that the advanced treatment system runs stably,and has high treatment efficiency.It has great economic and environmental benefits.

  9. 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.

  10. Catalytic activity of Au nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Britt Hvolbæk; Janssens, Ton V.W.; Clausen, Bjerne;

    2007-01-01

    Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change with par......Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change...... with particle size. We find that the fraction of low-coordinated Au atoms scales approximately with the catalytic activity, suggesting that atoms on the corners and edges of Au nanoparticles are the active sites. This effect is explained using density functional calculations....

  11. Catalytic Decoupling of Quantum Information

    DEFF Research Database (Denmark)

    Majenz, Christian; Berta, Mario; Dupuis, Frédéric

    2017-01-01

    The decoupling technique is a fundamental tool in quantum information theory with applications ranging from quantum thermodynamics to quantum many body physics to the study of black hole radiation. In this work we introduce the notion of catalytic decoupling, that is, decoupling in the presence...... of an uncorrelated ancilla system. This removes a restriction on the standard notion of decoupling, which becomes important for structureless resources, and yields a tight characterization in terms of the max-mutual information. Catalytic decoupling naturally unifies various tasks like the erasure of correlations...... and quantum state merging, and leads to a resource theory of decoupling....

  12. Simple, chemoselective, catalytic olefin isomerization.

    Science.gov (United States)

    Crossley, Steven W M; Barabé, Francis; Shenvi, Ryan A

    2014-12-01

    Catalytic amounts of Co(Sal(tBu,tBu))Cl and organosilane irreversibly isomerize terminal alkenes by one position. The same catalysts effect cycloisomerization of dienes and retrocycloisomerization of strained rings. Strong Lewis bases like amines and imidazoles, and labile functionalities like epoxides, are tolerated.

  13. Catalytic Asymmetric Bromocyclization of Polyenes.

    Science.gov (United States)

    Samanta, Ramesh C; Yamamoto, Hisashi

    2017-02-01

    The first catalytic asymmetric bromonium ion-induced polyene cyclization has been achieved by using a chiral BINOL-derived thiophosphoramide catalyst and 1,3-dibromo-5,5-dimethylhydantoin as an electrophilic bromine source. Bromocyclization products are obtained in high yields, with good enantiomeric ratios and high diastereoselectivity, and are abundantly found as scaffolds in natural products.

  14. Catalytic wet hydrogen peroxide oxidation of a petrochemical wastewater.

    Science.gov (United States)

    Pariente, M I; Melero, J A; Martínez, F; Botas, J A; Gallego, A I

    2010-01-01

    Continuous Catalytic Wet Hydrogen Peroxide Oxidation (CWHPO) for the treatment of a petrochemical industry wastewater has been studied on a pilot plant scale process. The installation, based on a catalytic fixed bed reactor (FBR) coupled with a stirred tank reactor (STR), shows an interesting alternative for the intensification of a continuous CWHPO treatment. Agglomerated SBA-15 silica-supported iron oxide (Fe(2)O(3)/SBA-15) was used as Fenton-like catalyst. Several variables such as the temperature and hydrogen peroxide concentration, as well as the capacity of the pilot plant for the treatment of inlet polluted streams with different dilution degrees were studied. Remarkable results in terms of TOC reduction and increased biodegradability were achieved using 160 degrees C and moderate hydrogen peroxide initial concentration. Additionally, a good stability of the catalyst was evidenced for 8 hours of treatment with low iron leaching (less than 1 mg/L) under the best operating conditions.

  15. Polymer and Membrane Design for Low Temperature Catalytic Reactions

    KAUST Repository

    Villalobos, Luis Francisco

    2016-02-29

    Catalytically active asymmetric membranes have been developed with high loadings of palladium nanoparticles located solely in the membrane\\'s ultrathin skin layer. The manufacturing of these membranes requires polymers with functional groups, which can form insoluble complexes with palladium ions. Three polymers have been synthesized for this purpose and a complexation/nonsolvent induced phase separation followed by a palladium reduction step is carried out to prepare such membranes. Parameters to optimize the skin layer thickness and porosity, the palladium loading in this layer, and the palladium nanoparticles size are determined. The catalytic activity of the membranes is verified with the reduction of a nitro-compound and with a liquid phase Suzuki-Miyaura coupling reaction. Very low reaction times are observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Polymer and Membrane Design for Low Temperature Catalytic Reactions.

    Science.gov (United States)

    Villalobos, Luis Francisco; Xie, Yihui; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor

    2016-04-01

    Catalytically active asymmetric membranes have been developed with high loadings of palladium nanoparticles located solely in the membrane's ultrathin skin layer. The manufacturing of these membranes requires polymers with functional groups, which can form insoluble complexes with palladium ions. Three polymers have been synthesized for this purpose and a complexation/nonsolvent induced phase separation followed by a palladium reduction step is carried out to prepare such membranes. Parameters to optimize the skin layer thickness and porosity, the palladium loading in this layer, and the palladium nanoparticles size are determined. The catalytic activity of the membranes is verified with the reduction of a nitro-compound and with a liquid phase Suzuki-Miyaura coupling reaction. Very low reaction times are observed.

  17. Template electrodeposition of catalytic nanomotors.

    Science.gov (United States)

    Wang, Joseph

    2013-01-01

    The combination of nanomaterials with electrode materials has opened new horizons in electroanalytical chemistry, and in electrochemistry in general. Over the past two decades we have witnessed an enormous activity aimed at designing new electrochemical devices based on nanoparticles, nanotubes or nanowires, and towards the use of electrochemical routes--particularly template-assisted electrodeposition--for preparing nanostructured materials. The power of template-assisted electrochemical synthesis is demonstrated in this article towards the preparation and the realization of self-propelled catalytic nanomotors, ranging from Pt-Au nanowire motors to polymer/Pt microtube engines. Design considerations affecting the propulsion behavior of such catalytic nanomotors are discussed along with recent bioanalytical and environmental applications. Despite recent major advances, artificial nanomotors have a low efficiency compared to their natural counterparts. Hopefully, the present Faraday Discussion will stimulate other electrochemistry teams to contribute to the fascinating area of artificial nanomachines.

  18. Radiation/Catalytic Augmented Combustion.

    Science.gov (United States)

    1980-09-01

    NATIO& NAk H(fJI At tl TANUAHTOb 19 A ~omm.81-0287 LVL RADIATION/CATALYTIC AUGMENTED COMBUST ION MOSHE LAVID CORPORATE RESEARCH-TECHNOLOGY FEASIBILITY...refinements as necessary. i. Perform cannular combustor experiments to Investigate ignition and flame attachment in flowing, liquid -fuel, unpremixed...stabilizer, with a sintered metal disk on the downstream side through which hot gases or products of partial fuel oxidation can be passed. Experimental

  19. Thermodynamics of catalytic nanoparticle morphology

    Science.gov (United States)

    Zwolak, Michael; Sharma, Renu; Lin, Pin Ann

    Metallic nanoparticles are an important class of industrial catalysts. The variability of their properties and the environment in which they act, from their chemical nature & surface modification to their dispersion and support, allows their performance to be optimized for many chemical processes useful in, e.g., energy applications and other areas. Their large surface area to volume ratio, as well as varying sizes and faceting, in particular, makes them an efficient source for catalytically active sites. These characteristics of nanoparticles - i.e., their morphology - can often display intriguing behavior as a catalytic process progresses. We develop a thermodynamic model of nanoparticle morphology, one that captures the competition of surface energy with other interactions, to predict structural changes during catalytic processes. Comparing the model to environmental transmission electron microscope images of nickel nanoparticles during carbon nanotube (and other product) growth demonstrates that nickel deformation in response to the nanotube growth is due to a favorable interaction with carbon. Moreover, this deformation is halted due to insufficient volume of the particles. We will discuss the factors that influence morphology and also how the model can be used to extract interaction strengths from experimental observations.

  20. Catalytic polarographic currents of oxidizers

    Energy Technology Data Exchange (ETDEWEB)

    Zajtsev, P.M.; Zhdanov, S.I.; Nikolaeva, T.D. (Vsesoyuznyj Nauchno-Issledovatel' skij Inst. Khimicheskikh Reaktivov i Osobo Chistykh Veshchestv, Moscow (USSR))

    1982-06-01

    The state of theory and practice of an important direction in polarography, i.e. catalytic currents of oxidizers-substrates that have found a wide application in the development of highly sensitive methods of determination of a large number of substrates, catalysts and polarographically nonactive ligands, is considered. Transition and some non-transition elements serve as catalysts of reactions that cause catalytic polarographic currents of substrates. Catalytic activity of an inorganic catalyst increases with the increase in the number of its d-orbit. Complex formation in most cases leads to the increase of catalyst activity, however, sometimes a reverse phenomenon takes place. For many catalysts the maximum activity is observed at pH values close to pK value of their hydrolysis. The properties of oxidizers-substrates is revealed by H/sub 2/O/sub 2/, ClO/sub 3//sup -/, BrO/sub 3//sup -/, IO/sub 3//sup -/, ClO/sub 4//sup -/, IO/sub 4//sup -/, NO/sub 2//sup -/, NO/sub 3//sup -/, NH/sub 2/OH, V(5), V(4), S/sub 2/O/sub 8//sup 2 -/, H/sub 2/SO/sub 4/, H/sub 2/C/sub 2/O/sub 4/, COHCOOH, alkenes compounds, organic halogen , sulfur- and amine-containing compounds.

  1. Entrepreneurial Couples

    DEFF Research Database (Denmark)

    Dahl, Michael S.; Van Praag, Mirjam; Thompson, Peter

    2015-01-01

    We study motivations for and outcomes of couples starting up a joint firm, using a sample of 1,069 Danish couples that established a joint enterprise between 2001 and 2010, while comparing them to a set of comparable firms and couples. The main motivation for joint entrepreneurship is to create...

  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. Catalytic synthesis of silicon carbide preceramic polymers: Polycarbosilanes

    Energy Technology Data Exchange (ETDEWEB)

    Berry, D.H.

    1991-11-01

    Polycarbosilanes are the most successful and widely studied class of polymer precursors for silicon carbide, but traditional methods for thier synthesis are inefficient and nonselective. This project is focused on developing transition metal catalysts for the synthesis of polycarbosilanes and other perceramic polymers. In recent work we have developed the first homogeneous transition metal catalysts for the dehydrogenative coupling of simple alkyl silanes to oligomeric and polymeric carbosilanes, H-(SiR{sub 2}CR{prime}{sub 2}){sub n}-SiR{sub 3}. Future work will help elucidate the mechanism of the catalytic process, explore the use of hydrogen acceptors as reaction accelerators, and develop new and more active catalysts.

  5. Acid-base bifunctional catalytic surfaces for nucleophilic addition reactions.

    Science.gov (United States)

    Motokura, Ken; Tada, Mizuki; Iwasawa, Yasuhiro

    2008-09-01

    This article illustrates the modification of oxide surfaces with organic amine functional groups to create acid-base bifunctional catalysts, summarizing our previous reports and also presenting new data. Immobilization of organic amines as bases on inorganic solid-acid surfaces afforded highly active acid-base bifunctional catalysts, which enabled various organic transformations including C--C coupling reactions, though these reactions did not proceed with either the homogeneous amine precursors or the acidic supports alone. Spectroscopic characterization, such as by solid-state MAS NMR and FTIR, revealed not only the interactions between acidic and basic sites but also bifunctional catalytic reaction mechanisms.

  6. Catalytic efficiency of enzymes: a theoretical analysis.

    Science.gov (United States)

    Hammes-Schiffer, Sharon

    2013-03-26

    This brief review analyzes the underlying physical principles of enzyme catalysis, with an emphasis on the role of equilibrium enzyme motions and conformational sampling. The concepts are developed in the context of three representative systems, namely, dihydrofolate reductase, ketosteroid isomerase, and soybean lipoxygenase. All of these reactions involve hydrogen transfer, but many of the concepts discussed are more generally applicable. The factors that are analyzed in this review include hydrogen tunneling, proton donor-acceptor motion, hydrogen bonding, pKa shifting, electrostatics, preorganization, reorganization, and conformational motions. The rate constant for the chemical step is determined primarily by the free energy barrier, which is related to the probability of sampling configurations conducive to the chemical reaction. According to this perspective, stochastic thermal motions lead to equilibrium conformational changes in the enzyme and ligands that result in configurations favorable for the breaking and forming of chemical bonds. For proton, hydride, and proton-coupled electron transfer reactions, typically the donor and acceptor become closer to facilitate the transfer. The impact of mutations on the catalytic rate constants can be explained in terms of the factors enumerated above. In particular, distal mutations can alter the conformational motions of the enzyme and therefore the probability of sampling configurations conducive to the chemical reaction. Methods such as vibrational Stark spectroscopy, in which environmentally sensitive probes are introduced site-specifically into the enzyme, provide further insight into these aspects of enzyme catalysis through a combination of experiments and theoretical calculations.

  7. 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

  8. Molecular catalytic coal liquid conversion

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.; Yang, Shiyong [Univ. of Chicago, IL (United States)

    1995-12-31

    This research, which is relevant to the development of new catalytic systems for the improvement of the quality of coal liquids by the addition of dihydrogen, is divided into two tasks. Task 1 centers on the activation of dihydrogen by molecular basic reagents such as hydroxide ion to convert it into a reactive adduct (OH{center_dot}H{sub 2}){sup {minus}} that can reduce organic molecules. Such species should be robust withstanding severe conditions and chemical poisons. Task 2 is focused on an entirely different approach that exploits molecular catalysts, derived from organometallic compounds that are capable of reducing monocyclic aromatic compounds under very mild conditions. Accomplishments and conclusions are discussed.

  9. 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...

  10. Entrepreneurial Couples

    DEFF Research Database (Denmark)

    Dahl, Michael S.; Van Praag, Mirjam; Thompson, Peter

    We study possible motivations for co-entrepenurial couples to start up a joint firm, using a sample of 1,069 Danish couples that established a joint enterprise between 2001 and 2010. We compare their pre-entry characteristics, firm performance and postdissolution private and financial outcomes...... with a selected set of comparable firms and couples. We find evidence that couples often establish a business together because one spouse – most commonly the female – has limited outside opportunities in the labor market. However, the financial benefits for each of the spouses, and especially the female...

  11. Entrepreneurial Couples

    DEFF Research Database (Denmark)

    Dahl, Michael S.; Van Praag, Mirjam; Thompson, Peter

    We study possible motivations for co-entrepenurial couples to start up a joint firm, us-ing a sample of 1,069 Danish couples that established a joint enterprise between 2001 and 2010. We compare their pre-entry characteristics, firm performance and post-dissolution private and financial outcomes...... with a selected set of comparable firms and couples. We find evidence that couples often establish a business together because one spouse - most commonly the female - has limited outside opportunities in the labor market. However, the financial benefits for each of the spouses, and especially the female...

  12. Entrepreneurial Couples

    DEFF Research Database (Denmark)

    Dahl, Michael S.; Van Praag, Mirjam; Thompson, Peter

    2015-01-01

    We study possible motivations for co-entreprenurial couples to start up a joint firm, using a sample of 1,069 Danish couples that established a joint enterprise between 2001 and 2010. We compare their pre-entry characteristics, firm performance and post-dissolution private and financial outcomes...... with a selected set of comparable firms and couples. We find evidence that couples often establish a business together because one spouse – most commonly the female – has limited outside opportunities in the labor market. However, the financial benefits for each of the spouses, and especially the female...

  13. Atmospheric methanol measurement using selective catalytic methanol to formaldehyde conversion

    Directory of Open Access Journals (Sweden)

    S. J. Solomon

    2005-01-01

    Full Text Available A novel atmospheric methanol measurement technique, employing selective gas-phase catalytic conversion of methanol to formaldehyde followed by detection of the formaldehyde product, has been developed and tested. The effects of temperature, gas flow rate, gas composition, reactor-bed length, and reactor-bed composition on the methanol conversion efficiency of a molybdenum-rich, iron-molybdate catalyst [Mo-Fe-O] were studied. Best results were achieved using a 1:4 mixture (w/w of the catalyst in quartz sand. Optimal methanol to formaldehyde conversion (>95% efficiency occurred at a catalyst housing temperature of 345°C and an estimated sample-air/catalyst contact time of <0.2 seconds. Potential interferences arising from conversion of methane and a number of common volatile organic compounds (VOC to formaldehyde were found to be negligible under most atmospheric conditions and catalyst housing temperatures. Using the new technique, atmospheric measurements of methanol were made at the University of Bremen campus from 1 to 15 July 2004. Methanol mixing ratios ranged from 1 to 5 ppb with distinct maxima at night. Formaldehyde mixing ratios, obtained in conjunction with methanol by periodically bypassing the catalytic converter, ranged from 0.2 to 1.6 ppb with maxima during midday. These results suggest that selective, catalytic methanol to formaldehyde conversion, coupled with existing formaldehyde measurement instrumentation, is an inexpensive and effective means for monitoring atmospheric methanol.

  14. Atmospheric methanol measurement using selective catalytic methanol to formaldehyde conversion

    Directory of Open Access Journals (Sweden)

    S. J. Solomon

    2005-05-01

    Full Text Available A novel atmospheric methanol measurement technique, employing selective gas-phase catalytic conversion of methanol to formaldehyde followed by detection of the formaldehyde product, has been developed and tested. The effects of temperature, gas flow rate, gas composition, reactor-bed length, and reactor-bed composition on the methanol conversion efficiency of a molybdenum-rich, iron-molybdate catalyst [Mo-Fe-O] were studied. Best results were achieved using a 1:4 mixture (w/w of the catalyst in quartz sand. Optimal methanol to formaldehyde conversion (>95% efficiency occurred at a catalyst housing temperature of 345°C and an estimated sample-air/catalyst contact time of <0.2 s. Potential interferences arising from conversion of methane and a number of common volatile organic compounds (VOC to formaldehyde were found to be negligible under most atmospheric conditions and catalyst housing temperatures. Using the new technique, atmospheric measurements of methanol were made at the University of Bremen campus from 1 to 15 July 2004. Methanol mixing ratios ranged from 1 to 5 ppb with distinct maxima at night. Formaldehyde mixing ratios, obtained in conjunction with methanol by periodically bypassing the catalytic converter, ranged from 0.2 to 1.6 ppb with maxima during midday. These results suggest that selective, catalytic methanol to formaldehyde conversion, coupled with existing formaldehyde measurement instrumentation, is an inexpensive and effective means for monitoring atmospheric methanol.

  15. Catalytic microrotor driven by geometrical asymmetry

    Science.gov (United States)

    Yang, Mingcheng; Ripoll, Marisol; Chen, Ke

    2015-02-01

    An asymmetric gear with homogeneous surface properties is, here, presented as a prototype to fabricate catalytic microrotors. The driving torque arises from the diffusiophoretic effect induced by the concentration gradients generated by catalytic chemical reactions at the gear surface. This torque produces a spontaneous and unidirectional rotation of the asymmetric gear. By means of mesoscopic simulations, we prove and characterize this scenario. The gear rotational velocity is determined by the gear-solvent interactions, the gear geometry, the solvent viscosity, and the catalytic reaction ratio. Our work presents a simple way to design self-propelled microrotors, alternative to existing catalytic bi-component, or thermophoretic ones.

  16. Nanostructured Catalytic Reactors for Air Purification Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This SBIR Phase I project proposes the development of lightweight compact nanostructured catalytic reactors for air purification from toxic gaseous organic...

  17. Nanostructured Catalytic Reactors for Air Purification Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This SBIR Phase II project proposes the development of lightweight compact nanostructured catalytic reactors for air purification from toxic gaseous organic...

  18. Catalytic conversion of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, J.E.

    1992-06-30

    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  19. Catalytic reforming feed characterisation technique

    Energy Technology Data Exchange (ETDEWEB)

    Larraz Mora, R.; Arvelo Alvarez, R. [Univ. of La Laguna, Chemical Engineering Dept., La Laguna (Spain)

    2002-09-01

    The catalytic reforming of naphtha is one of the major refinery processes, designed to increase the octane number of naphtha or to produce aromatics. The naphtha used as catalytic reformer feedstock usually contains a mixture of paraffins, naphthenes, and aromatics in the carbon number range C{sub 6} to C{sub 10}. The detailed chemical composition of the feed is necessary to predict the aromatics and hydrogen production as well as the operation severity. The analysis of feed naphtha is usually reported in terms of its ASTM distillation curve and API or specific gravity. Since reforming reactions are described in terms of lumped chemical species (paraffins, naphthenes and aromatics), a feed characterisation technique should be useful in order to predict reforming operating conditions and detect feed quality changes. Unfortunately online analyzer applications as cromatography or recently introduced naphtha NMR [1] are scarce in most of refineries. This work proposes an algorithmic characterisation method focusing on its main steps description. The method could help on the subjects previously described, finally a calculation example is shown. (orig.)

  20. Metal hybrid nanoparticles for catalytic organic and photochemical transformations.

    Science.gov (United States)

    Song, Hyunjoon

    2015-03-17

    In order to understand heterogeneous catalytic reactions, model catalysts such as a single crystalline surface have been widely studied for many decades. However, catalytic systems that actually advance the reactions are three-dimensional and commonly have multiple components including active metal nanoparticles and metal oxide supports. On the other hand, as nanochemistry has rapidly been developed and been applied to various fields, many researchers have begun to discuss the impact of nanochemistry on heterogeneous catalysis. Metal hybrid nanoparticles bearing multiple components are structurally very close to the actual catalysts, and their uniform and controllable morphology is suitable for investigating the relationship between the structure and the catalytic properties in detail. In this Account, we introduce four typical structures of metal hybrid nanoparticles that can be used to conduct catalytic organic and photochemical reactions. Metal@silica (or metal oxide) yolk-shell nanoparticles, in which metal cores exist in internal voids surrounded by thin silica (or metal oxide) shells, exhibited extremely high thermal and chemical stability due to the geometrical protection of the silica layers against the metal cores. The morphology of the metal cores and the pore density of the hollow shells were precisely adjusted to optimize the reaction activity and diffusion rates of the reactants. Metal@metal oxide core-shell nanoparticles and inverted structures, where the cores supported the shells serving an active surface, exhibited high activity with no diffusion barriers for the reactants and products. These nanostructures were used as effective catalysts for various organic and gas-phase reactions, including hydrogen transfer, Suzuki coupling, and steam methane reforming. In contrast to the yolk- and core-shell structures, an asymmetric arrangement of distinct domains generated acentric dumbbells and tipped rods. A large domain of each component added multiple

  1. 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.

  2. 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.

  3. 四川什邡市某水厂臭氧-生物活性炭深度处理工艺分析%Process of Advanced Water Treatment with Ozone-Biological Activated Carbon in Shifang Water Treatment Plant in Shichuan Province of China

    Institute of Scientific and Technical Information of China (English)

    罗本福; 宁海燕; 杨曦

    2013-01-01

    Ozone-Biological Activated Carbon (BAC/O3 ) process design was introduced in one first bulited water treatmen plant in Shifang Shichuan China.This paper discussed the experience and measures for O 3/BAC technology project.If the thecholgy for separa-ting oxygen from air was provided in project location , when the ozone consumption Q o3≤60 kgo3/h , purchase of liquid oxygen as the raw material would be more economical , when Qo3 >60 kgo3/h, adopting the separated oxygen from air whould be better .In pre-ozona-tion reactor, O3 charging quantity Q had more effect on the ozone oxidation effect than contact time T ,but if the raw water needed to kill alga, adviced T≥5 min;In post-ozonation reactor,usually divided into three phases , the best dosing ratio was 4∶3∶3,and the CT value (CT≥4 min・ mg/L) had representation meaning to kill “two bug”.The key indicators value of the Activated carbon adsorption and structure properties were introduced:iodine value was 900 mg・ g-1 , and JiaLan value was 150 mg・ g-1 , or specific surface area of 1000 1000 m 2・ g-1 , total pore volume was 0.6 cc・ g-1 , etc.; The light seal cover should be bulited above carbon filter , 500 mm sand was added under the carbon layer and design filter speed should be reduced to ensure safety operation and reduce the risk of mi -crobial penetration filter layer.%  对四川什邡市某水厂臭氧-生物活性炭(O3/BAC)深度处理工艺进行分析,阐述了O3/BAC工艺的工程经验和措施,具体工艺方案为:在有空气分离制氧企业的城市,当臭氧耗量Q≤60 kgO3/h时选择外购液氧,反之可考虑现场空气分离制氧;预臭氧氧化效果与O3加注量Q的相关性大于接触时间T的影响,若原水需杀藻,T建议≥5 min;主臭氧接触池三段式最佳投加比例为4∶3∶3,控制CT值(CT≥4 min・ mg/L)对杀灭“两虫”有表征意义;活性炭吸附与结构性能的关键指标建议值为:碘值≥900

  4. Catalytic synthesis of silicon carbide preceramic polymers: Polycarbosilanes

    Energy Technology Data Exchange (ETDEWEB)

    Berry, D.H.

    1992-10-01

    Polycarbosilanes are the most successful and widely studied class of polymer precursors for silicon carbide, but traditional methods for their synthesis are inefficient and nonselective. This project is focused on developing transition metal catalysts for the synthesis of polycarbosilanes and other preceramic polymers. In recent work we have developed the first homogeneous transition metal catalysts for the dehydrogenative coupling of simple alkyl silanes to oligomeric and polymeric carbosilanes, H-(SiR[sub 2]CR[prime][sub 2])n-SiR[sub 3]. The coupling of alkylgermanes, however, yields the corresponding oligomeric poly(germanes) (Ge-Ge). Future work will help elucidate the mechanisms of these catalytic process, explore the use of hydrogen acceptors as reaction accelerators, and develop new and more active catalysts.

  5. Catalytic synthesis of silicon carbide preceramic polymers: Polycarbosilanes. Final technical report, March 1, 1991--August 31, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Berry, D.H.

    1997-02-01

    This effort has focused on the development of new systems for the catalytic formation of organosilicon monomers and polymers. Several new classes of ruthenium phosphine complexes containing one, two, or three silicon ligands have been prepared, and which exhibit unique catalytic reactivity for (1) the dehydrogenative coupling of tertiary alkyl silanes to polycarbonsilanes, (2) dehydrogenative coupling of secondary and primary alkyl and aryl silanes to polysilanes, and (3) the dehydrogenative heterocoupling of silanes with substituted arenes to yield aryl silanes. In addition, germanium analogs of the ruthenium silyl complexes have been found to be effective catalysts for the unprecedented demethanative coupling of alkyl germanes to high molecular weight polygermanes. For each of these new reactions, key mechanistic features of the catalytic processes have been elucidated, and the complexes have been extensively studied in terms of relevant stoichiometric reactivity and structural features.

  6. Electrochemical promotion of catalytic reactions

    Science.gov (United States)

    Imbihl, R.

    2010-05-01

    The electrochemical promotion of heterogeneously catalyzed reactions (EPOC) became feasible through the use of porous metal electrodes interfaced to a solid electrolyte. With the O 2- conducting yttrium stabilized zirconia (YSZ), the Na + conducting β″-Al 2O 3 (β-alumina), and several other types of solid electrolytes the EPOC effect has been demonstrated for about 100 reaction systems in studies conducted mainly in the mbar range. Surface science investigations showed that the physical basis for the EPOC effect lies in the electrochemically induced spillover of oxygen and alkali metal, respectively, onto the surface of the metal electrodes. For the catalytic promotion effect general concepts and mechanistic schemes were proposed but these concepts and schemes are largely speculative. Applying surface analytical tools to EPOC systems the proposed mechanistic schemes can be verified or invalidated. This report summarizes the progress which has been achieved in the mechanistic understanding of the EPOC effect.

  7. Catalytic Graphitization of Phenolic Resin

    Institute of Scientific and Technical Information of China (English)

    Mu Zhao; Huaihe Song

    2011-01-01

    The catalytic graphitization of thermal plastic phenolic-formaldehyde resin with the aid of ferric nitrate (FN) was studied in detail. The morphologies and structural features of the products including onion-like carbon nanoparticles and bamboo-shaped carbon nanotubes were investigated by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction and Raman spectroscopy measurements. It was found that with the changes of loading content of FN and residence time at 1000℃, the products exhibited various morphologies. The TEM images showed that bamboo-shaped carbon nanotube consisted of tens of bamboo sticks and onion-like carbon nanoparticle was made up of quasi-spherically concentrically closed carbon nanocages.

  8. Unsteady processes in catalytic reactors

    Energy Technology Data Exchange (ETDEWEB)

    Matros, Yu.Sh.

    1985-01-01

    In recent years a realization has occurred that reaction and reactor dynamics must be considered when designing and operating catalytic reactors. In this book, the author has focussed on both the processes occurring on individual porous-catalyst particles as well as the phenomena displayed by collections of these particles in fixed-bed reactors. The major topics discussed include the effects of unsteady-state heat and mass transfer, the influence of inhomogeneities and stagnant regions in fixed beds, and reactor operation during forced cycling of operating conditions. Despite the title of the book, attention is also paid to the determination of the number and stability of fixed-bed steady states, with the aim of describing the possibility of controlling reactors at unstable steady states. However, this development is somewhat dated, given the recent literature on multiplicity phenomena and process control.

  9. Non-catalytic recuperative reformer

    Energy Technology Data Exchange (ETDEWEB)

    Khinkis, Mark J.; Kozlov, Aleksandr P.; Kurek, Harry

    2015-12-22

    A non-catalytic recuperative reformer has a flue gas flow path for conducting hot flue gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is embedded in the flue gas flow path to permit heat transfer from the hot flue gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorific fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, extended surfaces of metal material such as stainless steel or metal alloy that are high in nickel content are included within at least a portion of the reforming mixture flow path.

  10. 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.)

  11. Method of fabricating a catalytic structure

    Science.gov (United States)

    Rollins, Harry W.; Petkovic, Lucia M.; Ginosar, Daniel M.

    2009-09-22

    A precursor to a catalytic structure comprising zinc oxide and copper oxide. The zinc oxide has a sheet-like morphology or a spherical morphology and the copper oxide comprises particles of copper oxide. The copper oxide is reduced to copper, producing the catalytic structure. The catalytic structure is fabricated by a hydrothermal process. A reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent is formed. The reaction mixture is heated under confined volume conditions to produce the precursor. The copper oxide in the precursor is reduced to copper. A method of hydrogenating a carbon oxide using the catalytic structure is also disclosed, as is a system that includes the catalytic structure.

  12. Instantaneous carbon-carbon bond formation using a microchannel reactor with a catalytic membrane.

    Science.gov (United States)

    Uozumi, Yasuhiro; Yamada, Yoichi M A; Beppu, Tomohiko; Fukuyama, Naoshi; Ueno, Masaharu; Kitamori, Takehiko

    2006-12-20

    Instantaneous catalytic carbon-carbon bond forming reactions were achieved in a microchannel reactor having a polymeric palladium complex membrane. The catalytic membrane was constructed inside the microchannel via self-assembling complexation at the interface between the organic and aqueous phases flowing laminarly, where non-cross-linked polymer-bound phosphine and ammonium tetrachloropalladate dissolved, respectively. A palladium-catalyzed coupling reaction of aryl halides and arylboronic acids was performed using the microchannel reactor to give quantitative yields of biaryls within 4 s of retention time in the defined channel region.

  13. Nonadiabatic Coupling

    Science.gov (United States)

    Kryachko, Eugene S.

    The general features of the nonadiabatic coupling and its relation to molecular properties are surveyed. Some consequences of the [`]equation of motion', formally expressing a [`]smoothness' of a given molecular property within the diabatic basis, are demonstrated. A particular emphasis is made on the relation between a [`]smoothness' of the electronic dipole moment and the generalized Mulliken-Hush formula for the diabatic electronic coupling.

  14. Revolutionary systems for catalytic combustion and diesel catalytic particulate traps.

    Energy Technology Data Exchange (ETDEWEB)

    Stuecker, John Nicholas; Witze, Peter O.; Ferrizz, Robert Matthew; Cesarano, Joseph, III; Miller, James Edward

    2004-12-01

    This report is a summary of an LDRD project completed for the development of materials and structures conducive to advancing the state of the art for catalyst supports and diesel particulate traps. An ancillary development for bio-medical bone scaffolding was also realized. Traditionally, a low-pressure drop catalyst support, such as a ceramic honeycomb monolith, is used for catalytic reactions that require high flow rates of gases at high-temperatures. A drawback to the traditional honeycomb monoliths under these operating conditions is poor mass transfer to the catalyst surface in the straight-through channels. ''Robocasting'' is a unique process developed at Sandia National Laboratories that can be used to manufacture ceramic monoliths with alternative 3-dimensional geometries, providing tortuous pathways to increase mass transfer while maintaining low-pressure drops. These alternative 3-dimensional geometries may also provide a foundation for the development of self-regenerating supports capable of trapping and combusting soot particles from a diesel engine exhaust stream. This report describes the structures developed and characterizes the improved catalytic performance that can result. The results show that, relative to honeycomb monolith supports, considerable improvement in mass transfer efficiency is observed for robocast samples synthesized using an FCC-like geometry of alternating rods. Also, there is clearly a trade-off between enhanced mass transfer and increased pressure drop, which can be optimized depending on the particular demands of a given application. Practical applications include the combustion of natural gas for power generation, production of syngas, and hydrogen reforming reactions. The robocast lattice structures also show practicality for diesel particulate trapping. Preliminary results for trapping efficiency are reported as well as the development of electrically resistive lattices that can regenerate the structure

  15. Development of Catalytic Cooking Plates

    Energy Technology Data Exchange (ETDEWEB)

    Hjelm, Anna-Karin; Silversand, Fredrik [CATATOR AB, Lund (Sweden); Tena, Emmanuel; Berger, Marc [Gaz de France (France)

    2004-04-01

    Gas catalytic combustion for gas stoves or cooking plates (closed catalytic burner system with ceramic plates) is a very promising technique in terms of ease of cleaning, power modulation and emissions. Previous investigations show that wire mesh catalysts, prepared and supplied by Catator AB (CAT), seem to be very well suited for such applications. Beside significantly reducing the NOx-emissions, these catalysts offer important advantages such as good design flexibility, low pressure drop and high heat transfer capacity, where the latter leads to a quick thermal response. Prior to this project, Gaz de France (GdF) made a series of measurements with CAT's wire mesh catalysts in their gas cooking plates and compared the measured performance with similar results obtained with theirs cordierite monolith catalysts. Compared to the monolith catalyst, the wire mesh catalyst was found to enable very promising results with respect to both emission levels (<10 mg NO{sub x} /kWh, <5 mg CO/kWh) and life-time (>8000 h vs. 700 h at 200 kW/m{sup 2}). It was however established that the radiation and hence, the thermal efficiency of the cooking plate, was significantly less than is usually measured in combination with the monolith (15 % vs. 32 %). It was believed that the latter could be improved by developing new burner designs based on CAT's wire mesh concept. As a consequence, a collaboration project between GdF, CAT and the Swedish Gas Technology AB was created. This study reports on the design, the construction and the evaluation of new catalytic burners, based on CAT's wire mesh catalysts, used for the combustion of natural gas in gas cooking stoves. The evaluation of the burners was performed with respect to key factors such as thermal efficiency, emission quality and pressure drop, etc, by the use of theoretical simulations and experimental tests. Impacts of parameters such as the the wire mesh number, the wire mesh structure (planar or folded), the

  16. Catalytic Wittig and aza-Wittig reactions

    Directory of Open Access Journals (Sweden)

    Zhiqi Lao

    2016-11-01

    Full Text Available This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines.

  17. Halogen Chemistry on Catalytic Surfaces.

    Science.gov (United States)

    Moser, Maximilian; Pérez-Ramírez, Javier

    2016-01-01

    Halogens are key building blocks for the manufacture of high-value products such as chemicals, plastics, and pharmaceuticals. The catalytic oxidation of HCl and HBr is an attractive route to recover chlorine and bromine in order to ensure the sustainability of the production processes. Very few materials withstand the high corrosiveness and the strong exothermicity of the reactions and among them RuO2 and CeO2-based catalysts have been successfully applied in HCl oxidation. The search for efficient systems for HBr oxidation was initiated by extrapolating the results of HCl oxidation based on the chemical similarity of these reactions. Interestingly, despite its inactivity in HCl oxidation, TiO2 was found to be an outstanding HBr oxidation catalyst, which highlighted that the latter reaction is more complex than previously assumed. Herein, we discuss the results of recent comparative studies of HCl and HBr oxidation on both rutile-type (RuO2, IrO2, and TiO2) and ceria-based catalysts using a combination of advanced experimental and theoretical methods to provide deeper molecular-level understanding of the reactions. This knowledge aids the design of the next-generation catalysts for halogen recycling.

  18. 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.

  19. Catalytic models developed through social work

    DEFF Research Database (Denmark)

    Jensen, Mogens

    2015-01-01

    The article develops the concept of catalytic processes in relation to social work with adolescents in an attempt to both reach a more nuanced understanding of social work and at the same time to develop the concept of catalytic processes in psychology. The social work is pedagogical treatment...... of adolescents placed in out-of-home care and is characterised using three situated cases as empirical data. Afterwards the concept of catalytic processes is briefly presented and then applied in an analysis of pedagogical treatment in the three cases. The result is a different conceptualisation of the social...... work with new possibilities of development of the work, but also suggestions for development of the concept of catalytic processes....

  20. Catalytic converters as a source of platinum

    Directory of Open Access Journals (Sweden)

    A. Fornalczyk

    2011-10-01

    Full Text Available The increase of Platinum Group Metals demand in automotive industry is connected with growing amount of cars equipped with the catalytic converters. The paper presents the review of available technologies during recycling process. The possibility of removing platinum from the used catalytic converters applying pyrometallurgical and hyrdometallurgical methods were also investigated. Metals such as Cu, Pb, Ca, Mg, Cd were used in the pyrometallurgical research (catalytic converter was melted with Cu, Pb and Ca or Mg and Cd vapours were blown through the whole carrier. In hydrometallurgical research catalytic converters was dissolved in aqua regia. Analysis of Pt contents in the carrier before and after the process was performed by means of atomic absorption spectroscopy. Obtained result were discussed.

  1. Catalytic Asymmetric Synthesis of Phosphine Boronates

    NARCIS (Netherlands)

    Hornillos, Valentin; Vila, Carlos; Otten, Edwin; Feringa, Ben L.

    2015-01-01

    The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of ,-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good y

  2. 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

  3. MOBILE COMPLEX FOR CATALYTIC THERMAL WASTE TREATMENT

    Directory of Open Access Journals (Sweden)

    Vedi V.E.

    2012-12-01

    Full Text Available The design and purpose of the basic units of the mobile waste processing complex “MPK” are described. Experimental data of catalytic purification of exhaust gases are presented. Experimental data on catalytic clearing of final gases of a designed mobile incinerator plant are shown. It is defined, that concentrating of parasitic bridging in waste gases of the complex are considerably smaller, rather than allowed by normative documents.

  4. Temperature Modulation of a Catalytic Gas Sensor

    OpenAIRE

    Eike Brauns; Eva Morsbach; Sebastian Kunz; Marcus Baeumer; Walter Lang

    2014-01-01

    The use of catalytic gas sensors usually offers low selectivity, only based on their different sensitivities for various gases due to their different heats of reaction. Furthermore, the identification of the gas present is not possible, which leads to possible misinterpretation of the sensor signals. The use of micro-machined catalytic gas sensors offers great advantages regarding the response time, which allows advanced analysis of the sensor response. By using temperature modulation, additi...

  5. Non-equilibrium model for catalytic distillation process

    Institute of Scientific and Technical Information of China (English)

    Feng WANG; Ning ZHAO; Junping LI; Fukui XIAO; Wei WEI; Yuhan SUN

    2008-01-01

    A new improved tri-diagonal method was developed for the non-equilibrium stage model of the catalytic distillation by coupling consumptive reaction coefficient. The reactions in the distillation column were divided into generative reaction and consumptive reac-tion. The non-equilibrium stage model was introduced for the catalytic distillation process of the dimethyl car-bonate (DMC) synthesis by urea methanolysis over solid based catalyst, and the improved tri-diagonal method was used to solve the model equations. Comparison of pre-dicted results with experiment data shows that the mean relative error of the yield of DMC was 3.78% under dif-ferent conditions such as different operating pressures and reaction temperatures. The improved tri-diagonal matrix method could avoid the negative values of the liquid com-positions during the calculations and restrain the fluc-tuation of compositions by slowing down the variations of the values in the iteration. The modeling results show that the improved tri-diagonal method was appropriate for system containing a wide range of boiling point com-ponents and a different rate of reactions.

  6. 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.

  7. Adsorbent catalytic nanoparticles and methods of using the same

    Energy Technology Data Exchange (ETDEWEB)

    Slowing, Igor Ivan; Kandel, Kapil

    2017-01-31

    The present invention provides an adsorbent catalytic nanoparticle including a mesoporous silica nanoparticle having at least one adsorbent functional group bound thereto. The adsorbent catalytic nanoparticle also includes at least one catalytic material. In various embodiments, the present invention provides methods of using and making the adsorbent catalytic nanoparticles. In some examples, the adsorbent catalytic nanoparticles can be used to selectively remove fatty acids from feedstocks for biodiesel, and to hydrotreat the separated fatty acids.

  8. From Electronic Structure to Catalytic Activity: A Single Descriptor for Adsorption and Reactivity on Transition-Metal Carbides

    DEFF Research Database (Denmark)

    Vojvodic, A.; Hellman, Anders; Ruberto, C.

    2009-01-01

    Adsorption and catalytic properties of the polar (111) surface of transition-metal carbides (TMC's) are investigated by density-functional theory. Atomic and molecular adsorption are rationalized with the concerted-coupling model, in which two types of TMC surface resonances (SR's) play key roles...

  9. Transient and sustained elementary flux mode networks on a catalytic string-based chemical evolution model.

    Science.gov (United States)

    Pereira, José A

    2014-08-01

    Theoretical models designed to test the metabolism-first hypothesis for prebiotic evolution have yield strong indications about the hypothesis validity but could sometimes use a more extensive identification between model objects and real objects towards a more meaningful interpretation of results. In an attempt to go in that direction, the string-based model SSE ("steady state evolution") was developed, where abstract molecules (strings) and catalytic interaction rules are based on some of the most important features of carbon compounds in biological chemistry. The system is open with a random inflow and outflow of strings but also with a permanent string food source. Although specific catalysis is a key aspect of the model, used to define reaction rules, the focus is on energetics rather than kinetics. Standard energy change tables were constructed and used with standard formation reactions to track energy flows through the interpretation of equilibrium constant values. Detection of metabolic networks on the reaction system was done with elementary flux mode (EFM) analysis. The combination of these model design and analysis options enabled obtaining metabolic and catalytic networks showing several central features of biological metabolism, some more clearly than in previous models: metabolic networks with stepwise synthesis, energy coupling, catalysts regulation, SN2 coupling, redox coupling, intermediate cycling, coupled inverse pathways (metabolic cycling), autocatalytic cycles and catalytic cascades. The results strongly suggest that the main biological metabolism features, including the genotype-phenotype interpretation, are caused by the principles of catalytic systems and are prior to modern genetic systems principles. It also gives further theoretical support to the thesis that the basic features of biologic metabolism are a consequence of the time evolution of a random catalyst search working on an open system with a permanent food source. The importance

  10. Catalytically stabilized combustion of lean methane-air-mixtures: a numerical model

    Energy Technology Data Exchange (ETDEWEB)

    Dogwiler, U.; Benz, P.; Mantharas, I. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    The catalytically stabilized combustion of lean methane/air mixtures has been studied numerically under conditions closely resembling the ones prevailing in technical devices. A detailed numerical model has been developed for a laminar, stationary, 2-D channel flow with full heterogeneous and homogeneous reaction mechanisms. The computations provide direct information on the coupling between heterogeneous-homogeneous combustion and in particular on the means of homogeneous ignitions and stabilization. (author) 4 figs., 3 refs.

  11. Kinetically controlled E-selective catalytic olefin metathesis.

    Science.gov (United States)

    Nguyen, Thach T; Koh, Ming Joo; Shen, Xiao; Romiti, Filippo; Schrock, Richard R; Hoveyda, Amir H

    2016-04-29

    A major shortcoming in olefin metathesis, a chemical process that is central to research in several branches of chemistry, is the lack of efficient methods that kinetically favor E isomers in the product distribution. Here we show that kinetically E-selective cross-metathesis reactions may be designed to generate thermodynamically disfavored alkenyl chlorides and fluorides in high yield and with exceptional stereoselectivity. With 1.0 to 5.0 mole % of a molybdenum-based catalyst, which may be delivered in the form of air- and moisture-stable paraffin pellets, reactions typically proceed to completion within 4 hours at ambient temperature. Many isomerically pure E-alkenyl chlorides, applicable to catalytic cross-coupling transformations and found in biologically active entities, thus become easily and directly accessible. Similarly, E-alkenyl fluorides can be synthesized from simpler compounds or more complex molecules.

  12. CFD SIMULATION OF FLUID CATALYTIC CRACKING IN DOWNER REACTORS

    Institute of Scientific and Technical Information of China (English)

    Fei Liu; Fei Wei; Yu Zheng; Yong Jin

    2006-01-01

    A mathematical model has been developed for the simulation of gas-particle flow and fluid catalytic cracking in downer reactors. The model takes into account both cracking reaction and flow behavior through a four-lump reaction kinetics coupled with two-phase turbulent flow. The prediction results show that the relatively large change of gas velocity affects directly the axial distribution of solids velocity and void fraction, which significantly interact with the chemical reaction. Furthermore, model simulations are carried out to determine the effects of such parameters on product yields, as bed diameter, reaction temperature and the ratio of catalyst to oil, which are helpful for optimizing the yields of desired products. The model equations are coded and solved on CFX4.4.

  13. SOFC system with integrated catalytic fuel processing

    Science.gov (United States)

    Finnerty, Caine; Tompsett, Geoff. A.; Kendall, Kevin; Ormerod, R. Mark

    In recent years, there has been much interest in the development of solid oxide fuel cell technology operating directly on hydrocarbon fuels. The development of a catalytic fuel processing system, which is integrated with the solid oxide fuel cell (SOFC) power source is outlined here. The catalytic device utilises a novel three-way catalytic system consisting of an in situ pre-reformer catalyst, the fuel cell anode catalyst and a platinum-based combustion catalyst. The three individual catalytic stages have been tested in a model catalytic microreactor. Both temperature-programmed and isothermal reaction techniques have been applied. Results from these experiments were used to design the demonstration SOFC unit. The apparatus used for catalytic characterisation can also perform in situ electrochemical measurements as described in previous papers [C.M. Finnerty, R.H. Cunningham, K. Kendall, R.M. Ormerod, Chem. Commun. (1998) 915-916; C.M. Finnerty, N.J. Coe, R.H. Cunningham, R.M. Ormerod, Catal. Today 46 (1998) 137-145]. This enabled the performance of the SOFC to be determined at a range of temperatures and reaction conditions, with current output of 290 mA cm -2 at 0.5 V, being recorded. Methane and butane have been evaluated as fuels. Thus, optimisation of the in situ partial oxidation pre-reforming catalyst was essential, with catalysts producing high H 2/CO ratios at reaction temperatures between 873 K and 1173 K being chosen. These included Ru and Ni/Mo-based catalysts. Hydrocarbon fuels were directly injected into the catalytic SOFC system. Microreactor measurements revealed the reaction mechanisms as the fuel was transported through the three-catalyst device. The demonstration system showed that the fuel processing could be successfully integrated with the SOFC stack.

  14. SOFC system with integrated catalytic fuel processing

    Energy Technology Data Exchange (ETDEWEB)

    Finnerty, C.; Tompsett, G.A.; Kendall, K.; Ormerod, R.M. [Birchall Centre for Inorganic Chemistry and Materials Science, Keele Univ. (United Kingdom)

    2000-03-01

    In recent years, there has been much interest in the development of solid oxide fuel cell technology operating directly on hydrocarbon fuels. The development of a catalytic fuel processing system, which is integrated with the solid oxide fuel cell (SOFC) power source is outlined here. The catalytic device utilises a novel three-way catalytic system consisting of an in situ pre-reformer catalyst, the fuel cell anode catalyst and a platinum-based combustion catalyst. The three individual catalytic stages have been tested in a model catalytic microreactor. Both temperature-programmed and isothermal reaction techniques have been applied. Results from these experiments were used to design the demonstration SOFC unit. The apparatus used for catalytic characterisation can also perform in situ electrochemical measurements as described in previous papers [C.M. Finnerty, R.H. Cunningham, K. Kendall, R.M. Ormerod, Chem. Commun. (1998) 915-916; C.M. Finnerty, N.J. Coe, R.H. Cunningham, R.M. Ormerod, Catal. Today 46 (1998) 137-145]. This enabled the performance of the SOFC to be determined at a range of temperatures and reaction conditions, with current output of 290 mA cm{sup -2} at 0.5 V, being recorded. Methane and butane have been evaluated as fuels. Thus, optimisation of the in situ partial oxidation pre-reforming catalyst was essential, with catalysts producing high H{sub 2}/CO ratios at reaction temperatures between 873 K and 1173 K being chosen. These included Ru and Ni/Mo-based catalysts. Hydrocarbon fuels were directly injected into the catalytic SOFC system. Microreactor measurements revealed the reaction mechanisms as the fuel was transported through the three-catalyst device. The demonstration system showed that the fuel processing could be successfully integrated with the SOFC stack. (orig.)

  15. Theoretical study of catalytic efficiency of a Diels-Alderase catalytic antibody: an indirect effect produced during the maturation process.

    Science.gov (United States)

    Martí, Sergio; Andrés, Juan; Moliner, Vicent; Silla, Estanislao; Tuñón, Iñaki; Bertrán, Juan

    2008-01-01

    The Diels-Alder reaction is one of the most important and versatile transformations available to organic chemists for the construction of complex natural products, therapeutics agents, and synthetic materials. Given the lack of efficient enzymes capable of catalyzing this kind of reaction, it is of interest to ask whether a biological catalyst could be designed from an antibody-combining site. In the present work, a theoretical study of the different behavior of a germline catalytic antibody (CA) and its matured form, 39 A-11, that catalyze a Diels-Alder reaction has been carried out. A free-energy perturbation technique based on a hybrid quantum-mechanics/molecular-mechanics scheme, together with internal energy minimizations, has allowed free-energy profiles to be obtained for both CAs. The profiles show a smaller barrier for the matured form, which is in agreement with the experimental observation. Free-energy profiles were obtained with this methodology, thereby avoiding the much more demanding two-dimensional calculations of the energy surfaces that are normally required to study this kind of reaction. Structural analysis and energy evaluations of substrate-protein interactions have been performed from averaged structures, which allows understanding of how the single mutations carried out during the maturation process can be responsible for the observed fourfold enhancement of the catalytic rate constant. The conclusion is that the mutation effect in this studied germline CA produces a complex indirect effect through coupled movements of the backbone of the protein and the substrate.

  16. Catalytic coal liquefaction. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Weller, S W

    1981-01-01

    Monolith catalysts of MoO/sub 3/-CoO-Al/sub 2/O/sub 3/ were prepared and tested for coal liquefaction in a stirred autoclave. In general, the monolith catalysts were not as good as particulate catalysts prepared on Corning alumina supports. Measurement of O/sub 2/ chemisorption and BET surface area has been made on a series of Co/Mo/Al/sub 2/O/sub 3/ catalysts obtained from PETC. The catalysts were derived from Cyanamid 1442A and had been tested for coal liquefaction in batch autoclaves and continuous flow units. MoO/sub 3/-Al/sub 2/O/sub 3/ catalysts over the loading range 3.9 to 14.9 wt % MoO/sub 3/ have been studied with respect to BET surface (before and after reduction), O/sub 2/ chemisorption at -78/sup 0/C, redox behavior at 500/sup 0/C, and activity for cyclohexane dehydrogenation at 500/sup 0/C. In connection with the fate of tin catalysts during coal liquefaction, calculations have been made of the relative thermodynamic stability of SnCl/sub 2/, Sn, SnO/sub 2/, and SnS in the presence of H/sub 2/, HCl, H/sub 2/S and H/sub 2/O. Ferrous sulfate dispersed in methylnaphthalene has been shown to be reduced to ferrous sulfide under typical coal hydroliquefaction conditions (1 hour, 450/sup 0/C, 1000 psi initial p/sub H/sub 2//). This suggests that ferrous sulfide may be the common catalytic ingredient when either (a) ferrous sulfate impregnated on powdered coal, or (b) finely divided iron pyrite is used as the catalyst. Old research on impregnated ferrous sulfate, impregnated ferrous halides, and pyrite is consistent with this assumption. Eight Co/Mo/Al/sub 2/O/sub 3/ catalysts from commercial suppliers, along with SnCl/sub 2/, have been studied for the hydrotreating of 1-methylnaphthalene (1-MN) in a stirred autoclave at 450 and 500/sup 0/C.

  17. Simultaneous probing of bulk liquid phase and catalytic gas-liquid-solid interface under working conditions using attenuated total reflection infrared spectroscopy

    Science.gov (United States)

    Meemken, Fabian; Müller, Philipp; Hungerbühler, Konrad; Baiker, Alfons

    2014-08-01

    Design and performance of a reactor set-up for attenuated total reflection infrared (ATR-IR) spectroscopy suitable for simultaneous reaction monitoring of bulk liquid and catalytic solid-liquid-gas interfaces under working conditions are presented. As advancement of in situ spectroscopy an operando methodology for gas-liquid-solid reaction monitoring was developed that simultaneously combines catalytic activity and molecular level detection at the catalytically active site of the same sample. Semi-batch reactor conditions are achieved with the analytical set-up by implementing the ATR-IR flow-through cell in a recycle reactor system and integrating a specifically designed gas feeding system coupled with a bubble trap. By the use of only one spectrometer the design of the new ATR-IR reactor cell allows for simultaneous detection of the bulk liquid and the catalytic interface during the working reaction. Holding two internal reflection elements (IRE) the sample compartments of the horizontally movable cell are consecutively flushed with reaction solution and pneumatically actuated, rapid switching of the cell (<1 s) enables to quasi simultaneously follow the heterogeneously catalysed reaction at the catalytic interface on a catalyst-coated IRE and in the bulk liquid on a blank IRE. For a complex heterogeneous reaction, the asymmetric hydrogenation of 2,2,2-trifluoroacetophenone on chirally modified Pt catalyst the elucidation of catalytic activity/enantioselectivity coupled with simultaneous monitoring of the catalytic solid-liquid-gas interface is shown. Both catalytic activity and enantioselectivity are strongly dependent on the experimental conditions. The opportunity to gain improved understanding by coupling measurements of catalytic performance and spectroscopic detection is presented. In addition, the applicability of modulation excitation spectroscopy and phase-sensitive detection are demonstrated.

  18. Simultaneous probing of bulk liquid phase and catalytic gas-liquid-solid interface under working conditions using attenuated total reflection infrared spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Meemken, Fabian; Müller, Philipp; Hungerbühler, Konrad; Baiker, Alfons, E-mail: baiker@chem.ethz.ch [Department of Chemistry and Applied Biosciences, Institute for Chemical and Bioengineering, ETH Zürich, Hönggerberg, HCI, CH-8093 Zürich (Switzerland)

    2014-08-15

    Design and performance of a reactor set-up for attenuated total reflection infrared (ATR-IR) spectroscopy suitable for simultaneous reaction monitoring of bulk liquid and catalytic solid-liquid-gas interfaces under working conditions are presented. As advancement of in situ spectroscopy an operando methodology for gas-liquid-solid reaction monitoring was developed that simultaneously combines catalytic activity and molecular level detection at the catalytically active site of the same sample. Semi-batch reactor conditions are achieved with the analytical set-up by implementing the ATR-IR flow-through cell in a recycle reactor system and integrating a specifically designed gas feeding system coupled with a bubble trap. By the use of only one spectrometer the design of the new ATR-IR reactor cell allows for simultaneous detection of the bulk liquid and the catalytic interface during the working reaction. Holding two internal reflection elements (IRE) the sample compartments of the horizontally movable cell are consecutively flushed with reaction solution and pneumatically actuated, rapid switching of the cell (<1 s) enables to quasi simultaneously follow the heterogeneously catalysed reaction at the catalytic interface on a catalyst-coated IRE and in the bulk liquid on a blank IRE. For a complex heterogeneous reaction, the asymmetric hydrogenation of 2,2,2-trifluoroacetophenone on chirally modified Pt catalyst the elucidation of catalytic activity/enantioselectivity coupled with simultaneous monitoring of the catalytic solid-liquid-gas interface is shown. Both catalytic activity and enantioselectivity are strongly dependent on the experimental conditions. The opportunity to gain improved understanding by coupling measurements of catalytic performance and spectroscopic detection is presented. In addition, the applicability of modulation excitation spectroscopy and phase-sensitive detection are demonstrated.

  19. Atomically Precise Metal Nanoclusters for Catalytic Application

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Rongchao [Carnegie Mellon Univ., Pittsburgh, PA (United States)

    2016-11-18

    The central goal of this project is to explore the catalytic application of atomically precise gold nanoclusters. By solving the total structures of ligand-protected nanoclusters, we aim to correlate the catalytic properties of metal nanoclusters with their atomic/electronic structures. Such correlation unravel some fundamental aspects of nanocatalysis, such as the nature of particle size effect, origin of catalytic selectivity, particle-support interactions, the identification of catalytically active centers, etc. The well-defined nanocluster catalysts mediate the knowledge gap between single crystal model catalysts and real-world conventional nanocatalysts. These nanoclusters also hold great promise in catalyzing certain types of reactions with extraordinarily high selectivity. These aims are in line with the overall goals of the catalytic science and technology of DOE and advance the BES mission “to support fundamental research to understand, predict, and ultimately control matter and energy at the level of electrons, atoms, and molecules”. Our group has successfully prepared different sized, robust gold nanoclusters protected by thiolates, such as Au25(SR)18, Au28(SR)20, Au38(SR)24, Au99(SR)42, Au144(SR)60, etc. Some of these nanoclusters have been crystallographically characterized through X-ray crystallography. These ultrasmall nanoclusters (< 2 nm diameter) exhibit discrete electronic structures due to quantum size effect, as opposed to quasicontinuous band structure of conventional metal nanoparticles or bulk metals. The available atomic structures (metal core plus surface ligands) of nanoclusters serve as the basis for structure-property correlations. We have investigated the unique catalytic properties of nanoclusters (i.e. not observed in conventional nanogold catalysts) and revealed the structure-selectivity relationships. Highlights of our

  20. A novel liquid system of catalytic hydrogenation

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    On the basis that endothermic aqueous-phase reforming of oxygenated hydrocarbons for H2 production and exothermic liquid phase hydrogenation of organic compounds are carried out under extremely close conditions of temperature and pressure over the same type of catalyst, a novel liquid system of catalytic hydrogenation has been proposed, in which hydrogen produced from aqueous-phase reforming of oxygenated hydrocarbons is in situ used for liquid phase hydrogenation of organic compounds. The usage of active hydrogen generated from aqueous-phase reforming of oxygenated hydrocarbons for liquid catalytic hydrogenation of organic compounds could lead to increasing the selectivity to H2 in the aqueous-phase reforming due to the prompt removal of hydrogen on the active centers of the catalyst. Meanwhile, this novel liquid system of catalytic hydrogenation might be a potential method to improve the selectivity to the desired product in liquid phase catalytic hydrogenation of organic compounds. On the other hand, for this novel liquid system of catalytic hydrogenation, some special facilities for H2 generation, storage and transportation in traditional liquid phase hydrogenation industry process are yet not needed. Thus, it would simplify the working process of liquid phase hydrogenation and increase the energy usage and hydrogen productivity.

  1. Catalytic Combustor for Fuel-Flexible Turbine

    Energy Technology Data Exchange (ETDEWEB)

    Laster, W. R.; Anoshkina, E.

    2008-01-31

    Under the sponsorship of the U. S. Department of Energy’s National Energy Technology Laboratory, Siemens Westinghouse has conducted a three-year program to develop an ultra low NOx, fuel flexible catalytic combustor for gas turbine application in IGCC. The program is defined in three phases: Phase 1- Implementation Plan, Phase 2- Validation Testing and Phase 3 – Field Testing. Both Phase 1 and Phase 2 of the program have been completed. In IGCC power plants, the gas turbine must be capable of operating on syngas as a primary fuel and an available back-up fuel such as natural gas. In this program the Rich Catalytic Lean (RCLTM) technology is being developed as an ultra low NOx combustor. In this concept, ultra low NOx is achieved by stabilizing a lean premix combustion process by using a catalytic reactor to oxidize a portion of the fuel, increasing the temperature of fuel/air mixture prior to the main combustion zone. In Phase 1, the feasibility of the catalytic concept for syngas application has been evaluated and the key technology issues identified. In Phase II the technology necessary for the application of the catalytic concept to IGCC fuels was developed through detailed design and subscale testing. Phase III (currently not funded) will consist of full-scale combustor basket testing on natural gas and syngas.

  2. Catalytic Combustor for Fuel-Flexible Turbine

    Energy Technology Data Exchange (ETDEWEB)

    W. R. Laster; E. Anoshkina

    2008-01-31

    Under the sponsorship of the U. S. Department of Energy's National Energy Technology Laboratory, Siemens Westinghouse has conducted a three-year program to develop an ultra low NOx, fuel flexible catalytic combustor for gas turbine application in IGCC. The program is defined in three phases: Phase 1 - Implementation Plan, Phase 2 - Validation Testing and Phase 3 - Field Testing. Both Phase 1 and Phase 2 of the program have been completed. In IGCC power plants, the gas turbine must be capable of operating on syngas as a primary fuel and an available back-up fuel such as natural gas. In this program the Rich Catalytic Lean (RCLTM) technology is being developed as an ultra low NOx combustor. In this concept, ultra low NOx is achieved by stabilizing a lean premix combustion process by using a catalytic reactor to oxidize a portion of the fuel, increasing the temperature of fuel/air mixture prior to the main combustion zone. In Phase 1, the feasibility of the catalytic concept for syngas application has been evaluated and the key technology issues identified. In Phase II the technology necessary for the application of the catalytic concept to IGCC fuels was developed through detailed design and subscale testing. Phase III (currently not funded) will consist of full-scale combustor basket testing on natural gas and syngas.

  3. Convective stability in the presence of a catalytic chemical reaction. I.

    Science.gov (United States)

    Wankat, P. C.; Schowalter, W. R.

    1971-01-01

    A linear analysis of hydrodynamic stability has been applied to a problem in which a fluid mixture is contained between two horizontal planes. One species diffuses to the lower plane where it is destroyed by a rapid exothermic or endothermic catalytic reaction. Results show that important coupling takes place between thermal and concentration fields. This coupling gives rise to unusual stabilizing or destabilizing effects, depending upon the value of Lewis number. Several examples are discussed. It is also shown how the results can be applied to other problems involving heat and mass transfer.

  4. 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

  5. Catalytic microreactors for portable power generation

    Energy Technology Data Exchange (ETDEWEB)

    Karagiannidis, Symeon [Paul Scherer Institute, Villigen (Switzerland)

    2011-07-01

    ''Catalytic Microreactors for Portable Power Generation'' addresses a problem of high relevance and increased complexity in energy technology. This thesis outlines an investigation into catalytic and gas-phase combustion characteristics in channel-flow, platinum-coated microreactors. The emphasis of the study is on microreactor/microturbine concepts for portable power generation and the fuels of interest are methane and propane. The author carefully describes numerical and experimental techniques, providing a new insight into the complex interactions between chemical kinetics and molecular transport processes, as well as giving the first detailed report of hetero-/homogeneous chemical reaction mechanisms for catalytic propane combustion. The outcome of this work will be widely applied to the industrial design of micro- and mesoscale combustors. (orig.)

  6. Catalytic nanoarchitectonics for environmentally compatible energy generation

    Directory of Open Access Journals (Sweden)

    Hideki Abe

    2016-01-01

    Full Text Available Environmentally compatible energy management is one of the biggest challenges of the 21st century. Low-temperature conversion of chemical to electrical energy is of particular importance to minimize the impact to the environment while sustaining the consumptive economy. In this review, we shed light on one of the most versatile energy-conversion technologies: heterogeneous catalysts. We establish the integrity of structural tailoring in heterogeneous catalysts at different scales in the context of an emerging paradigm in materials science: catalytic nanoarchitectonics. Fundamental backgrounds of energy-conversion catalysis are first provided together with a perspective through state-of-the-art energy-conversion catalysis including catalytic exhaust remediation, fuel-cell electrocatalysis and photosynthesis of solar fuels. Finally, the future evolution of catalytic nanoarchitectonics is overviewed: possible combinations of heterogeneous catalysts, organic molecules and even enzymes to realize reaction-selective, highly efficient and long-life energy conversion technologies which will meet the challenge we face.

  7. Gene targeting of CK2 catalytic subunits

    Science.gov (United States)

    Lou, David Y.; Toselli, Paul; Landesman-Bollag, Esther; Dominguez, Isabel

    2013-01-01

    Protein kinase CK2 is a highly conserved and ubiquitous serine–threonine kinase. It is a tetrameric enzyme that is made up of two regulatory CK2β subunits and two catalytic subunits, either CK2α/CK2α, CK2α/ CK2α′, or CK2α′/CK2α′. Although the two catalytic subunits diverge in their C termini, their enzymatic activities are similar. To identify the specific function of the two catalytic subunits in development, we have deleted them individually from the mouse genome by homologous recombination. We have previously reported that CK2α′is essential for male germ cell development, and we now demonstrate that CK2α has an essential role in embryogenesis, as mice lacking CK2α die in mid-embryogenesis, with cardiac and neural tube defects. PMID:18594950

  8. Reactivity of organic compounds in catalytic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Minachev, Kh.M.; Bragin, O.V.

    1978-01-01

    A comprehensive review of 1976 Soviet research on catalysis delivered to the 1977 annual session of the USSR Academy of Science Council on Catalysis (Baku 6/16-20/77) covers hydrocarbon reactions, including hydrogenation and hydrogenolysis, dehydrogenation, olefin dimerization and disproportionation, and cyclization and dehydrocyclization (e.g., piperylene cyclization and ethylene cyclotrimerization); catalytic and physicochemical properties of zeolites, including cracking, dehydrogenation, and hydroisomerization catalytic syntheses and conversion of heterocyclic and functional hydrocarbon derivatives, including partial and total oxidation (e.g., of o-xylene to phthalic anhydride); syntheses of thiophenes from alkanes and hydrogen sulfide over certain dehydrogenation catalysts; catalytic syntheses involving carbon oxides ( e.g., the development of a new heterogeneous catalyst for hydroformylation of olefins), and of Co-MgO zeolitic catalysts for synthesis of aliphatic hydrocarbons from carbon dioxide and hydrogen, and fabrication of high-viscosity lubricating oils over bifunctional aluminosilicate catalysts.

  9. Catalytic Organic Transformations Mediated by Actinide Complexes

    Directory of Open Access Journals (Sweden)

    Isabell S. R. Karmel

    2015-10-01

    Full Text Available This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field.

  10. Gene targeting of CK2 catalytic subunits.

    Science.gov (United States)

    Seldin, David C; Lou, David Y; Toselli, Paul; Landesman-Bollag, Esther; Dominguez, Isabel

    2008-09-01

    Protein kinase CK2 is a highly conserved and ubiquitous serine-threonine kinase. It is a tetrameric enzyme that is made up of two regulatory CK2beta subunits and two catalytic subunits, either CK2alpha/CK2alpha, CK2alpha/CK2alpha', or CK2alpha'/CK2alpha'. Although the two catalytic subunits diverge in their C termini, their enzymatic activities are similar. To identify the specific function of the two catalytic subunits in development, we have deleted them individually from the mouse genome by homologous recombination. We have previously reported that CK2alpha' is essential for male germ cell development, and we now demonstrate that CK2alpha has an essential role in embryogenesis, as mice lacking CK2alpha die in mid-embryogenesis, with cardiac and neural tube defects.

  11. Temperature modulation of a catalytic gas sensor.

    Science.gov (United States)

    Brauns, Eike; Morsbach, Eva; Kunz, Sebastian; Baeumer, Marcus; Lang, Walter

    2014-10-29

    The use of catalytic gas sensors usually offers low selectivity, only based on their different sensitivities for various gases due to their different heats of reaction. Furthermore, the identification of the gas present is not possible, which leads to possible misinterpretation of the sensor signals. The use of micro-machined catalytic gas sensors offers great advantages regarding the response time, which allows advanced analysis of the sensor response. By using temperature modulation, additional information about the gas characteristics can be measured and drift effects caused by material shifting or environmental temperature changes can be avoided. In this work a miniaturized catalytic gas sensor which offers a very short response time (electronic device was developed, since theory shows that harmonics induced by the electronics must be avoided to generate a comprehensible signal.

  12. Highly Dense Isolated Metal Atom Catalytic Sites

    DEFF Research Database (Denmark)

    Chen, Yaxin; Kasama, Takeshi; Huang, Zhiwei

    2015-01-01

    Atomically dispersed noble-metal catalysts with highly dense active sites are promising materials with which to maximise metal efficiency and to enhance catalytic performance; however, their fabrication remains challenging because metal atoms are prone to sintering, especially at a high metal...... loading. A dynamic process of formation of isolated metal atom catalytic sites on the surface of the support, which was achieved starting from silver nanoparticles by using a thermal surface-mediated diffusion method, was observed directly by using in situ electron microscopy and in situ synchrotron X......-ray diffraction. A combination of electron microscopy images with X-ray absorption spectra demonstrated that the silver atoms were anchored on five-fold oxygen-terminated cavities on the surface of the support to form highly dense isolated metal active sites, leading to excellent reactivity in catalytic oxidation...

  13. Porous media for catalytic renewable energy conversion

    Science.gov (United States)

    Hotz, Nico

    2012-05-01

    A novel flow-based method is presented to place catalytic nanoparticles into a reactor by sol-gelation of a porous ceramic consisting of copper-based nanoparticles, silica sand, ceramic binder, and a gelation agent. This method allows for the placement of a liquid precursor containing the catalyst into the final reactor geometry without the need of impregnating or coating of a substrate with the catalytic material. The so generated foam-like porous ceramic shows properties highly appropriate for use as catalytic reactor material, e.g., reasonable pressure drop due to its porosity, high thermal and catalytic stability, and excellent catalytic behavior. The catalytic activity of micro-reactors containing this foam-like ceramic is tested in terms of their ability to convert alcoholic biofuel (e.g. methanol) to a hydrogen-rich gas mixture with low concentrations of carbon monoxide (up to 75% hydrogen content and less than 0.2% CO, for the case of methanol). This gas mixture is subsequently used in a low-temperature fuel cell, converting the hydrogen directly to electricity. A low concentration of CO is crucial to avoid poisoning of the fuel cell catalyst. Since conventional Polymer Electrolyte Membrane (PEM) fuel cells require CO concentrations far below 100 ppm and since most methods to reduce the mole fraction of CO (such as Preferential Oxidation or PROX) have CO conversions of up to 99%, the alcohol fuel reformer has to achieve initial CO mole fractions significantly below 1%. The catalyst and the porous ceramic reactor of the present study can successfully fulfill this requirement.

  14. Voltage-dependent motion of the catalytic region of voltage-sensing phosphatase monitored by a fluorescent amino acid.

    Science.gov (United States)

    Sakata, Souhei; Jinno, Yuka; Kawanabe, Akira; Okamura, Yasushi

    2016-07-05

    The cytoplasmic region of voltage-sensing phosphatase (VSP) derives the voltage dependence of its catalytic activity from coupling to a voltage sensor homologous to that of voltage-gated ion channels. To assess the conformational changes in the cytoplasmic region upon activation of the voltage sensor, we genetically incorporated a fluorescent unnatural amino acid, 3-(6-acetylnaphthalen-2-ylamino)-2-aminopropanoic acid (Anap), into the catalytic region of Ciona intestinalis VSP (Ci-VSP). Measurements of Anap fluorescence under voltage clamp in Xenopus oocytes revealed that the catalytic region assumes distinct conformations dependent on the degree of voltage-sensor activation. FRET analysis showed that the catalytic region remains situated beneath the plasma membrane, irrespective of the voltage level. Moreover, Anap fluorescence from a membrane-facing loop in the C2 domain showed a pattern reflecting substrate turnover. These results indicate that the voltage sensor regulates Ci-VSP catalytic activity by causing conformational changes in the entire catalytic region, without changing their distance from the plasma membrane.

  15. Thermal and catalytic pyrolysis of plastic waste

    Directory of Open Access Journals (Sweden)

    Débora Almeida

    2016-02-01

    Full Text Available Abstract The amount of plastic waste is growing every year and with that comes an environmental concern regarding this problem. Pyrolysis as a tertiary recycling process is presented as a solution. Pyrolysis can be thermal or catalytical and can be performed under different experimental conditions. These conditions affect the type and amount of product obtained. With the pyrolysis process, products can be obtained with high added value, such as fuel oils and feedstock for new products. Zeolites can be used as catalysts in catalytic pyrolysis and influence the final products obtained.

  16. Catalytic gasification of oil-shales

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.; Avakyan, T. [I.M. Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation); Strizhakova, Yu. [Samara State Univ. (Russian Federation)

    2012-07-01

    Nowadays, the problem of complex usage of solid fossil fuels as raw materials for obtaining of motor fuels and chemical products is becoming increasingly important. A one of possible solutions of the problem is their gasification with further processing of gaseous and liquid products. In this work we have investigated the process of thermal and catalytic gasification of Baltic and Kashpir oil-shales. We have shown that, as compared with non-catalytic process, using of nickel catalyst in the reaction increases the yield of gas, as well as hydrogen content in it, and decreases the amount of liquid products. (orig.)

  17. Heterogeneous Catalytic Ozonization of Sulfosalicylic Acid

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    This paper describes the potential of heterogeneous catalytic ozonization of sulfo-salicylic acid (SSal). It was found that catalytic ozonization in the presence of Mn-Zr-O (a modified manganese dioxide supported on silica gel) had significantly enhanced the removal rate (72%) of total organic carbon (TOC) compared with that of ozonization alone (19%). The efficient removal rate of TOC was probably due to increasing the adsorption ability of catalyst and accelerating decomposition of ozone to produce more powerful oxidants than ozone.

  18. Palladium-Catalyzed Heck Coupling Reaction of Aryl Bromides in Aqueous Media Using Tetrahydropyrimidinium Salts as Carbene Ligands

    Directory of Open Access Journals (Sweden)

    İsmail Özdemir

    2010-01-01

    Full Text Available An efficient and stereoselective catalytic system for the Heck cross coupling reaction using novel 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (1, LHX and Pd(OAc2 loading has been reported. The palladium complexes derived from the salts 1a-f prepared in situ exhibit good catalytic activity in the Heck coupling reaction of aryl bromides under mild conditions.

  19. Aged nano-structured platinum based catalyst: effect of chemical treatment on adsorption and catalytic activity.

    Science.gov (United States)

    Shim, Wang Geun; Nahm, Seung Won; Park, Hyuk Ryeol; Yun, Hyung Sun; Seo, Seong Gyu; Kim, Sang Chai

    2011-02-01

    To examine the effect of chemical treatment on the adsorption and catalytic activity of nanostructured platinum based catalyst, the aged commercial Pt/AC catalyst was pretreated with sulfuric acid (H2SO4) and a cleaning agent (Hexane). Several reliable methods such as nitrogen adsorption, X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and inductively coupled plasma (ICP) were employed to characterize the aged Pt/AC catalyst and its chemically pretreated Pt/AC catalysts. The catalytic and adsorption activities of nano-structured heterogeneous Pt/AC catalyst were investigated on the basis of toluene oxidation and adsorption isotherm data. In addition, the adsorption isotherms of toluene were used to calculate the adsorption energy distribution functions for the parent catalyst and its pre-treated nano-structured Pt/AC catalysts. It was found that sulfuric acid aqueous treatment can enhance the catalytic performance of aged Pt/AC catalyst toward catalytic oxidation of toluene. It was also shown that a comparative analysis of the energy distribution functions for nano-structured Pt/AC catalysts as well as the pore size distribution provides valuable information about their structural and energetic heterogeneity.

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

    Directory of Open Access Journals (Sweden)

    Matthias Roos

    2011-09-01

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

  1. Dual-Bed Catalytic System for Direct Conversion of Methane to Liquid Hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    N.A.S.Amin; Sriraj Ammasi

    2006-01-01

    A dual-bed catalytic system is proposed for the direct conversion of methane to liquid hydrocarbons. In this system, methane is converted in the first stage to oxidative coupling of methane (OCM) products by selective catalytic oxidation with oxygen over La-supported MgO catalyst. The second bed, comprising of the HZSM-5 zeolite catalyst, is used for the oligomerization of OCM light hydrocarbon products to liquid hydrocarbons. The effects of temperature (650-800 ℃), methane to oxygen ratio (4-10), and SiO2/Al2O3 ratio of the HZSM-5 zeolite catalyst on the process are studied. At higher reaction temperatures, there is considerable dealumination of HZSM-5, and thus its catalytic performance is reduced. The acidity of HZSM-5 in the second bed is responsible for the oligomerization reaction that leads to the formation of liquid hydrocarbons. The activities of the oligomerization sites were unequivocally affected by the SiO2/Al2O3 ratio. The relation between the acidity and the activity of HZSM-5 is studied by means of TPD-NH3 techniques. The rise in oxygen concentration is not beneficial for the C5+ selectivity, where the combustion reaction of intermediate hydrocarbon products that leads to the formation of carbon oxide (CO+CO2) products is more dominant than the oligomerization reaction. The dual-bed catalytic system is highly potential for directly converting methane to liquid fuels.

  2. 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.

  3. Final Technical Report [Development of Catalytic Alkylation and Fluoroalkylation Methods

    Energy Technology Data Exchange (ETDEWEB)

    Vicic, David A.

    2014-05-01

    In the early stages of this DOE-funded research project, we sought to prepare and study a well-defined nickel-alkyl complex containing tridentate nitrogen donor ligands. We found that reaction of (TMEDA)NiMe2 (1) with terpyridine ligand cleanly led to the formation of (terpyridyl)NiMe (2), which we also determined to be an active alkylation catalyst. The thermal stability of 2 was unlike that seen for any of the active pybox ligands, and enabled a number of key studies on alkyl transfer reactions to be performed, providing new insights into the mechanism of nickel-mediated alkyl-alkyl cross-coupling reactions. In addition to the mechanistic studies, we showed that the terpyridyl nickel compounds can catalytically cross-couple alkyl iodides in yields up to 98% and bromides in yields up to 46 %. The yields for the bromides can be increased up to 67 % when the new palladium catalyst [(tpy’)Pd-Ph]I is used. The best route to the targeted [(tpy)NiBr] (1) was found to involve the comproportionation reaction of [(dme)NiBr{sub 2}] and [Ni(COD){sub 2}] in the presence of two equivalents of terpyridine. This reaction was driven to high yields of product formation (72 % isolated) by the precipitation of 1 from THF solvent.

  4. Catalytic processes for space station waste conversion

    Science.gov (United States)

    Schoonover, M. W.; Madsen, R. A.

    1986-01-01

    Catalytic techniques for processing waste products onboard space vehicles were evaluated. The goal of the study was the conversion of waste to carbon, wash water, oxygen and nitrogen. However, the ultimate goal is conversion to plant nutrients and other materials useful in closure of an ecological life support system for extended planetary missions. The resulting process studied involves hydrolysis at 250 C and 600 psia to break down and compact cellulose material, distillation at 100 C to remove water, coking at 450 C and atmospheric pressure, and catalytic oxidation at 450 to 600 C and atmospheric pressure. Tests were conducted with a model waste to characterize the hydrolysis and coking processes. An oxidizer reactor was sized based on automotive catalytic conversion experience. Products obtained from the hydrolysis and coking steps included a solid residue, gases, water condensate streams, and a volatile coker oil. Based on the data obtained, sufficient component sizing was performed to make a preliminary comparison of the catalytic technique with oxidation for processing waste for a six-man spacecraft. Wet oxidation seems to be the preferred technique from the standpoint of both component simplicity and power consumption.

  5. 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...... understanding of the nature of the electrochemical promotion is also presented....

  6. Shungite carbon catalytic effect on coal treatment

    Energy Technology Data Exchange (ETDEWEB)

    Grigorieva, E.N.; Rozhkova, N.N. [Russian Academy of Sciences, Moscow (Russian Federation). Institute for High Temperature

    1999-07-01

    The catalytic ability of shungite carbon in reactions of coal organic matter models appeared to be due to its fullerene structure only. Transition metal sulphides present in shungite carbon are not active in the conditions of coal treatment. Shungite carbon was shown to exhibit an acceleration of thermolysis of coal and organic matter models, mainly dehydrogenation. 5 refs., 1 tabs.

  7. Catalytic site interactions in yeast OMP synthase

    DEFF Research Database (Denmark)

    Hansen, Michael Riis; Barr, Eric W.; Jensen, Kaj Frank;

    2014-01-01

    45 (2006) 5330-5342]. This behavior was investigated in the yeast enzyme by mutations in the conserved catalytic loop and 5-phosphoribosyl-1-diphosphate (PRPP) binding motif. Although the reaction is mechanistically sequential, the wild-type (WT) enzyme shows parallel lines in double reciprocal...

  8. Catalytic Amination of Alcohols, Aldehydes, and Ketones

    Science.gov (United States)

    Klyuev, M. V.; Khidekel', M. L.

    1980-01-01

    Data on the catalytic amination of alcohols and carbonyl compounds are examined, the catalysts for these processes are described, and the problems of their effectiveness, selectivity, and stability are discussed. The possible mechanisms of the reactions indicated are presented. The bibliography includes 266 references.

  9. Catalytic Asymmetric Synthesis of Phosphine Boronates.

    Science.gov (United States)

    Hornillos, Valentín; Vila, Carlos; Otten, Edwin; Feringa, Ben L

    2015-06-26

    The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of α,β-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good yields and high enantiomeric excess. The synthetic utility of the products is demonstrated through stereospecific transformations into multifunctional optically active compounds.

  10. SELECTIVE CATALYTIC REDUCTION MERCURY FIELD SAMPLING PROJECT

    Science.gov (United States)

    A lack of data still exists as to the effect of selective catalytic reduction (SCR), selective noncatalytic reduction (SNCR), and flue gas conditioning on the speciation and removal of mercury (Hg) at power plants. This project investigates the impact that SCR, SNCR, and flue gas...

  11. Performance characterization of a hydrogen catalytic heater.

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Terry Alan; Kanouff, Michael P.

    2010-04-01

    This report describes the performance of a high efficiency, compact heater that uses the catalytic oxidation of hydrogen to provide heat to the GM Hydrogen Storage Demonstration System. The heater was designed to transfer up to 30 kW of heat from the catalytic reaction to a circulating heat transfer fluid. The fluid then transfers the heat to one or more of the four hydrogen storage modules that make up the Demonstration System to drive off the chemically bound hydrogen. The heater consists of three main parts: (1) the reactor, (2) the gas heat recuperator, and (3) oil and gas flow distribution manifolds. The reactor and recuperator are integrated, compact, finned-plate heat exchangers to maximize heat transfer efficiency and minimize mass and volume. Detailed, three-dimensional, multi-physics computational models were used to design and optimize the system. At full power the heater was able to catalytically combust a 10% hydrogen/air mixture flowing at over 80 cubic feet per minute and transfer 30 kW of heat to a 30 gallon per minute flow of oil over a temperature range from 100 C to 220 C. The total efficiency of the catalytic heater, defined as the heat transferred to the oil divided by the inlet hydrogen chemical energy, was characterized and methods for improvement were investigated.

  12. The Catalytic Asymmetric Intramolecular Stetter Reaction.

    Science.gov (United States)

    de Alaniz, Javier Read; Rovis, Tomislav

    2009-05-01

    This account chronicles our efforts at the development of a catalytic asymmetric Stetter reaction using chiral triazolium salts as small molecule organic catalysts. Advances in the mechanistically related azolium-catalyzed asymmetric benzoin reaction are discussed, particularly as they apply to catalyst design. A chronological treatise of reaction discovery, catalyst optimization and reactivity extension follows.

  13. Selectivity of catalytic methods of determination.

    Science.gov (United States)

    Otto, M; Mueller, H; Werner, G

    1978-03-01

    By means of catalytic analytical methods, extremely low levels can be determined at low cost and with a high sensitivity that is equal to that of physical methods of trace analysis. The selectivity of the catalytic determinations, is, however, usually rather lower than that of other methods of trace analysis. The selectivity can sometimes be improved by modification of the indicator reaction through variation of the reagents and their concentrations, or by use of masking reagents or activators, or by combination with a separation method. Modification of the indicator reaction can be exemplified by the selective determination of osmium and ruthenium by their catalysis of the nitrate oxidation of 1-naphthylamine. By variation of the nitrate concentration and the use of 1,10-phenanthroline and 8-hydroxyquinoline as complexing agents it is possible to determine these two elements simultaneously. An especially significant increase in the selectivity is made possible by use of a preliminary separation step. If the ion to be determined is separated by solvent extraction and then catalytically determined directly in the extract, a very specific determination is possible; this technique has been called "extractive catalytic determination". This method has been used for determination of molybdenum (0.5 ng/ml) in sea-water, iron (5 ng/ml) in heavy metal salts, and copper (3 ng/ml) in the presence of numerous elements.

  14. Catalytic Activity of Metal and Metal-Oxide Catalysts in Oxidative Coupling of CH4 with CO2 under Pulse Corona Plasma%等离子体条件下金属和金属氧化物对甲烷氧化反应的催化活性

    Institute of Scientific and Technical Information of China (English)

    张秀玲; 朱爱民; 刘中凡; 李学慧; 宫为民

    2003-01-01

    @@ The uses of methane, the major component in natural gas, have been investigated by many research groups throughout the world. A number of catalysts, single or binary, have been proposed for the oxidative coupling of CH4 with CO2 as the oxidant[1~6]. Binary metal-oxide catalysts, such as La2O3-ZnO and CaO-ZnO, showed higher C2 hydrocarbon selectivity (>80%) with low CH4 conversion (<6%) at high temperatures (750~850 ℃)[7~9].

  15. Simultaneous probing of bulk liquid phase and catalytic gas-liquid-solid interface under working conditions using attenuated total reflection infrared spectroscopy.

    Science.gov (United States)

    Meemken, Fabian; Müller, Philipp; Hungerbühler, Konrad; Baiker, Alfons

    2014-08-01

    Design and performance of a reactor set-up for attenuated total reflection infrared (ATR-IR) spectroscopy suitable for simultaneous reaction monitoring of bulk liquid and catalytic solid-liquid-gas interfaces under working conditions are presented. As advancement of in situ spectroscopy an operando methodology for gas-liquid-solid reaction monitoring was developed that simultaneously combines catalytic activity and molecular level detection at the catalytically active site of the same sample. Semi-batch reactor conditions are achieved with the analytical set-up by implementing the ATR-IR flow-through cell in a recycle reactor system and integrating a specifically designed gas feeding system coupled with a bubble trap. By the use of only one spectrometer the design of the new ATR-IR reactor cell allows for simultaneous detection of the bulk liquid and the catalytic interface during the working reaction. Holding two internal reflection elements (IRE) the sample compartments of the horizontally movable cell are consecutively flushed with reaction solution and pneumatically actuated, rapid switching of the cell (interface on a catalyst-coated IRE and in the bulk liquid on a blank IRE. For a complex heterogeneous reaction, the asymmetric hydrogenation of 2,2,2-trifluoroacetophenone on chirally modified Pt catalyst the elucidation of catalytic activity/enantioselectivity coupled with simultaneous monitoring of the catalytic solid-liquid-gas interface is shown. Both catalytic activity and enantioselectivity are strongly dependent on the experimental conditions. The opportunity to gain improved understanding by coupling measurements of catalytic performance and spectroscopic detection is presented. In addition, the applicability of modulation excitation spectroscopy and phase-sensitive detection are demonstrated.

  16. Cross—Coupling of Aryl Iodides with Malononitrile Catalyzed by Palladium N—Heterocyclic Carbene Complex System

    Institute of Scientific and Technical Information of China (English)

    高诚伟; 陶晓春; 等

    2002-01-01

    Eight N-heterocyclic carbenes (NHC),generated in situ from their imidazolium salts,as ligands of palladium complexes were used for the catalytic coupling of iodobenzene with malononi-trile anion,It was found that 1,3-bis(2,4,6-trimethylphenyl)-imidazolium chloride (IMesHCl)-Pd2(dba)3 catalytic system has the highest activity to obtain phenyl malononitrile among the imidazolium salts.The substituted iodoarenes reacted with malononitrile anions by using the catalytic system to give cross-coupling products in yields from 50% to 96%.

  17. 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.

  18. 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.  ……

  19. Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

    Energy Technology Data Exchange (ETDEWEB)

    Klier, Kamil; Herman, Richard G

    2005-11-30

    This research focused on catalytic synthesis of unsymmetrical ethers as a part of a larger program involving oxygenated products in general, including alcohols, ethers, esters, carboxylic acids and their derivatives that link together environmentally compliant fuels, monomers, and high-value chemicals. The catalysts studied here were solid acids possessing strong Brnsted acid functionalities. The design of these catalysts involved anchoring the acid groups onto inorganic oxides, e.g. surface-grafted acid groups on zirconia, and a new class of mesoporous solid acids, i.e. propylsulfonic acid-derivatized SBA-15. The former catalysts consisted of a high surface concentration of sulfate groups on stable zirconia catalysts. The latter catalyst consists of high surface area, large pore propylsulfonic acid-derivatized silicas, specifically SBA-15. In both cases, the catalyst design and synthesis yielded high concentrations of acid sites in close proximity to one another. These materials have been well-characterization in terms of physical and chemical properties, as well as in regard to surface and bulk characteristics. Both types of catalysts were shown to exhibit high catalytic performance with respect to both activity and selectivity for the bifunctional coupling of alcohols to form ethers, which proceeds via an efficient SN2 reaction mechanism on the proximal acid sites. This commonality of the dual-site SN2 reaction mechanism over acid catalysts provides for maximum reaction rates and control of selectivity by reaction conditions, i.e. pressure, temperature, and reactant concentrations. This research provides the scientific groundwork for synthesis of ethers for energy applications. The synthesized environmentally acceptable ethers, in part derived from natural gas via alcohol intermediates, exhibit high cetane properties, e.g. methylisobutylether with cetane No. of 53 and dimethylether with cetane No. of 55-60, or high octane properties, e.g. diisopropylether with

  20. Study on the Carbon-Methanation and Catalytic Activity of Ru/AC for Ammonia Synthesis

    Institute of Scientific and Technical Information of China (English)

    祝一锋; 李小年; 季德春; 刘化章

    2004-01-01

    The effects of promoters K, Ba, Sm on the resistance to carbon-methanation and catalytic activity of ruthenium supported on active carbon (Ru/AC) for ammonia synthesis have been studied by means of TG-DTG (thermalgravity-differential thermalgravity), temperature-programmed desorption, and activity test. Promoters Ba,K, and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly. Much higher activity can be reached for Ru/AC catalyst with bi- or tri-promoters. Indeed, the triply promoted catalyst showed the highest activity, coupled to a surprisingly high resistance to methanation. The ability of resistance of promoter to methanation of Ru/AC catalyst is dependent on the adsorption intensity of hydrogen. The strong adsorption of hydrogen would enhance methanation and impact the adsorption of nitrogen, which results in the decrease of catalytic activity.

  1. Computer-aided modeling framework – a generic modeling template for catalytic membrane fixed bed reactors

    DEFF Research Database (Denmark)

    Fedorova, Marina; Sin, Gürkan; Gani, Rafiqul

    2013-01-01

    This work focuses on development of computer-aided modeling framework. The framework is a knowledge-based system that is built on a generic modeling language and structured based on workflows for different general modeling tasks. The overall objective of this work is to support the model developers...... and users to generate and test models systematically, efficiently and reliably. In this way, development of products and processes can be faster, cheaper and very efficient. In this contribution, as part of the framework a generic modeling template for the systematic derivation of problem specific catalytic...... membrane fixed bed models is developed. The application of the modeling template is highlighted with a case study related to the modeling of a catalytic membrane reactor coupling dehydrogenation of ethylbenzene with hydrogenation of nitrobenzene....

  2. Synthetic and Thermodynamic Investigations of Ancillary Ligand Influence on Catalytic Organometallic Systems. Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Nolan, Steven

    2003-03-20

    During the grant period we have been involved in synthesizing and experimentally determining solution enthalpy values associated with partially fluorinated ligands. This has lead to the publication of manuscripts dealing with synthetic, calorimetric and catalytic behavior of partially fluorinated ligands. The collaboration with Los Alamos researchers has lead to the publication of catalytic results in sc CO{sub 2} which have proven very interesting. Furthermore, we have also examined ligands that behave as phosphine mimics. The N-heterocyclic carbenes have been explored as alternatives for tertiary phosphines and have resulted in the design and construction of efficient palladium and nickel system capable of performing C-C and C-N cross coupling reactions. The initial studies in this areas were made possible by exploratory work conducted under the DOE/EPSCoR grant.

  3. Synthesis,Characterization and Catalytic Properties of Mesoporous HPMo/SiO2 Composite

    Institute of Scientific and Technical Information of China (English)

    YAN Xuemin; YAN Jiabao; MEI Ping; LEI Jiaheng

    2008-01-01

    A novel mesoporous HPMo/SiO2 composite was synthesized by the sol-gel method with triblock copolymer EO20PO70EO20 as template.The properties of the product were characterized by X-ray diffraction,transmission electron microscopy,N2 adsorption-desorption isotherms,Fourier transform infrared spectrometer and inductively-coupled plasma analysis.The experimental results show that the product has a very ordered hexagonal mesostructure,and the HPMo is immobilized into the framework of silica.The final mesoporous composite shows excellent stability in polar solvents.Results of catalytic tests indicate that the composite is an effective catalyst for oxidation of dibenzothiophen,and there are few activity losses even after the third cycle of uses.The high catalytic activity and good insolubility make it a promising catalyst in oxidative desulfurization process.

  4. Synthesis and characterization of vanadium nanoparticles on activated carbon and their catalytic activity in thiophene hydrodesulphurization

    Energy Technology Data Exchange (ETDEWEB)

    Pinto, Susana [Centro de Catalisis, Petroleo y Petroquimica, Escuela de Quimica, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 40679 (Venezuela); Centro de Quimica Organometalica y Macromolecular, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 47778 (Venezuela); D' Ornelas, Lindora [Centro de Quimica Organometalica y Macromolecular, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 47778 (Venezuela); Betancourt, Paulino [Centro de Catalisis, Petroleo y Petroquimica, Escuela de Quimica, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 40679 (Venezuela)], E-mail: pbetanco@strix.ciens.ucv.ve

    2008-06-30

    Vanadium nanoparticles ({approx}7 nm) stabilized on activated carbon were synthesized by the reduction of VCl{sub 3}.3THF with K[BEt{sub 3}H]. This material was characterized by inductive coupled plasma-atomic emission spectroscopy (ICP-AES), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) analyses. The catalytic performance of the carbon-supported vanadium was studied using thiophene hydrodesulfurization (HDS) as model reaction at 300 deg. C and P = 1 atm. The catalytic activity of the vanadium carbide phase on the activated carbon carrier was more significant than that of the reference catalysts, alumina supported NiMoS. The method proposed for the synthesis of such a catalyst led to an excellent performance of the HDS process.

  5. Molecular basis of the general base catalysis of an α/β-hydrolase catalytic triad.

    Science.gov (United States)

    Sun, Yueru; Yin, Shuhui; Feng, Yitao; Li, Jie; Zhou, Jiahai; Liu, Changdong; Zhu, Guang; Guo, Zhihong

    2014-05-30

    The serine-histidine-aspartate triad is well known for its covalent, nucleophilic catalysis in a diverse array of enzymatic transformations. Here we show that its nucleophilicity is shielded and its catalytic role is limited to being a specific general base by an open-closed conformational change in the catalysis of (1R,6R)-2-succinyl-6-hydroxy-2,4-cyclohexadiene-1-carboxylate synthase (or MenH), a typical α/β-hydrolase fold enzyme in the vitamin K biosynthetic pathway. This enzyme is found to adopt an open conformation without a functional triad in its ligand-free form and a closed conformation with a fully functional catalytic triad in the presence of its reaction product. The open-to-closed conformational transition involves movement of half of the α-helical cap domain, which causes extensive structural changes in the α/β-domain and forces the side chain of the triad histidine to adopt an energetically disfavored gauche conformation to form the functional triad. NMR analysis shows that the inactive open conformation without a triad prevails in ligand-free solution and is converted to the closed conformation with a properly formed triad by the reaction product. Mutation of the residues crucial to this open-closed transition either greatly decreases or completely eliminates the enzyme activity, supporting an important catalytic role for the structural change. These findings suggest that the open-closed conformational change tightly couples formation of the catalytic triad to substrate binding to enhance the substrate specificities and simultaneously shield the nucleophilicity of the triad, thus allowing it to expand its catalytic power beyond the nucleophilic catalysis.

  6. PREPARATION AND CATALYTIC ACTIVITY OF BIOACTIVE FIBERS

    Institute of Scientific and Technical Information of China (English)

    Yu-yuan Yao; Wen-xing Chen; Bao-yan Zhao; Shen-shui Lü

    2006-01-01

    Two kinds of water-soluble metallophthalocyanines, binuclear cobalt phthalocyanine (Co2Pc2) and binuclear ferric phthalocyanine (Fe2Pc2), were synthesized through phenylanhydride-urea route and characterized by elemental analysis and FT-IR spectra. Binuclear metallophthalocyanine derivatives (Mt2Pc2) were immobilized on silk fibers and modified viscose fibers to construct bioactive fibers of mimic enzyme. Mt2Pc2 was used as the active center ofbioactive fibers, viscose and silk fibers as the microenvironments. The catalytic oxidation ability of bioactive fibers on the malodors of methanthiol and hydrogen sulfide was investigated at room temperature. The experimental results indicated that the catalytic activity of such bioactive fibers was closely correlative to the types ofbioactive fibers and substrates.

  7. Janus droplet as a catalytic micromotor

    CERN Document Server

    Shklyaev, Sergey

    2015-01-01

    Self-propulsion of a Janus droplet in a solution of surfactant, which reacts on a half of a drop surface, is studied theoretically. The droplet acts as a catalytic motor creating a concentration gradient, which generates its surface-tension-driven motion; the self-propulsion speed is rather high, $60\\; {\\rm \\mu m/s}$ and more. This catalytic motor has several advantages over other micromotors: simple manufacturing, easily attained neutral buoyancy. In contrast to a single-fluid droplet, which demonstrates a self-propulsion as a result of symmetry breaking instability, for Janus one no stability threshold exists; hence, the droplet radius can be scaled down to micrometers. The paper was finalized and submitted by Denis S. Goldobin after Sergey Sklyaev had sadly passed away on June 2, 2014.

  8. Control of a catalytic fluid cracker

    Energy Technology Data Exchange (ETDEWEB)

    Arbel, A.; Huang, Z.; Rinard, I.; Shinnar, R.

    1993-12-13

    Control offers an important tool for savings in refineries, mainly by integration of process models into on-line control. This paper is part of a research effort to better understand problems of partial control; control of a Fluid Catalytic Cracker (FCC) is used as example. Goal is to understand better the control problems of an FCC in context of model based control of a refinery, and to understand the general problem of designing partial control systems.

  9. Materials for High-Temperature Catalytic Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Ersson, Anders

    2003-04-01

    Catalytic combustion is an environmentally friendly technique to combust fuels in e.g. gas turbines. Introducing a catalyst into the combustion chamber of a gas turbine allows combustion outside the normal flammability limits. Hence, the adiabatic flame temperature may be lowered below the threshold temperature for thermal NO{sub X} formation while maintaining a stable combustion. However, several challenges are connected to the application of catalytic combustion in gas turbines. The first part of this thesis reviews the use of catalytic combustion in gas turbines. The influence of the fuel has been studied and compared over different catalyst materials. The material section is divided into two parts. The first concerns bimetallic palladium catalysts. These catalysts showed a more stable activity compared to their pure palladium counterparts for methane combustion. This was verified both by using an annular reactor at ambient pressure and a pilot-scale reactor at elevated pressures and flows closely resembling the ones found in a gas turbine combustor. The second part concerns high-temperature materials, which may be used either as active or washcoat materials. A novel group of materials for catalysis, i.e. garnets, has been synthesised and tested in combustion of methane, a low-heating value gas and diesel fuel. The garnets showed some interesting abilities especially for combustion of low-heating value, LHV, gas. Two other materials were also studied, i.e. spinels and hexa aluminates, both showed very promising thermal stability and the substituted hexa aluminates also showed a good catalytic activity. Finally, deactivation of the catalyst materials was studied. In this part the sulphur poisoning of palladium, platinum and the above-mentioned complex metal oxides has been studied for combustion of a LHV gas. Platinum and surprisingly the garnet were least deactivated. Palladium was severely affected for methane combustion while the other washcoat materials were

  10. Selective Catalytic Reduction of NO with Methane

    Institute of Scientific and Technical Information of China (English)

    Xiang Gao; Qi Yu; Limin Chen

    2003-01-01

    The removal of nitrogen oxides from exhaust gases has attracted great attention in recent years, and many approaches have been developed depending on the application. Methane, the main component of natural gas, has great potential as a NO reductant. In this paper, a number of catalysts previous reported for this catalytic reduction of NO have been reviewed, including a direct comparison of the relative activities and effective factors of the catalysts. Reaction mechanisms have also been explored preliminarily.

  11. Zeolitic catalytic conversion of alochols to hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

    2017-01-03

    A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.

  12. Catalytic fast pyrolysis of lignocellulosic biomass

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Changjun; Wang, Huamin; Karim, Ayman M.; Sun, Junming; Wang, Yong

    2014-11-21

    Increasing energy demand, especially in the transportation sector, and soaring CO2 emissions necessitate the exploitation of renewable sources of energy. Despite the large variety of new energy Q3 carriers, liquid hydrocarbon still appears to be the most attractive and feasible form of transportation fuel taking into account the energy density, stability and existing infrastructure. Biomass is an abundant, renewable source of energy; however, utilizing it in a cost-effective way is still a substantial challenge. Lignocellulose is composed of three major biopolymers, namely cellulose, hemicellulose and lignin. Fast pyrolysis of biomass is recognized as an efficient and feasible process to selectively convert lignocellulose into a liquid fuel—bio-oil. However bio-oil from fast pyrolysis contains a large amount of oxygen, distributed in hundreds of oxygenates. These oxygenates are the cause of many negative properties, such as low heating values, high corrosiveness, high viscosity, and instability; they also greatly Q4 limit the application of bio-oil particularly as transportation fuel. Hydrocarbons derived from biomass are most attractive because of their high energy density and compatibility with the existing infrastructure. Thus, converting lignocellulose into transportation fuels via catalytic fast pyrolysis has attracted much attention. Many studies related to catalytic fast pyrolysis of biomass have been published. The main challenge of this process is the development of active and stable catalysts that can deal with a large variety of decomposition intermediates from lignocellulose. This review starts with the current understanding of the chemistry in fast pyrolysis of lignocellulose and focuses on the development of catalysts in catalytic fast pyrolysis. Recent progress in the experimental studies on catalytic fast pyrolysis of biomass is also summarized with the emphasis on bio-oil yields and quality.

  13. Thermal and catalytic pyrolysis of plastic waste

    OpenAIRE

    Débora Almeida; Maria de Fátima Marques

    2016-01-01

    Abstract The amount of plastic waste is growing every year and with that comes an environmental concern regarding this problem. Pyrolysis as a tertiary recycling process is presented as a solution. Pyrolysis can be thermal or catalytical and can be performed under different experimental conditions. These conditions affect the type and amount of product obtained. With the pyrolysis process, products can be obtained with high added value, such as fuel oils and feedstock for new products. Zeolit...

  14. Catalytic pyrolysis of olive mill wastewater sludge

    Science.gov (United States)

    Abdellaoui, Hamza

    From 2008 to 2013, an average of 2,821.4 kilotons/year of olive oil were produced around the world. The waste product of the olive mill industry consists of solid residue (pomace) and wastewater (OMW). Annually, around 30 million m3 of OMW are produced in the Mediterranean area, 700,000 m3 year?1 in Tunisia alone. OMW is an aqueous effluent characterized by an offensive smell and high organic matter content, including high molecular weight phenolic compounds and long-chain fatty acids. These compounds are highly toxic to micro-organisms and plants, which makes the OMW a serious threat to the environment if not managed properly. The OMW is disposed of in open air evaporation ponds. After evaporation of most of the water, OMWS is left in the bottom of the ponds. In this thesis, the effort has been made to evaluate the catalytic pyrolysis process as a technology to valorize the OMWS. The first section of this research showed that 41.12 wt. % of the OMWS is mostly lipids, which are a good source of energy. The second section proved that catalytic pyrolysis of the OMWS over red mud and HZSM-5 can produce green diesel, and 450 °C is the optimal reaction temperature to maximize the organic yields. The last section revealed that the HSF was behind the good fuel-like properties of the OMWS catalytic oils, whereas the SR hindered the bio-oil yields and quality.

  15. Studies of catalytic coal gasification with steam

    Directory of Open Access Journals (Sweden)

    Porada Stanisław

    2016-09-01

    Full Text Available One of the promising processes, belonging to the so-called clean coal technologies, is catalytic coal gasification. The addition of a catalyst results in an increased process rate, in which synthesis gas is obtained. Therefore, the subject of this research was catalytic gasification of low-ranking coal which, due to a high reactivity, meets the requirements for fuels used in the gasification process. Potassium and calcium cations in an amount of 0.85, 1.7 and 3.4% by weight were used as catalytically active substances. Isothermal measurements were performed at 900°C under a pressure of 2 MPa using steam as a gasifying agent. On the basis of kinetic curves, the performance of main gasification products as well as carbon conversion degree were determined. The performed measurements allowed the determination of the type and amount of catalyst that ensure the most efficient gasification process of the coal ‘Piast’ in an atmosphere of steam.

  16. Highly sensitive catalytic spectrophotometric determination of ruthenium

    Science.gov (United States)

    Naik, Radhey M.; Srivastava, Abhishek; Prasad, Surendra

    2008-01-01

    A new and highly sensitive catalytic kinetic method (CKM) for the determination of ruthenium(III) has been established based on its catalytic effect on the oxidation of L-phenylalanine ( L-Pheala) by KMnO 4 in highly alkaline medium. The reaction has been followed spectrophotometrically by measuring the decrease in the absorbance at 526 nm. The proposed CKM is based on the fixed time procedure under optimum reaction conditions. It relies on the linear relationship where the change in the absorbance (Δ At) versus added Ru(III) amounts in the range of 0.101-2.526 ng ml -1 is plotted. Under the optimum conditions, the sensitivity of the proposed method, i.e. the limit of detection corresponding to 5 min is 0.08 ng ml -1, and decreases with increased time of analysis. The method is featured with good accuracy and reproducibility for ruthenium(III) determination. The ruthenium(III) has also been determined in presence of several interfering and non-interfering cations, anions and polyaminocarboxylates. No foreign ions interfered in the determination ruthenium(III) up to 20-fold higher concentration of foreign ions. In addition to standard solutions analysis, this method was successfully applied for the quantitative determination of ruthenium(III) in drinking water samples. The method is highly sensitive, selective and very stable. A review of recently published catalytic spectrophotometric methods for the determination of ruthenium(III) has also been presented for comparison.

  17. A revolution in micropower : the catalytic nanodiode.

    Energy Technology Data Exchange (ETDEWEB)

    Cross, Karen Charlene; Heller, Edwin J.; Figiel, Jeffrey James; Coker, Eric Nicholas; Creighton, James Randall; Koleske, Daniel David; Bogart, Katherine Huderle Andersen; Coltrin, Michael Elliott; Pawlowski, Roger Patrick; Baucom, Kevin C.

    2010-11-01

    Our ability to field useful, nano-enabled microsystems that capitalize on recent advances in sensor technology is severely limited by the energy density of available power sources. The catalytic nanodiode (reported by Somorjai's group at Berkeley in 2005) was potentially an alternative revolutionary source of micropower. Their first reports claimed that a sizable fraction of the chemical energy may be harvested via hot electrons (a 'chemicurrent') that are created by the catalytic chemical reaction. We fabricated and tested Pt/GaN nanodiodes, which eventually produced currents up to several microamps. Our best reaction yields (electrons/CO{sub 2}) were on the order of 10{sup -3}; well below the 75% values first reported by Somorjai (we note they have also been unable to reproduce their early results). Over the course of this Project we have determined that the whole concept of 'chemicurrent', in fact, may be an illusion. Our results conclusively demonstrate that the current measured from our nanodiodes is derived from a thermoelectric voltage; we have found no credible evidence for true chemicurrent. Unfortunately this means that the catalytic nanodiode has no future as a micropower source.

  18. Aziridine- and Azetidine-Pd Catalytic Combinations. Synthesis and Evaluation of the Ligand Ring Size Impact on Suzuki-Miyaura Reaction Issues

    Directory of Open Access Journals (Sweden)

    Hamza Boufroura

    2017-01-01

    Full Text Available The synthesis of new vicinal diamines based on aziridine and azetidine cores as well as the comparison of their catalytic activities as ligand in the Suzuki-Miyaura coupling reaction are described in this communication. The synthesis of three- and four-membered ring heterocycles substituted by a methylamine pendant arm is detailed from the parent nitrile derivatives. Complexation to palladium under various conditions has been examined affording vicinal diamines or amine-imidate complexes. The efficiency of four new catalytic systems is compared in the preparation of variously substituted biaryls. Aziridine- and azetidine-based catalytic systems allowed Suzuki-Miyaura reactions from aryl halides including chlorides with catalytic loadings until 0.001% at temperatures ranging from 100 °C to r.t. The evolution of the Pd-metallacycle ring strain moving from azetidine to aziridine in combination with a methylamine or an imidate pendant arm impacted the Suzuki-Miyaura reaction issue.

  19. Effect of nitrogen-containing impurities on the activity of perovskitic catalysts for the catalytic combustion of methane.

    Science.gov (United States)

    Buchneva, Olga; Gallo, Alessandro; Rossetti, Ilenia

    2012-11-05

    LaMnO(3), either pure or doped with 10 mol % Sr, has been prepared by flame pyrolysis in nanostructured form. Such catalysts have been tested for the catalytic flameless combustion of methane, achieving very high catalytic activity. The resistance toward poisoning by some model N-containing impurities has been checked in order to assess the possibility of operating the flameless catalytic combustion with biogas, possibly contaminated by S- or N-based compounds. This would be a significant improvement from the environmental point of view because the application of catalytic combustion to gas turbines would couple improved energy conversion efficiency and negligible noxious emissions, while the use of biogas would open the way to energy production from a renewable source by means of very efficient technologies. A different behavior has been observed for the two catalysts; namely, the undoped sample was more or less heavily poisoned, whereas the Sr-doped sample showed slightly increasing activity upon dosage of N-containing compounds. A possible reaction mechanism has been suggested, based on the initial oxidation of the organic backbone, with the formation of NO. The latter may adsorb more or less strongly depending on the availability of surface oxygen vacancies (i.e., depending on doping). Decomposition of NO may leave additional activated oxygen species on the surface, available for low-temperature methane oxidation and so improving the catalytic performance.

  20. Environmental Topology and Water Availability Modulates the Catalytic Activity of β-Galactosidase Entrapped in a Nanosporous Silicate Matrix.

    Science.gov (United States)

    Burgos, M Ines; Velasco, Manuel I; Acosta, Rodolfo H; Perillo, María A

    2016-11-04

    In the present work we studied the catalytic activity of E. coli β-Gal confined in a nanoporous silicate matrix (Eβ-Gal) at different times after the beginning of the sol-gel polymerization process. Enzyme kinetic experiments with two substrates (ONPG and PNPG) that differed in the rate-limiting steps of the reaction mechanism for their β-Gal-catalyzed hydrolysis, measurements of transverse relaxation times (T2) of water protons through (1)H-NMR, and scanning electron microscopy analysis of the gel nanostructure, were performed. In conjunction, results provided evidence that water availability is crucial for the modulation observed in the catalytic activity of β-Gal as long as water participate in the rate limiting step of the reaction (only with ONPG). In this case, a biphasic rate vs. substrate concentration was obtained exhibiting one phase with catalytic rate constant (kcA), similar to that observed in solution, and another phase with a higher and aging-dependent catalytic rate constant (kcB). More structured water populations (lower T2) correlates with higher catalytic rate constants (kcB). The T2-kcB negative correlation observed along the aging of gels within the 15-days period assayed reinforces the coupling between water structure and the hydrolysis catalysis inside gels.

  1. Integrable Couplings of the Coupled Burgers Hierarchy

    Institute of Scientific and Technical Information of China (English)

    XIATie-Cheng; CHENXiao-Hong; CHENDeng-Yuan; ZHANGYu-Feng

    2004-01-01

    In this letter, a new loop algebra G is constructed, from which a new isospectral problem is established. It follows that integrable couplings of the well-known coupled Burgers hierarchy are obtained.

  2. Concept and progress in coupling of dehydrogenation and hydrogenation reactions through catalysts

    Indian Academy of Sciences (India)

    C V Pramod; C Raghavendra; K Hari Prasad Reddy; G V Ramesh Babu; K S Rama Rao; B David Raju

    2014-03-01

    This review focuses on the importance of coupling of catalytic reactions which involves dehydrogenation and hydrogenation simultaneously and the study of catalytic materials that are designed, adopted and/or modified for these reactions. The special features of these reactions are minimization of H2 utilization and reduction in production cost. Structural and textural properties also play a decisive role in this kind of coupled reactions. This particular review although not comprehensive discusses the significant progress made in the area of coupled reactions and also helps future researchers or engineers to find out the improvements required in areas such as advancements in catalytic material preparation, design of the new reactors and the application of new technologies.

  3. Coupling strength versus coupling impact in nonidentical bidirectionally coupled dynamics

    Science.gov (United States)

    Laiou, Petroula; Andrzejak, Ralph G.

    2017-01-01

    The understanding of interacting dynamics is important for the characterization of real-world networks. In general, real-world networks are heterogeneous in the sense that each node of the network is a dynamics with different properties. For coupled nonidentical dynamics symmetric interactions are not straightforwardly defined from the coupling strength values. Thus, a challenging issue is whether we can define a symmetric interaction in this asymmetric setting. To address this problem we introduce the notion of the coupling impact. The coupling impact considers not only the coupling strength but also the energy of the individual dynamics, which is conveyed via the coupling. To illustrate this concept, we follow a data-driven approach by analyzing signals from pairs of coupled model dynamics using two different connectivity measures. We find that the coupling impact, but not the coupling strength, correctly detects a symmetric interaction between pairs of coupled dynamics regardless of their degree of asymmetry. Therefore, this approach allows us to reveal the real impact that one dynamics has on the other and hence to define symmetric interactions in pairs of nonidentical dynamics.

  4. Coupling coefficients for coupled-cavity lasers

    Energy Technology Data Exchange (ETDEWEB)

    Lang, R.J.; Yariv, A.

    1987-03-01

    The authors derive simple, analytic formulas for the field coupling coefficients in a two-section coupled-cavity laser using a local field rate equation treatment. They show that there is a correction to the heuristic formulas based on power flow calculated by Marcuse; the correction is in agreement with numerical calculations from a coupled-mode approach.

  5. Modeling the oxidative coupling of methane:Heterogeneous chemistry coupled with 3D flow field simulation

    Institute of Scientific and Technical Information of China (English)

    Yaghobi Nakisa; Ghoreishy Mir Hamid Reza

    2009-01-01

    The oxidative coupling of methane (OCM) over titanate perovskite catalyst has been developed by three-dimensional numerical simulations of flow field coupled with heat transfer as well as heterogeneous kinetic model.The reaction was assumed to take place both in the gas phase and on the catalytic surface.Kinetic rate constants were experimentally obtained using a ten step kinetic model.The simulation results agree quite well with the data of OCM experiments,which were used to investigate the effect of temperature on the selectivity and conversion obtained in the methane oxidative coupling process.The conversion of methane linearly increased with temperature and the selectivity of C2 was practically constant in the temperature range of 973-1073 K.The study shows that CFD tools make it possible to implement the heterogeneous kinetic model even for high exothermic reaction such as OCM.

  6. Heterogeneous catalytic materials solid state chemistry, surface chemistry and catalytic behaviour

    CERN Document Server

    Busca, Guido

    2014-01-01

    Heterogeneous Catalytic Materials discusses experimental methods and the latest developments in three areas of research: heterogeneous catalysis; surface chemistry; and the chemistry of catalysts. Catalytic materials are those solids that allow the chemical reaction to occur efficiently and cost-effectively. This book provides you with all necessary information to synthesize, characterize, and relate the properties of a catalyst to its behavior, enabling you to select the appropriate catalyst for the process and reactor system. Oxides (used both as catalysts and as supports for cata

  7. One-pot synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines using supported gold and base as catalysts

    DEFF Research Database (Denmark)

    Kegnæs, Søren; Mielby, Jerrik Jørgen; Mentzel, Uffe Vie

    2012-01-01

    Synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines via intermediate formation of methyl esters is highly efficient and selective when using a catalytic system comprised of supported gold nanoparticles and added base in methanol.......Synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines via intermediate formation of methyl esters is highly efficient and selective when using a catalytic system comprised of supported gold nanoparticles and added base in methanol....

  8. Dynamical quorum sensing and synchronization in collections of excitable and oscillatory catalytic particles

    Science.gov (United States)

    Tinsley, M. R.; Taylor, A. F.; Huang, Z.; Wang, F.; Showalter, K.

    2010-06-01

    We present experimental studies of interacting excitable and oscillatory catalytic particles in well-stirred and spatially distributed systems. A number of distinct paths to synchronized oscillatory behavior are described. We present an example of a Kuramoto type transition in a well-stirred system with a collective rhythm emerging on increasing the number density of oscillatory particles. Groups of spatially distributed oscillatory particles become entrained to a common frequency by organizing centers. Quorum sensing type transitions are found in populations of globally and locally coupled excitable particles, with a sharp transition from steady state to fully synchronized behavior at a critical density or group size.

  9. 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.

  10. Novel catalytic and mechanistic studies on wastewater denitrification with hydrogen.

    Science.gov (United States)

    Theologides, C P; Olympiou, G G; Savva, P G; Pantelidou, N A; Constantinou, B K; Chatziiona, V K; Valanidou, L Y; Piskopianou, C T; Costa, C N

    2014-01-01

    The present work reports up-to-date information regarding the reaction mechanism of the catalytic hydrogenation of nitrates in water media. In the present mechanistic study, an attempt is made, for the first time, to elucidate the crucial role of several catalysts and reaction parameters in the mechanism of the NO(3)(-)/H(2) reaction. Steady-state isotopic transient kinetic analysis (SSITKA) experiments coupled with ex situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) were performed on supported Pd-Cu catalysts for the NO(3)(-)/H(2) and NO(3)(-)/H(2)/O(2) reactions. The latter experiments revealed that the formation and surface coverage of various adsorbed active intermediate N-species on the support or Pd/Cu metal surface is significantly favored in the presence of TiO(2) in the support mixture and in the presence of oxygen in the reaction's gaseous feed stream. The differences in the reactivity of these adsorbed N-species, found in the present work, adequately explain the large effect of the chemical composition of the support and the gas feed composition on catalyst behaviour (activity and selectivity). The present study leads to solid mechanistic evidence concerning the presence of a hydrogen spillover process from the metal to the support. Moreover, this study shows that Cu clusters are active sites for the reduction of nitrates to nitrites.

  11. Catalytic bioscavengers in nerve agent poisoning: A promising approach?

    Science.gov (United States)

    Worek, Franz; Thiermann, Horst; Wille, Timo

    2016-02-26

    The repeated use of the nerve agent sarin against civilians in Syria in 2013 emphasizes the continuing threat by chemical warfare agents. Multiple studies demonstrated a limited efficacy of standard atropine-oxime treatment in nerve agent poisoning and called for the development of alternative and more effective treatment strategies. A novel approach is the use of stoichiometric or catalytic bioscavengers for detoxification of nerve agents in the systemic circulation prior to distribution into target tissues. Recent progress in the design of enzyme mutants with reversed stereo selectivity resulting in improved catalytic activity and their use in in vivo studies supports the concept of catalytic bioscavengers. Yet, further research is necessary to improve the catalytic activity, substrate spectrum and in vivo biological stability of enzyme mutants. The pros and cons of catalytic bioscavengers will be discussed in detail and future requirements for the development of catalytic bioscavengers will be proposed.

  12. Catalytic Synthesis Methods for Triazolopyrimidine Derivatives

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A new method for catalyzed synthesis of triazolopyrimidine derivatives is reported. Aikylamine reaction with dialkyl cyanodithioiminocarbonate was catalyzed by quaternary ammonium salts at room temperature to yield 3-alkylamine-5-amino-1,2,4-triazole in good quality and high yields. After imidization and reaction with an α,β-unsaturated acid derivative, the reaction intermediate was hydrolyzed in the presence of a Lewis acid to obtain the target product. This novel catalytic method for triazolopyrimidine derivatives can be carried out under inexpen-sive and mild conditions, and is safe and environmentally friendly. IH NMR results for all intermediates are re-ported.

  13. Thin film porous membranes for catalytic sensors

    Energy Technology Data Exchange (ETDEWEB)

    Hughes, R.C.; Boyle, T.J.; Gardner, T.J. [and others

    1997-06-01

    This paper reports on new and surprising experimental data for catalytic film gas sensing resistors coated with nanoporous sol-gel films to impart selectivity and durability to the sensor structure. This work is the result of attempts to build selectivity and reactivity to the surface of a sensor by modifying it with a series of sol-gel layers. The initial sol-gel SiO{sub 2} layer applied to the sensor surprisingly showed enhanced O{sub 2} interaction with H{sub 2} and reduced susceptibility to poisons such as H{sub 2}S.

  14. Catalytic Synthesis of Nitriles in Continuous Flow

    DEFF Research Database (Denmark)

    Nordvang, Emily Catherine

    , alternative path to acetonitrile from ethanol via the oxidative dehydrogenation of ethylamine. The catalytic activity and product ratios of the batch and continuous flow reactions are compared and the effect of reaction conditions on the reaction is investigated. The effects of ammonia in the reaction...... dehydrogenation of ethylamine and post-reaction purging.Chapter 4 outlines the application of RuO2/Al2O3 catalysts to the oxidative dehydrogenation of benzylamine in air, utilizing a new reaction setup. Again, batch and continuous flow reactions are compared and the effects of reaction conditions, ammonia...

  15. 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.

  16. Catalytic wet oxidation of black liquor

    OpenAIRE

    Viader Riera, Gerard

    2012-01-01

    The major aspects of wet air oxidation and catalytic wet air oxidation have been reviewed in this work paying special attention to the reaction mechanisms, kinetics and the industrial process. In the experimental section a set of heterogeneous catalysts have been tested in the wet oxidation of non-wood black liquor. The oxidation runs were performed batchwise in a laboratory-scale mechanically stirred slurry reactor for 1 h at a temperature of 170°C and total pressure of 12 bar. Pure oxygen w...

  17. Catalytic enantioselective synthesis of quaternary carbon stereocentres

    Science.gov (United States)

    Quasdorf, Kyle W.; Overman, Larry E.

    2014-12-01

    Quaternary carbon stereocentres--carbon atoms to which four distinct carbon substituents are attached--are common features of molecules found in nature. However, before recent advances in chemical catalysis, there were few methods of constructing single stereoisomers of this important structural motif. Here we discuss the many catalytic enantioselective reactions developed during the past decade for the synthesis of single stereoisomers of such organic molecules. This progress now makes it possible to incorporate quaternary stereocentres selectively in many organic molecules that are useful in medicine, agriculture and potentially other areas such as flavouring, fragrances and materials.

  18. 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 differ...... different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis....

  19. Study and Analysis on Naphtha Catalytic Reforming Reactor Simulation

    Institute of Scientific and Technical Information of China (English)

    Liang Ke min; Song Yongji; Pan Shiwei

    2004-01-01

    A naphtha catalytic reforming unit with four reactors connected in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reaction characteristics based on idealizing the complex naphtha mixture to represent the paraffin, naphthene, and aromatic groups with individual compounds. The simulation results based on above models agree very well with actual operating data of process unit.

  20. A study on naphtha catalytic reforming reactor simulation and analysis

    Institute of Scientific and Technical Information of China (English)

    LIANG Ke-min; GUO Hai-yan; PAN Shi-wei

    2005-01-01

    A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation unit data.

  1. Catalytic wet air oxidation of phenol over Co-doped Fe3O4 nanoparticles

    Science.gov (United States)

    Song, Xu Chun; Zheng, Yi Fan; Yin, Hao Yong

    2013-08-01

    The Fe3O4 nanoparticles doped with cobalt ions have been successfully synthesized by the co-precipitation process. The X-ray diffraction, inductively coupled plasma, scanning electron microscopy, and transmission electron microscopy were used to characterize the as-prepared nanoparticles. The results show that the phase structure of the nanoparticles is spinel structure of pure Fe3O4 with the particle size ranging from 40 to 50 nm. The Co-doping concentration can be controlled by changing the atomic ratio of the stock materials. The catalytic activity of the Co-doped Fe3O4 was further investigated by decomposing the phenol in liquid phase. The results show that cobalt ions doping can improve the catalytic efficiency of Fe3O4 nanoparticles in phenol degradation with catalytic reaction fitting the first-order kinetics. According to the estimated reaction rate of Co-doped Fe3O4 nanoparticles at different temperatures, the activation energy was calculated to be 45.63 kJ/mol.

  2. Quorum Sensing and Synchronization in Populations of Coupled Chemical Oscillators

    Science.gov (United States)

    Taylor, Annette F.; Tinsley, Mark R.; Showalter, Kenneth

    2013-12-01

    Experiments and simulations of populations of coupled chemical oscillators, consisting of catalytic particles suspended in solution, provide insights into density-dependent dynamics displayed by many cellular organisms. Gradual synchronization transitions, the "switching on" of activity above a threshold number of oscillators (quorum sensing) and the formation of synchronized groups (clusters) of oscillators have been characterized. Collective behavior is driven by the response of the oscillators to chemicals emitted into the surrounding solution.

  3. Catalytically favorable surface patterns in Pt-Au nanoclusters

    KAUST Repository

    Mokkath, Junais Habeeb

    2013-01-01

    Motivated by recent experimental demonstrations of novel PtAu nanoparticles with highly enhanced catalytic properties, we present a systematic theoretical study that explores principal catalytic indicators as a function of the particle size and composition. We find that Pt electronic states in the vicinity of the Fermi level combined with a modified electron distribution in the nanoparticle due to Pt-to-Au charge transfer are the origin of the outstanding catalytic properties. From our model we deduce the catalytically favorable surface patterns that induce ensemble and ligand effects. © The Royal Society of Chemistry 2013.

  4. Facile preparation of modified carbon black-LaMnO3 hybrids and the effect of covalent coupling on the catalytic activity for oxygen reduction reaction%改性炭黑-LaMnO3复合材料的制备及其共价复合效应对氧还原性能的影响

    Institute of Scientific and Technical Information of China (English)

    刘景军; 金学民; 宋薇薇; 王峰; 王楠; 宋夜

    2014-01-01

    以Vulcan XC-72炭黑为载体,通过对炭载体石墨化处理和表面化学修饰,将其与化学沉淀法制备的纳米级LaMnO3颗粒共混,再经特定温度下煅烧,制备出改性炭黑-LaMnO3复合材料. X射线光电子能谱和热重分析表明,当煅烧温度在300°C时,炭载体与LaMnO3纳米颗粒之间形成了大量C-O-M (M = La, Mn)化学键.扫描电子显微镜和高分辨透射电子显微镜分析发现,纯相LaMnO3纳米颗粒主要呈现短棒、三支棒或竹节棒的形貌特征,炭载体则为具有完整石墨层的空心球结构, LaMnO3均匀分散在炭载体上.在25°C,1 mol/L NaOH溶液中的电化学测试结果表明,成分比(LaMnO3:C)为2:3的复合材料具有很高的氧还原电催化活性,氧还原反应电子数为3.81,中间产物H2O2产率为9.5%,其活性接近商业Pt/C催化剂(E-TEK).高的氧还原电催化活性主要归因于LaMnO3纳米颗粒与炭载体之间形成了大量共价键.%Covalent coupling between LaMnO3 nanoparticles and carbon black to produce a composite catalyst for oxygen reduction reaction (ORR) was achieved by physical mixing of modified carbon and per-ovskite-type LaMnO3 nanoparticles, followed by sintering at different temperatures. Perovskite-type LaMnO3 nanoparticles were first synthesized via chemical precipitation, and the carbon sup-port (Vulcan XC-72) was modified using graphitization, followed by HNO3 and ammonia treatments. The morphology and electronic states of the carbon black-LaMnO3 hybrid catalyst were character-ized by scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The loaded LaMnO3 particles featured rod-like, three bars-like, and bamboo rod-like structures and were homogeneously dispersed in the carbon matrix that featured a hollow spherical structure. At a sintering temperature of about 300 °C, C-O-M (M = La, Mn) bonds formed at the interface between the carbon and LaMnO3 nanoparticles. Electrochemical measurements in 1

  5. Catalytic performance and thermostability of chloroperoxidase in reverse micelle: achievement of a catalytically favorable enzyme conformation.

    Science.gov (United States)

    Wang, Yali; Wu, Jinyue; Ru, Xuejiao; Jiang, Yucheng; Hu, Mancheng; Li, Shuni; Zhai, Quanguo

    2011-06-01

    The catalytic performance of chloroperoxidase (CPO) in peroxidation of 2, 2'-azinobis-(-3 ethylbenzothiazoline-6-sulfononic acid) diammonium salt (ABTS) and oxidation of indole in a reverse micelle composed of surfactant-water-isooctane-pentanol was investigated and optimized in this work. Some positive results were obtained as follows: the peroxidation activity of CPO was enhanced 248% and 263%, while oxidation activity was enhanced 215% and 222% in cetyltrimethylammonium bromide (CTABr) reverse micelle medium and dodecyltrimethylammonium bromide (DTABr) medium, respectively. Thermostability was also greatly improved in reverse micelle: at 40 °C, CPO essentially lost all its activity after 5 h incubation, while 58-76% catalytic activity was retained for both reactions in the two reverse micelle media. At 50 °C, about 44-75% catalytic activity remained for both reactions in reverse micelle after 2 h compared with no observed activity in pure buffer under the same conditions. The enhancement of CPO activity was dependent mainly on the surfactant concentration and structure, organic solvent ratio (V(pentanol)/V(isooctane)), and water content in the reverse micelle. The obtained kinetic parameters showed that the catalytic turnover frequency (k(cat)) was increased in reverse micelle. Moreover, the lower K(m) and higher k(cat)/K(m) demonstrated that both the affinity and specificity of CPO to substrates were improved in reverse micelle media. Fluorescence, circular dichroism (CD) and UV-vis spectra assays indicated that a catalytically favorable conformation of enzyme was achieved in reverse micelle, including the strengthening of the protein α-helix structure, and greater exposure of the heme prosthetic group for easy access of the substrate in bulk solution. These results are promising in view of the industrial applications of this versatile biological catalyst.

  6. 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...

  7. Cutoff lensing: predicting catalytic sites in enzymes

    Science.gov (United States)

    Aubailly, Simon; Piazza, Francesco

    2015-10-01

    Predicting function-related amino acids in proteins with unknown function or unknown allosteric binding sites in drug-targeted proteins is a task of paramount importance in molecular biomedicine. In this paper we introduce a simple, light and computationally inexpensive structure-based method to identify catalytic sites in enzymes. Our method, termed cutoff lensing, is a general procedure consisting in letting the cutoff used to build an elastic network model increase to large values. A validation of our method against a large database of annotated enzymes shows that optimal values of the cutoff exist such that three different structure-based indicators allow one to recover a maximum of the known catalytic sites. Interestingly, we find that the larger the structures the greater the predictive power afforded by our method. Possible ways to combine the three indicators into a single figure of merit and into a specific sequential analysis are suggested and discussed with reference to the classic case of HIV-protease. Our method could be used as a complement to other sequence- and/or structure-based methods to narrow the results of large-scale screenings.

  8. Computational and Physical Analysis of Catalytic Compounds

    Science.gov (United States)

    Wu, Richard; Sohn, Jung Jae; Kyung, Richard

    2015-03-01

    Nanoparticles exhibit unique physical and chemical properties depending on their geometrical properties. For this reason, synthesis of nanoparticles with controlled shape and size is important to use their unique properties. Catalyst supports are usually made of high-surface-area porous oxides or carbon nanomaterials. These support materials stabilize metal catalysts against sintering at high reaction temperatures. Many studies have demonstrated large enhancements of catalytic behavior due to the role of the oxide-metal interface. In this paper, the catalyzing ability of supported nano metal oxides, such as silicon oxide and titanium oxide compounds as catalysts have been analyzed using computational chemistry method. Computational programs such as Gamess and Chemcraft has been used in an effort to compute the efficiencies of catalytic compounds, and bonding energy changes during the optimization convergence. The result illustrates how the metal oxides stabilize and the steps that it takes. The graph of the energy computation step(N) versus energy(kcal/mol) curve shows that the energy of the titania converges faster at the 7th iteration calculation, whereas the silica converges at the 9th iteration calculation.

  9. Structured materials for catalytic and sensing applications

    Science.gov (United States)

    Hokenek, Selma

    The optical and chemical properties of the materials used in catalytic and sensing applications directly determine the characteristics of the resultant catalyst or sensor. It is well known that a catalyst needs to have high activity, selectivity, and stability to be viable in an industrial setting. The hydrogenation activity of palladium catalysts is known to be excellent, but the industrial applications are limited by the cost of obtaining catalyst in amounts large enough to make their use economical. As a result, alloying palladium with a cheaper, more widely available metal while maintaining the high catalytic activity seen in monometallic catalysts is, therefore, an attractive option. Similarly, the optical properties of nanoscale materials used for sensing must be attuned to their application. By adjusting the shape and composition of nanoparticles used in such applications, very fine changes can be made to the frequency of light that they absorb most efficiently. The design, synthesis, and characterization of (i) size controlled monometallic palladium nanoparticles for catalytic applications, (ii) nickel-palladium bimetallic nanoparticles and (iii) silver-palladium nanoparticles with applications in drug detection and biosensing through surface plasmon resonance, respectively, will be discussed. The composition, size, and shape of the nanoparticles formed were controlled through the use of wet chemistry techniques. After synthesis, the nanoparticles were analyzed using physical and chemical characterization techniques such as X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and Scanning Transmission Electron Microscopy- Energy-Dispersive Spectrometry (STEM-EDX). The Pd and Ni-Pd nanoparticles were then supported on silica for catalytic testing using mass spectrometry. The optical properties of the Ag-Pd nanoparticles in suspension were further investigated using ultraviolet-visible spectrometry (UV-Vis). Monometallic palladium particles have

  10. 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.

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

    Science.gov (United States)

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

    2015-10-01

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

  12. An alternative synthetic approach for efficient catalytic conversion of syngas to ethanol.

    Science.gov (United States)

    Yue, Hairong; Ma, Xinbin; Gong, Jinlong

    2014-05-20

    Ethanol is an attractive end product and a versatile feedstock because a widespread market exists for its commercial use as a fuel additive or a potential substitute for gasoline. Currently, ethanol is produced primarily by fermentation of biomass-derived sugars, particularly those containing six carbons, but coproducts 5-carbon sugars and lignin remain unusable. Another major process for commercial production of ethanol is hydration of ethylene over solid acidic catalysts, yet not sustainable considering the depletion of fossil fuels. Catalytic conversion of synthetic gas (CO + H2) could produce ethanol in large quantities. However, the direct catalytic conversion of synthetic gas to ethanol remains challenging, and no commercial process exists as of today although the research has been ongoing for the past 90 years, since such the process suffers from low yield and poor selectivity due to slow kinetics of the initial C-C bond formation and fast chain growth of the C2 intermediates. This Account describes recent developments in an alternative approach for the synthesis of ethanol via synthetic gas. This process is an integrated technology consisting of the coupling of CO with methanol to form dimethyl oxalate and the subsequent hydrogenation to yield ethanol. The byproduct of the second step (methanol) can be separated and used in circulation as the feedstock for the coupling step. The coupling reaction of carbon monoxide for producing dimethyl oxalate takes place under moderate reaction conditions with high selectivity (∼95%), which ideally leads to a self-closing, nonwaste, catalytic cycling process. This Account also summarizes the progress on the development of copper-based catalysts for the hydrogenation reaction with remarkable efficiencies and stability. The unique lamellar structure and the cooperative effect between surface Cu(0) and Cu(+) species are responsible for the activity of the catalyst with high yield of ethanol (∼91%). The understanding of

  13. Cross-Coupling of Aryl Iodides with Malononitrile Catalyzed by Palladium N-Heterocyclic Carbene Complex System

    Institute of Scientific and Technical Information of China (English)

    GAO,Cheng-Wei(高诚伟); TAO,Xiao-Chun(陶晓春); LIU,Tao-Ping(刘涛平); HUANG,Ji-Ling(黄吉玲); QIAN,Yan-Long(钱延龙)

    2002-01-01

    Eight N-heterocyclic carbenes (NHC), generated in situ from their imidazolium salts, as ligands of palladium complexes were used for the catalytic coupling of iodobenzene with malononitrile anion. It was found that 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride (IMesHC1)-Pd2(dba)3 catalytic system has the highest activity to obtain phenyl malononitrile among the imidazolium salts. The substituted iodoarenes reacted with malononitrile anions by using the catalytic system to give crosscoupling products in yields from 50% to 96%.

  14. Fabrication of Au–Pd nanoparticles/graphene oxide and their excellent catalytic performance

    Energy Technology Data Exchange (ETDEWEB)

    He, Yongqiang, E-mail: heyongqiang@126.com [Department of Applied Chemistry, Yuncheng University, Yuncheng 044000 (China); Zhang, Nana; Zhang, Lei [School of Science, Tianjin University, Tianjin 300072 (China); Gong, Qiaojuan [Department of Applied Chemistry, Yuncheng University, Yuncheng 044000 (China); Yi, Maocong [School of Science, Tianjin University, Tianjin 300072 (China); Wang, Wei [School of Chemical Engineering, Tianjin University, Tianjin 300072 (China); Qiu, Haixia, E-mail: qhx@tju.edu.cn [School of Science, Tianjin University, Tianjin 300072 (China); Gao, Jianping [School of Science, Tianjin University, Tianjin 300072 (China)

    2014-03-01

    Graphical abstract: - Highlights: • Au and Pd nanoparticles loaded on GO were fabricated without adding any reducing agents. • The Au–Pd NPs/GO were excellent catalysts for the reduction of 4-nitrophenol. • The Au–Pd NPs/GO showed superior catalytic activity for the Suzuki reaction. • The Au–Pd NPs/GO exhibit good reusability. - Abstract: A simple method to fabricate clean Au–Pd nanoparticles on graphene oxide (Au–Pd NPs/GO) without using any reducing agent or surfactant has been developed. GO simultaneously reduced the Au and Pd precursors to form a stable suspension of the Au–Pd NPs/GO. The nanoparticles were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and inductively coupled plasma. The Au–Pd NPs/GO exhibited catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol and for the Suzuki–Miyaura coupling reaction of chlorobenzene and phenylboronic acid in aqueous media.

  15. Catalytic synthesis of ammonia using vibrationally excited nitrogen molecules

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Henriksen, Niels Engholm; Billing, Gert D.

    1992-01-01

    The dissociation of nitrogen is the rate-limiting step in the catalytic synthesis of ammonia. Theoretical calculations have shown that the dissociative sticking probability of molecular nitrogen on catalytic active metal surfaces is enhanced by orders of magnitude when the molecules...

  16. Functionalized TUD-1: synthesis, characterization and (photo-)catalytic performance

    NARCIS (Netherlands)

    Hamdy M. Saad, M.S.

    2005-01-01

    The new mesoporous material; TUD-1 is chosen of which the synthesis, characterization, and functionalization for (photo)-catalytic performance are extensively investigated in this study. The synthesis of the new catalytic materials M TUD-1 (M = Ti, V, Cr, Mo, Fe, Co and Cu) is carried out through an

  17. Catalytic systems of cumene oxidation based on multiwalled carbon nanotubes

    Science.gov (United States)

    Kobotaeva, N. S.; Skorokhodova, T. S.; Ryabova, N. V.

    2015-03-01

    Catalytic systems for cumene oxidation were prepared on the basis of silver-activated carbon nanotubes. Silver lies on the surface of the carbon nanotubes in the nanocrystalline state and has a size of 15-20 nm. The use of the obtained catalytic systems in cumene oxidation with molecular oxygen allowed a considerable decrease in the oxidation temperature and an increase in selectivity.

  18. Propulsion Mechanism of Catalytic Microjet Engines

    Science.gov (United States)

    Fomin, Vladimir M.; Hippler, Markus; Magdanz, Veronika; Soler, Lluís; Sanchez, Samuel; Schmidt, Oliver G.

    2014-01-01

    We describe the propulsion mechanism of the catalytic microjet engines that are fabricated using rolled-up nanotech. Microjets have recently shown numerous potential applications in nanorobotics but currently there is a lack of an accurate theoretical model that describes the origin of the motion as well as the mechanism of self-propulsion. The geometric asymmetry of a tubular microjet leads to the development of a capillary force, which tends to propel a bubble toward the larger opening of the tube. Because of this motion in an asymmetric tube, there emerges a momentum transfer to the fluid. In order to compensate this momentum transfer, a jet force acting on the tube occurs. This force, which is counterbalanced by the linear drag force, enables tube velocities of the order of 100 μm/s. This mechanism provides a fundamental explanation for the development of driving forces that are acting on bubbles in tubular microjets. PMID:25177214

  19. Stoichiometric and Catalytic Synthesis of Alkynylphosphines

    Directory of Open Access Journals (Sweden)

    Annie-Claude Gaumont

    2012-12-01

    Full Text Available Alkynylphosphines or their borane complexes are available either through C–P bond forming reactions or through modification of the phosphorus or the alkynyl function of various alkynyl phosphorus derivatives. The latter strategy, and in particular the one involving phosphoryl reduction by alanes or silanes, is the method of choice for preparing primary and secondary alkynylphosphines, while the former strategy is usually employed for the synthesis of tertiary alkynylphosphines or their borane complexes. The classical C–P bond forming methods rely on the reaction between halophosphines or their borane complexes with terminal acetylenes in the presence of a stoichiometric amount of organometallic bases, which precludes the access to alkynylphosphines bearing sensitive functional groups. In less than a decade, efficient catalytic procedures, mostly involving copper complexes and either an electrophilic or a nucleophilic phosphorus reagent, have emerged. By proceeding under mild conditions, these new methods have allowed a significant broadening of the substituent scope and structure complexity.

  20. Soluble organic nanotubes for catalytic systems

    Science.gov (United States)

    Xiong, Linfeng; Yang, Kunran; Zhang, Hui; Liao, Xiaojuan; Huang, Kun

    2016-03-01

    In this paper, we report a novel method for constructing a soluble organic nanotube supported catalyst system based on single-molecule templating of core-shell bottlebrush copolymers. Various organic or metal catalysts, such as sodium prop-2-yne-1-sulfonate (SPS), 1-(2-(prop-2-yn-1-yloxy)ethyl)-1H-imidazole (PEI) and Pd(OAc)2 were anchored onto the tube walls to functionalize the organic nanotubes via copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Depending on the ‘confined effect’ and the accessible cavity microenvironments of tubular structures, the organic nanotube catalysts showed high catalytic efficiency and site-isolation features. We believe that the soluble organic nanotubes will be very useful for the development of high performance catalyst systems due to their high stability of support, facile functionalization and attractive textural properties.

  1. Catalytic creativity. The case of Linus Pauling.

    Science.gov (United States)

    Nakamura, J; Csikszentmihalyi, M

    2001-04-01

    This article illustrates how creativity is constituted by forces beyond the innovating individual, drawing examples from the career of the eminent chemist Linus Pauling. From a systems perspective, a scientific theory or other product is creative only if the innovation gains the acceptance of a field of experts and so transforms the culture. In addition to this crucial selective function vis-à-vis the completed work, the social field can play a catalytic role, fostering productive interactions between person and domain throughout a career. Pauling's case yields examples of how variously the social field contributes to creativity, shaping the individual's standards of judgment and providing opportunities, incentives, and critical evaluation. A formidable set of strengths suited Pauling for his scientific achievements, but examination of his career qualifies the notion of a lone genius whose brilliance carries the day.

  2. Catalytic Acylation of Ethylidenecyclohexane over Zeolite Catalysts

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Some environmentally friendly catalysts such as HY and H-β zeolites,various cation-exchanged β zeolites,and some other solids have been used in the acylation reaction of ethylidenecyclohexane with acetic anhydride at room temperature to synthesize 3-(1-cyclohexenyl)-2-butanone instead of conventional catalysts.The effect of the amount of HY zeolite used on the acylation reaction was investigated.The yield of the acylated product was 72% in the case of n(ethylidenecyclohexane)∶n(acetic anhydride)∶m(HY zeolite)=1 mmol∶10 mmol∶0.100 g,reaction temperature:25 ℃,and reaction time:2 h.The regenerated HY zeolite showed almost the same catalytic activity as the fresh zeolite.

  3. Progress of catalytic wet air oxidation technology

    Directory of Open Access Journals (Sweden)

    Guolin Jing

    2016-11-01

    Full Text Available Catalytic wet air oxidation (CWAO is one of the most economical and environmental-friendly advanced oxidation process for high strength, toxic, hazardous and non-biodegradable contaminants under milder conditions, which is developed on the basic of wet air oxidation. Various heterogeneous catalysts including noble metals and metal oxides have been extensively studied to enhance the efficiency of CWAO. The advances in the research on wastewater treatment by CWAO process are summarized in aspects of reaction mechanism investigation, reaction kinetics study and catalyst development. It is pointed out that the preparation of active and stable catalysts, the investigation on reaction mechanisms and the study on reaction kinetics models are very important for the promotion of CWAO application.

  4. Catalytic coal gasification: an emerging technology.

    Science.gov (United States)

    Hirsch, R L; Gallagher, J E; Lessard, R R; Wesslhoft, R D

    1982-01-08

    Catalytic coal gasification is being developed as a more efficient and less costly approach to producing methane from coal. With a potassium catalyst all the reactions can take place at one temperature, so that endothermic and exothermic reactions can be integrated in a single reactor. A key aspect of the concept involves continuous recycling of product carbon monoxide and hydrogen to the gasifier following separation of methane. Development of the process has advanced steadily since the basic concept was proposed in 1971. A 23-day demonstration run was recently completed in a process development unit with a coal feed rate of 1 ton per day. The next major step in the program will be to design and construct a large pilot plant to bring the technology to commercial readiness in the late 1980's.

  5. Flame assisted synthesis of catalytic ceramic membranes

    DEFF Research Database (Denmark)

    Johansen, Johnny; Mosleh, Majid; Johannessen, Tue

    2004-01-01

    created in the flame, the monomers will nucleate homogeneously and agglomerate to form aggregates of large ensembles of monomers. The aggregates will then sinter together to form single particles. If the flame temperature and the residence time are sufficiently high, the formed oxide particles...... will be spherical due to the fast coalescence at the high temperatures in the flame. The primary product from the flame pyrolysis is an aerosol of metal oxide nanoparticles. The aerosol gas from the flame can be utilized for several different purposes, depending on the precursors fed to the flame. With the present...... technology it is possible to make supported catalysts, composite metal oxides, catalytically active surfaces, and porous ceramic membranes. Membrane layers can be formed by using a porous substrate tube (or surface) as a nano-particle filter. The aerosol gas from the flame is led through a porous substrate...

  6. Biofuel from fast pyrolysis and catalytic hydrodeoxygenation.

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, Douglas C.

    2015-09-04

    This review addresses recent developments in biomass fast pyrolysis bio-oil upgrading by catalytic hydrotreating. The research in the field has expanded dramatically in the past few years with numerous new research groups entering the field while existing efforts from others expand. The issues revolve around the catalyst formulation and operating conditions. Much work in batch reactor tests with precious metal catalysts needs further validation to verify long-term operability in continuous flow systems. The effect of the low level of sulfur in bio-oil needs more study to be better understood. Utilization of the upgraded bio-oil for feedstock to finished fuels is still in an early stage of understanding.

  7. Mutational analysis of a ras catalytic domain

    DEFF Research Database (Denmark)

    Willumsen, B M; Papageorge, A G; Kung, H F;

    1986-01-01

    transformation of NIH 3T3 cells with approximately the same efficiency as the wild-type v-rasH gene to those that failed to induce any detectable morphologic changes. Correlation of transforming activity with the location of the mutations enabled us to identify three nonoverlapping segments within the catalytic...... domain that were dispensable for transformation and six other segments that were required for transformation. Segments that were necessary for guanosine nucleotide (GDP) binding corresponded to three of the segments that were essential for transformation; two of the three segments share strong sequence...... localization. We speculate that this latter region interacts with the putative cellular target of ras. The results suggest that transforming ras proteins require membrane localization, guanosine nucleotide binding, and an additional undefined function that may represent interaction with their target....

  8. Catalytic hot gas cleaning of gasification gas

    Energy Technology Data Exchange (ETDEWEB)

    Simell, P. [VTT Energy, Espoo (Finland). Energy Production Technologies

    1997-12-31

    The aim of this work was to study the catalytic cleaning of gasification gas from tars and ammonia. In addition, factors influencing catalytic activity in industrial applications were studied, as well as the effects of different operation conditions and limits. Also the catalytic reactions of tar and ammonia with gasification gas components were studied. The activities of different catalyst materials were measured with laboratory-scale reactors fed by slip streams taken from updraft and fluid bed gasifiers. Carbonate rocks and nickel catalysts proved to be active tar decomposing catalysts. Ammonia decomposition was in turn facilitated by nickel catalysts and iron materials like iron sinter and iron dolomite. Temperatures over 850 deg C were required at 2000{sup -1} space velocity at ambient pressure to achieve almost complete conversions. During catalytic reactions H{sub 2} and CO were formed and H{sub 2}O was consumed in addition to decomposing hydrocarbons and ammonia. Equilibrium gas composition was almost achieved with nickel catalysts at 900 deg C. No deactivation by H{sub 2}S or carbon took place in these conditions. Catalyst blocking by particulates was avoided by using a monolith type of catalyst. The apparent first order kinetic parameters were determined for the most active materials. The activities of dolomite, nickel catalyst and reference materials were measured in different gas atmospheres using laboratory apparatus. This consisted of nitrogen carrier, toluene as tar model compound, ammonia and one of the components H{sub 2}, H{sub 2}O, CO, CO{sub 2}, CO{sub 2}+H{sub 2}O or CO+CO{sub 2}. Also synthetic gasification gas was used. With the dolomite and nickel catalyst the highest toluene decomposition rates were measured with CO{sub 2} and H{sub 2}O. In gasification gas, however, the rate was retarded due to inhibition by reaction products (CO, H{sub 2}, CO{sub 2}). Tar decomposition over dolomite was modelled by benzene reactions with CO{sub 2}, H

  9. Catalytic control of enzymatic fluorine specificity.

    Science.gov (United States)

    Weeks, Amy M; Chang, Michelle C Y

    2012-11-27

    The investigation of unique chemical phenotypes has led to the discovery of enzymes with interesting behaviors that allow us to explore unusual function. The organofluorine-producing microbe Streptomyces cattleya has evolved a fluoroacetyl-CoA thioesterase (FlK) that demonstrates a surprisingly high level of discrimination for a single fluorine substituent on its substrate compared with the cellularly abundant hydrogen analog, acetyl-CoA. In this report, we show that the high selectivity of FlK is achieved through catalysis rather than molecular recognition, where deprotonation at the C(α) position to form a putative ketene intermediate only occurs on the fluorinated substrate, thereby accelerating the rate of hydrolysis 10(4)-fold compared with the nonfluorinated congener. These studies provide insight into mechanisms of catalytic selectivity in a native system where the existence of two reaction pathways determines substrate rather than product selection.

  10. Transition-metal-free coupling reaction of vinylcyclopropanes with aldehydes catalyzed by tin hydride.

    Science.gov (United States)

    Ieki, Ryosuke; Kani, Yuria; Tsunoi, Shinji; Shibata, Ikuya

    2015-04-13

    Donor-acceptor cyclopropanes are useful building blocks for catalytic cycloaddition reactions with a range of electrophiles to give various cyclic products. In contrast, relatively few methods are available for the synthesis of homoallylic alcohols through coupling of vinylcyclopropanes (VCPs) with aldehydes, even with transition-metal catalysts. Here, we report that the hydrostannation of vinylcyclopropanes (VCPs) was effectively promoted by dibutyliodotin hydride (Bu2 SnIH). The resultant allylic tin compounds reacted easily with aldehydes. Furthermore, the use of Bu2 SnIH was effectively catalytic in the presence of hydrosilane as a hydride source, which established a coupling reaction of VCPs with aldehydes for the synthesis of homoallylic alcohols without the use of transition-metal catalysts. In contrast to conventional catalytic reactions of VCPs, the presented method allowed the use of several VCPs in addition to conventional donor-acceptor cyclopropanes.

  11. Plasma Catalytic Synthesis of Silver Nanoparticles

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yu-Tao; GUO Ying; MA Teng-Cai

    2011-01-01

    We present the experimental results of plasma catalytic synthesis of colloidal silver nanoparticles, using AgNO3 as the precursor, ethanol as the solvent and reducing agent, and poly vinyl pyrrolidone (PVP) as the macromolecular surfactant. The plasma is generated by an atmospheric argon dielectric barrier discharge jet. Silver nanoparticles are produced instantly once the plasma is ignited. The system is not heated so it is necessary to use traditional chemical methods. The samples are characterized by UV-visible absorbance and transmission electron microscopy. For glow discharge mode no obvious silver nanoparticles are observed. For low voltage filamentary streamer discharge mode a lot of silver nanoparticles with the mean diameter of ~3.5nm are generated and a further increase of the voltage causes the occurrence of agglomeration.%We present the experimental results of plasma catalytic synthesis of colloidal silver nanoparticles,using AgNO3 as the precursor,ethanol as the solvent and reducing agent,and poly vinyl pyrrolidone (PVP) as the macromolecular surfactant.The plasma is generated by an atmospheric argon dielectric barrier discharge jet.Silver nanoparticles are produced instantly once the plasma is ignited.The system is not heated so it is necessary to use traditional chemical methods.The samples are characterized by UV-visible absorbance and transmission electron microscopy.For glow discharge mode no obvious silver nanoparticles are observed.For low voltage filamentary streamer discharge mode a lot of silver nanoparticles with the mean diameter of ~3.5nm are generated and a further increase of the voltage causes the occurrence of agglomeration.The study of silver nanoparticles has been an extremely active area in recent years because of their important physical and chemical properties as a catalyst and antimicrobial reagent,for example.A number of methods for silver nanoparticle preparation have been developed,[1-3] among them chemical reduction is

  12. Catalytic combustion in small wood burning appliances

    Energy Technology Data Exchange (ETDEWEB)

    Oravainen, H. [VTT Energy, Jyvaeskylae (Finland)

    1996-12-31

    There is over a million hand fired small heating appliances in Finland where about 5,4 million cubic meters of wood fuel is used. Combustion in such heating appliances is a batch-type process. In early stages of combustion when volatiles are burned, the formation of carbon monoxide (CO) and other combustible gases are difficult to avoid when using fuels that have high volatile matter content. Harmful emissions are formed mostly after each fuel adding but also during char burnout period. When the CO-content in flue gases is, say over 0.5 %, also other harmful emissions will be formed. Methane (CH{sub 4}) and other hydrocarbons are released and the amount of polycyclic aromatic hydrocarbons (PAH)-compounds can be remarkable. Some PAH-compounds are very carcinogenic. It has been estimated that in Finland even more than 90 % of hydrocarbon and PAH emissions are due to small scale wood combustion. Emissions from transportation is excluded from these figures. That is why wood combustion has a net effect on greenhouse gas phenomena. For example carbon monoxide emissions from small scale wood combustion are two fold compared to that of energy production in power plants. Methane emission is of the same order as emission from transportation and seven fold compared with those of energy production. Emissions from small heating appliances can be reduced by developing the combustion techniques, but also by using other means, for example catalytic converters. In certain stages of the batch combustion, temperature is not high enough, gas mixing is not good enough and residence time is too short for complete combustion. When placed to a suitable place inside a heating appliance, a catalytic converter can oxidize unburned gases in the flue gas into compounds that are not harmful to the environment. (3 refs.)

  13. Methane Coupling Using Hydrogen Plasma and Pt/γ-Al2O3 Catalyst

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    In this paper, methane coupling at ambient temperature, under atmospheric pressure and in the presence of hydrogen was firstly investigated by using pulse corona plasma and Pt/γ-Al2O3 catalyst. Experimental results showed that Pt/γ-Al2O3 catalyst has catalytic activity for methane coupling to C2H4. Over sixty percent of outcomes of C2 hydrocarbons were detected to be ethylene.

  14. Direct palladium/copper oxidative cross-coupling of α-methylstyrene with acrylates

    Institute of Scientific and Technical Information of China (English)

    AL-MAKSOUD; Walid; DJAKOVITCH; Laurent; JAHJAH; Mohamad; PINEL; Catherine

    2010-01-01

    Fully palladium/copper catalytic oxidative cross-coupling of acrylates with α-methylstyrene was performed in a DMSO/AcOH(1:1) mixture at 60℃ in the air.This improves previous procedures which employed stoichiometric amounts of copper and oxygen.Thus various acrylates were effectively coupled to α-methylstyrene giving the expected compounds in moderate to good yields(44%-65%) as a mixture of E and Z isomers.

  15. Pd(II/HPMoV-Catalyzed Direct Oxidative Coupling Reaction of Benzenes with Olefins

    Directory of Open Access Journals (Sweden)

    Yasutaka Ishii

    2010-03-01

    Full Text Available The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc2/molybdovanadophosphoric acid (HPMoV as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted benzenes with olefins such as acrylates, aclrolein, and ethylene through the direct aromatic C-H bond activation.

  16. Fast, greener and scalable direct coupling of organolithium compounds with no additional solvents

    NARCIS (Netherlands)

    Pinxterhuis, Erik B.; Giannerini, Massimo; Hornillos, Valentin; Feringa, Ben L.

    2016-01-01

    Although the use of catalytic rather than stoichiometric amounts of metal mediator in cross-coupling reactions between organic halides and organometallic counterparts improves significantly the atom economy and waste production, the use of solvents and stoichiometric generation of main-group byprodu

  17. Modular Approach to Heterogenous Catalysis. Manipulation of Cross-Coupling Catalyst Activity.

    Science.gov (United States)

    Stibingerova, Iva; Voltrova, Svatava; Kocova, Sarka; Lindale, Matthew; Srogl, Jiri

    2016-01-15

    A new type of robust, heterogeneous, modular Pd catalyst with metal embedded in the gel matrix is presented. The regulatory element of its catalytic activity has been introduced via chemical changes in the gel. The concept is illustrated in a series of Suzuki-Miyaura cross-coupling reactions. The demonstrated catalyst activity variations depend on the structure of the gel.

  18. Efficient Sonogashira and Suzuki-Miyaura coupling reaction catalyzed by Pd-Nanoparticles

    Indian Academy of Sciences (India)

    Kishor E Balsane; Suresh S Shendage; Jayashree M Nagarkar

    2015-03-01

    The Pd nano particles were electrochemically deposited on nafion-graphene. They showed excellent catalytic activity towards Sonogashira and Suzuki-Miyaura cross-coupling reaction. Benzenediazonium salts were used as alternative to aromatic halide. The developed protocol offers recyclability, easy workups with short reaction time and good-to-excellent product yield.

  19. Synthesis of substituted pyrazoles via tandem cross-coupling/electrocyclization of enol triflates and diazoacetates.

    Science.gov (United States)

    Babinski, David J; Aguilar, Hector R; Still, Raymond; Frantz, Doug E

    2011-08-05

    The synthesis of 3,4,5-trisubstituted pyrazoles via a tandem catalytic cross-coupling/electrocyclization of enol triflates and diazoacetates is presented. The initial scope of this methodology is demonstrated on a range of differentially substituted acyclic and cyclic enol triflates as well as an elaborated set of diazoacetates to provide the corresponding pyrazoles with a high degree of structural complexity.

  20. Palladium-catalysed direct cross-coupling of secondary alkyllithium reagents

    NARCIS (Netherlands)

    Vila, Carlos; Giannerini, Massimo; Hornillos, Valentin; Fananas-Mastral, Martin; Feringa, Ben L.

    2014-01-01

    Palladium-catalysed cross-coupling of secondary C(sp(3)) organometallic reagents has been a long-standing challenge in organic synthesis, due to the problems associated with undesired isomerisation or the formation of reduction products. Based on our recently developed catalytic C-C bond formation w

  1. Palladium/Imidazolium Salts: A General and Highly Efficient Catalytic System for Coupling Reaction

    Institute of Scientific and Technical Information of China (English)

    YANG Chu-Luo; Steven P. Nolan

    2003-01-01

    @@ Nucleophilic N-heterocyclic carbenes have attracted considerable attention. These ligands are strong σ-donor with negligible π-accepting ability, and in this regard, they resemble electron-donor phosphines and can be addressed as "phosphine mimics". [ 1

  2. Catalytic production of methyl acrylates by gold-mediated cross coupling of unsaturated aldehydes with methanol

    Science.gov (United States)

    Karakalos, Stavros; Zugic, Branko; Stowers, Kara J.; Biener, Monika M.; Biener, Juergen; Friend, Cynthia M.; Madix, Robert J.

    2016-10-01

    Modern methods of esterification, one of the most important reactions in organic synthesis, are reaching their limits, as far as waste and expense are concerned. Novel chemical approaches to ester formation are therefore of importance. Here we report a simple procedure free of caustic reagents or byproducts for the facile direct oxidative methyl esterification of aldehydes over nanoporous Au catalysts. Complementary model studies on single crystal gold surfaces establish the fundamental reactions involved. We find that methanol more readily reacts with adsorbed active oxygen than do the aldehydes, but that once the aldehydes do react, they form strongly-bound acrylates that block reactive sites and decrease the yields of acrylic esters under steady flow conditions at 420 K. Significant improvements in yield can be achieved by operating at higher temperatures, which render the site-blocking acrylates unstable.

  3. Catalytic C-H bond silylation of aromatic heterocycles.

    Science.gov (United States)

    Toutov, Anton A; Liu, Wen-Bo; Betz, Kerry N; Stoltz, Brian M; Grubbs, Robert H

    2015-12-01

    This protocol describes a method for the direct silylation of the carbon-hydrogen (C-H) bond of aromatic heterocycles using inexpensive and abundant potassium tert-butoxide (KOt-Bu) as the catalyst. This catalytic cross-dehydrogenative coupling of simple hydrosilanes and various electron-rich aromatic heterocycles enables the synthesis of valuable silylated heteroarenes. The products thus obtained can be used as versatile intermediates, which facilitate the divergent synthesis of pharmaceutically relevant compound libraries from a single Si-containing building block. Moreover, a variety of complex Si-containing motifs, such as those produced by this protocol, are being actively investigated as next-generation therapeutic agents, because they can have improved pharmacokinetic properties compared with the original all-carbon drug molecules. Current competing methods for C-H bond silylation tend to be incompatible with functionalities, such as Lewis-basic heterocycles, that are often found in pharmaceutical substances; this leaves de novo synthesis as the principal strategy for preparation of the target sila-drug analog. Moreover, competing methods tend to be limited in the scope of hydrosilane that can be used, which restricts the breadth of silicon-containing small molecules that can be accessed. The approach outlined in this protocol enables the chemoselective and regioselective late-stage silylation of small heterocycles, including drugs and drug derivatives, with a broad array of hydrosilanes in the absence of precious metal catalysts, stoichiometric reagents, sacrificial hydrogen acceptors or high temperatures. Moreover, H2 is the only by-product generated. The procedure normally requires 48-75 h to be completed.

  4. Orion EFT-1 Catalytic Tile Experiment Overview and Flight Measurements

    Science.gov (United States)

    Salazar, Giovanni; Amar, Adam; Hyatt, Andrew; Rezin, Marc D.

    2016-01-01

    This paper describes the design and results of a surface catalysis flight experiment flown on the Orion Multipurpose Crew Vehicle during Exploration Flight Test 1 (EFT1). Similar to previous Space Shuttle catalytic tile experiments, the present test consisted of a highly catalytic coating applied to an instrumented TPS tile. However, the present catalytic tile experiment contained significantly more instrumentation in order to better resolve the heating overshoot caused by the change in surface catalytic efficiency at the interface between two distinct materials. In addition to collecting data with unprecedented spatial resolution of the "overshoot" phenomenon, the experiment was also designed to prove if such a catalytic overshoot would be seen in turbulent flow in high enthalpy regimes. A detailed discussion of the results obtained during EFT1 is presented, as well as the challenges associated with data interpretation of this experiment. Results of material testing carried out in support of this flight experiment are also shown. Finally, an inverse heat conduction technique is employed to reconstruct the flight environments at locations upstream and along the catalytic coating. The data and analysis presented in this work will greatly contribute to our understanding of the catalytic "overshoot" phenomenon, and have a significant impact on the design of future spacecraft.

  5. Numerical Study of Passive Catalytic Recombiner for Hydrogen Mitigation

    Directory of Open Access Journals (Sweden)

    Pavan K Sharma

    2010-10-01

    Full Text Available A significant amount of hydrogen is expected to be released within the containment of a water cooled power reactor after a severe accident. To reduce the risk of deflagration/detonation various means for hydrogen control have been adopted all over the world. Passive catalytic recombiner with vertical flat catalytic plate is one of such hydrogen mitigating device. Passive catalytic recombiners are designed for the removal of hydrogen generated in order to limit the impact of possible hydrogen combustion. Inside a passive catalytic recombiner, numerous thin steel sheets coated with catalyst material are vertically arranged at the bottom opening of a sheet metal housing forming parallel flow channels for the surrounding gas atmosphere. Already below conventional flammability limits, hydrogen and oxygen react exothermally on the catalytic surfaces forming harmless steam. Detailed numerical simulations and experiments are required for an in-depth knowledge of such plate type catalytic recombiners. Specific finite volume based in-house CFD code has been developed to model and analyse the working of these recombiner. The code has been used to simulate the recombiner device used in the Gx-test series of Battelle-Model Containment (B-MC experiments. The present paper briefly describes the working principle of such passive catalytic recombiner and salient feature of the CFD model developed at Bhabha Atomic Research Centre (BARC. Finally results of the calculations and comparison with existing data are discussed.

  6. Electromagnetic clutches and couplings

    CERN Document Server

    Vorob'Yeva, T M; Fry, D W; Higinbotham, W

    2013-01-01

    Electromagnetic Clutches and Couplings contains a detailed description of U.S.S.R. electromagnetic friction clutches, magnetic couplings, and magnetic particle couplings. This book is divided into four chapters. The first chapter discusses the design and construction of magnetic (solenoid-operated) couplings, which are very quick-acting devices and used in low power high-speed servo-systems. Chapter 2 describes the possible fields of application, design, construction, and utilization of magnetic particle couplings. The aspects of construction, design, and utilization of induction clutches (sli

  7. Pyridoxal-5'-phosphate-dependent catalytic antibodies.

    Science.gov (United States)

    Gramatikova, Svetlana; Mouratou, Barbara; Stetefeld, Jörg; Mehta, Perdeep K; Christen, Philipp

    2002-11-01

    Strategies for expanding the catalytic scope of antibodies include the incorporation of inorganic or organic cofactors into their binding sites. An obvious choice is pyridoxal-5'-phosphate (PLP), which is probably the most versatile organic cofactor of enzymes. Monoclonal antibodies against the hapten N(alpha)-(5'-phosphopyridoxyl)-L-lysine, a stable analog of the covalent coenzyme-substrate adducts were screened by a competition ELISA for binding of the PLP-amino acid Schiff base adduct. The Schiff base with its C4'-N alpha double bond is, in contrast to the hapten, a planar compound and is an obligatory intermediate in all PLP-dependent reactions of amino acids. This highly discriminating screening step eliminated all but 5 of 24 hapten-binding antibodies. The five remaining antibodies were tested for catalysis of the PLP-dependent alpha,beta-elimination reaction of beta-chloroalanine. Antibody 15A9 complied with this selection criterion and catalyzed in addition the cofactor-dependent transamination reaction of hydrophobic D-amino acids and oxo acids (k(cat)'=0.42 min(-1) with D-alanine at 25 degrees C). Homology modeling together with alanine scanning yielded a 3D model of Fab 15A9. The striking analogy between antibody 15A9 and PLP-dependent enzymes includes the following features: (1) The binding sites accommodate the planar coenzyme-amino acid adduct. (2) The bond at C alpha to be broken lies together with the C alpha-N bond in a plane orthogonal to the plane of coenzyme and imine bond. (3) The alpha-carboxylate group of the substrate is bound by an arginine residue. (4) The coenzyme-substrate adduct assumes a cisoid conformation. (5) PLP markedly contributes to catalytic efficiency, being a 10(4) times more efficient amino group acceptor than pyruvate. The protein moiety, however, ensures reaction as well as substrate specificity, and further accelerates the reaction (in 15A9 k(cat (Ab x PLP))'/k(cat (PLP))'=5 x 10(3)). The analogies of antibody 15A9 with

  8. Catalytic activity of carbons for methane decomposition reaction

    Energy Technology Data Exchange (ETDEWEB)

    Muradov, Nazim; Smith, Franklyn; T-Raissi, Ali [Florida Solar Energy Center, University of Central Florida, 1679 Clearlake Road, Cocoa, FL 32922 (United States)

    2005-05-15

    Catalytic decomposition of methane is an environmentally attractive approach to CO{sub 2}-free production of hydrogen. The objective of this work is to evaluate catalytic activity of a wide range of carbon materials for methane decomposition reaction and determine major factors governing their activity. It was demonstrated that the catalytic activity of carbon materials for methane decomposition is mostly determined by their structural and surface properties. Kinetics of methane decomposition reaction over disordered (amorphous) carbons such as carbon black and activated carbon were determined. The mechanism of carbon-catalyzed methane decomposition reaction and the nature of active sites on the carbon surface are discussed in this paper.

  9. Enhanced propylene production in FCC by novel catalytic materials

    Energy Technology Data Exchange (ETDEWEB)

    Kelkar, C.P.; Harris, D.; Xu, M.; Fu, J. [BASF Catalyst LLC, Iselin, NJ (United States)

    2007-07-01

    Fluid catalytic cracking is expected to increasingly supply the additional incremental requirements for propylene. The most efficient route to increase propylene yield from an FCC unit is through the use of medium pore zeolites such as ZSM-5. ZSM-5 zeolite cracks near linear olefins in the gasoline range to LPG olefins such as propylene and butylenes. This paper will describe catalytic approaches to increase gasoline range olefins and the chemistry of ZSM-5 to crack those olefins. The paper will also describe novel catalytic materials designed to increase propylene. (orig.)

  10. Bring into Full Play the Role of Catalytic Reforming Unit

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    This article after analyzing the current status of catalytic reforming technology in China puts forward a host of problems related with catalytic reforming capacity, feedstock, size and techno-economic indicators. To solve these problems it is proposed to properly increase the catalytic reforming capacity,extend the feedstock source, and eliminate the bottlenecks to boost the capacity of existing units, improve the operating and management level, as well as speed up R&D work, disseminate new technologies, new processes and novel catalysts.

  11. Controlled synthesis of porous platinum nanostructures for catalytic applications.

    Science.gov (United States)

    Cao, Yanqin; Zhang, Junwei; Yang, Yong; Huang, Zhengren; Long, Nguyen Viet; Nogami, Masayuki

    2014-02-01

    Porous platinum, that has outstanding catalytic and electrical properties and superior resistant characteristics to corrosion, has been widely applied in chemical, petrochemical, pharmaceutical, electronic, and automotive industries. As the catalytic activity and selectivity depend on the size, shape and structure of nanomaterials, the strategies for controlling these factors of platinum nanomaterials to get excellent catalytic properties are discussed. Here, recent advances in the design and preparation of various porous platinum nanostructures are reviewed, including wet-chemical synthesis, electro-deposition, galvanic replacement reaction and de-alloying technology. The applications of various platinum nanostructures are also discussed, especially in fuel cells.

  12. Study on the catalytic effect of NiO nanoparticles on the thermal decomposition of TEGDN/NC propellant.

    Science.gov (United States)

    Wei, Wenxian; Jiang, Xiaohong; Lu, Lude; Yang, Xujie; Wang, Xin

    2009-09-15

    The catalytic effect of NiO nanoparticles on the thermal decomposition of double-base propellant composed of nitrocellulose (NC) and triethylene glycol dinitrate (TEGDN) has been investigated by thermogravimetry-mass spectrometry (TG-MS) coupling technique. It was shown that adding 2% of NiO nanoparticles to TEGDN/NC propellant can accelerate the thermal decomposition process after around 188 degrees C TG-MS analysis indicated that NiO nanoparticles have resulted in the increase in intensity (peak area) of m/z=27, 28, and 29 MS signals, but the decrease in the intensity of m/z=18, 30, 44 and 46 (peak 2) MS signals during the thermal decompsition. The catalytic mechanism was also discussed in this paper.

  13. 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.

  14. 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

  15. Computational design of chemically propelled catalytic nanorotors.

    Science.gov (United States)

    Chen, Yanping; Shi, Yunfeng

    2013-08-14

    We designed catalytic nanorotors and investigated the rotational motion and energy conversion efficiency using reactive molecular dynamics in two dimensions. First, a two-arm nanorotor was constructed by decorating a slender beam with catalysts asymmetrically on its two long edges, while fixing the beam center as the rotational axis. Autonomous rotation was observed for the two-arm nanorotor immersing in a fuel environment. Here fuel molecules undergo exothermic combination reaction facilitated by the catalysts. It was found that the angular velocity increases with the catalyst coverage parabolically, while the rotary nanomotor efficiency stays roughly constant. These observations are consistent with a single-collision-momentum-transfer-based propulsion model. Furthermore, multi-arm nanorotors (up to eight arms) were constructed by carving radially distributed arms followed by decorating catalysts. For multi-arm nanorotors, both the angular velocity and the efficiency decrease as the number of arms increases. These behaviors contradict the aforementioned model, which are likely due to the deceleration from secondary collisions between products and the nanorotor arms. Our simulation results show that the optimal design for a nanorotor that maximizes its angular velocity and the motor efficiency is a two-arm nanorotor with nearly full coverage of catalysts.

  16. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    Science.gov (United States)

    Nicholas, Christpher P; Boldingh, Edwin P

    2013-12-17

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

  17. Microchannel Reactor System for Catalytic Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Adeniyi Lawal; Woo Lee; Ron Besser; Donald Kientzler; Luke Achenie

    2010-12-22

    We successfully demonstrated a novel process intensification concept enabled by the development of microchannel reactors, for energy efficient catalytic hydrogenation reactions at moderate temperature, and pressure, and low solvent levels. We designed, fabricated, evaluated, and optimized a laboratory-scale microchannel reactor system for hydrogenation of onitroanisole and a proprietary BMS molecule. In the second phase of the program, as a prelude to full-scale commercialization, we designed and developed a fully-automated skid-mounted multichannel microreactor pilot plant system for multiphase reactions. The system is capable of processing 1 – 10 kg/h of liquid substrate, and an industrially relevant immiscible liquid-liquid was successfully demonstrated on the system. Our microreactor-based pilot plant is one-of-akind. We anticipate that this process intensification concept, if successfully demonstrated, will provide a paradigm-changing basis for replacing existing energy inefficient, cost ineffective, environmentally detrimental slurry semi-batch reactor-based manufacturing practiced in the pharmaceutical and fine chemicals industries.

  18. Catalytic hydrolysis of cellulose into furans

    Science.gov (United States)

    Shi, Chengmei; Tao, Furong; Cui, Yuezhi

    2016-12-01

    Chromium chloride in 4-(3-methylimidazolium-1-yl)butane-1-sulfonic acid hydrogen sulfate (IL-1) was found to effectively catalyze the hydrolysis of microcrystalline cellulose (MCC) at 150°C for 300 min to achieve 87.8% conversion to a slate of products. With a catalytic amount of CrCl3, the yields of 5-hydroxymethyl furfural (HMF) and furfural were up to 32.4 and 15.2%, respectively, small molecules levulinic acid (LA, 10.8%) and the total reducing sugars (TRS, 10.7%) were also generated. Through LC-MSD analysis and mass spectra, dimer of furan compounds as the main by-products were speculated, and the components of gas products were methane, ethane, CO, CO2, and H2. We suggested that IL-1 and CrCl3 exhibited a coordination interaction; the formation of the intermediate via the hydride shift played a key role in the formation of HMF. The catalyst was recycled and exhibited constant activity for five successive trials.

  19. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    Energy Technology Data Exchange (ETDEWEB)

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-10-07

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

  20. Catalytic glycerol steam reforming for hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Dan, Monica, E-mail: monica.dan@itim-cj.ro; Mihet, Maria, E-mail: maria.mihet@itim-cj.ro; Lazar, Mihaela D., E-mail: diana.lazar@itim-cj.ro [National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103 Donat Street, 400293 Cluj Napoca (Romania)

    2015-12-23

    Hydrogen production from glycerol by steam reforming combine two major advantages: (i) using glycerol as raw material add value to this by product of bio-diesel production which is obtained in large quantities around the world and have a very limited utilization now, and (ii) by implication of water molecules in the reaction the efficiency of hydrogen generation is increased as each mol of glycerol produces 7 mol of H{sub 2}. In this work we present the results obtained in the process of steam reforming of glycerol on Ni/Al{sub 2}O{sub 3}. The catalyst was prepared by wet impregnation method and characterized through different methods: N{sub 2} adsorption-desorption, XRD, TPR. The catalytic study was performed in a stainless steel tubular reactor at atmospheric pressure by varying the reaction conditions: steam/carbon ratio (1-9), gas flow (35 ml/min -133 ml/min), temperature (450-650°C). The gaseous fraction of the reaction products contain: H{sub 2}, CH{sub 4}, CO, CO{sub 2}. The optimum reaction conditions as resulted from this study are: temperature 550°C, Gly:H{sub 2}O ratio 9:1 and Ar flow 133 ml/min. In these conditions the glycerol conversion to gaseous products was 43% and the hydrogen yield was 30%.

  1. Catalytic glycerol steam reforming for hydrogen production

    Science.gov (United States)

    Dan, Monica; Mihet, Maria; Lazar, Mihaela D.

    2015-12-01

    Hydrogen production from glycerol by steam reforming combine two major advantages: (i) using glycerol as raw material add value to this by product of bio-diesel production which is obtained in large quantities around the world and have a very limited utilization now, and (ii) by implication of water molecules in the reaction the efficiency of hydrogen generation is increased as each mol of glycerol produces 7 mol of H2. In this work we present the results obtained in the process of steam reforming of glycerol on Ni/Al2O3. The catalyst was prepared by wet impregnation method and characterized through different methods: N2 adsorption-desorption, XRD, TPR. The catalytic study was performed in a stainless steel tubular reactor at atmospheric pressure by varying the reaction conditions: steam/carbon ratio (1-9), gas flow (35 ml/min -133 ml/min), temperature (450-650°C). The gaseous fraction of the reaction products contain: H2, CH4, CO, CO2. The optimum reaction conditions as resulted from this study are: temperature 550°C, Gly:H2O ratio 9:1 and Ar flow 133 ml/min. In these conditions the glycerol conversion to gaseous products was 43% and the hydrogen yield was 30%.

  2. Catalytic extraction processing of contaminated scrap metal

    Energy Technology Data Exchange (ETDEWEB)

    Griffin, T.P.; Johnston, J.E.; Payea, B.M. [Molten Metal Technology, Inc., Waltham, MA (United States)] [and others

    1995-10-01

    The U.S. Department of Energy issued a Planned Research and Development Announcement (PRDA) in 1993, with the objective of identifying unique technologies which could be applied to the most hazardous waste streams at DOE sites. The combination of radioactive contamination with additional contamination by hazardous constituents such as those identified by the Resource Conservation and Recovery Act (RCRA) pose an especially challenging problem. Traditional remediation technologies are increasingly becoming less acceptable to stakeholders and regulators because of the risks they pose to public health and safety. Desirable recycling technologies were described by the DOE as: (1) easily installed, operated, and maintained; (2) exhibiting superior environmental performance; (3) protective of worker and public health and safety; (4) readily acceptable to a wide spectrum of evaluators; and (5) economically feasible. Molten Metal Technology, Inc. (MMT) was awarded a contract as a result of the PRDA initiative to demonstrate the applicability of Catalytic Extraction Processing (CEP), MMT`s proprietary elemental recycling technology, to DOE`s inventory of low level mixed waste. This includes DOE`s inventory of radioactively- and RCRA-contaminated scrap metal and other waste forms expected to be generated by the decontamination and decommissioning (D&D) of DOE sites.

  3. Describing spatiotemporal couplings in ultrashort pulses using coupling coefficients

    Institute of Scientific and Technical Information of China (English)

    Zeng Shu-Guang; Dan You-Quan; Zhang Bin; Sun Nian-Chun; Sui Zhan

    2011-01-01

    Three coupling coefficients are defined to describe spatiotemporal coupling in ultrashort pulses.With these coupling coefficients,the first-order spatiotemporal couplings of Gaussian pulse and beam are described analytically.Also,the first-order and the second-order spatiotemporal couplings caused by angular dispersion elements are studied using these coupling coefficients.It can be shown that these coupling coefficients are dimensionless and normalized,and readily indicate the severity of spatiotemporal coupling.

  4. Plasma Catalytic Extraction of Oxygen from the Martian Atmosphere Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Plasma catalytic techniques are proposed for the extraction of oxygen from the abundant carbon dioxide contained in the Martian atmosphere (95% CO2).. The Phase I...

  5. Synthesis and catalytic application of amino acid based dendritic macromolecules

    NARCIS (Netherlands)

    Koten, G. van; Gossage, R.A.; Jastrzebski, J.T.B.H.; Ameijde, J. van; Mulders, S.J.E.; Brouwer, Arwin J.; Liskamp, R.M.J.

    1999-01-01

    The use of amino acid based dendrimers as molecular scaffolds for the attachment of catalytically active organometallic Ni ''pincer'' complexes, via a urea functionality, is described; the dendrimer catalysts have comparable activity to their mononuclear (NCN)NiX analogues.

  6. Anodic aluminium oxide catalytic membranes for asymmetric epoxidation.

    Science.gov (United States)

    Cho, So-Hye; Walther, Nolan D; Nguyen, SonBinh T; Hupp, Joseph T

    2005-11-14

    Catechol-functionalized (salen)Mn complexes can be supported on mesoporous anodized aluminium oxide disks to yield catalytic membranes that are highly active in the enantioselective epoxidation of olefins when being deployed in a forced-through-flow reactor.

  7. Resolving the Structure of Active Sites on Platinum Catalytic Nanoparticles

    DEFF Research Database (Denmark)

    Chang, Lan Yun; Barnard, Amanda S.; Gontard, Lionel Cervera

    2010-01-01

    Accurate understanding of the structure of active sites is fundamentally important in predicting catalytic properties of heterogeneous nanocatalysts. We present an accurate determination of both experimental and theoretical atomic structures of surface monatomic steps on industrial platinum...

  8. The Catalytic Enantioselective Total Synthesis of (+)‐Liphagal

    DEFF Research Database (Denmark)

    Day, Joshua J.; McFadden, Ryan M.; Virgil, Scott C.;

    2011-01-01

    Ring a ding: The first catalytic enantioselective total synthesis of the meroterpenoid natural product (+)-liphagal is disclosed. The approach showcases a variety of technology including enantioselective enolate alkylation, a photochemical alkyne-alkene [2+2] reaction, microwaveassisted metal cat...

  9. Enantiocontrol in Macrocycle Formation from Catalytic MetalCarbene Transformations

    Institute of Scientific and Technical Information of China (English)

    DOYLE, Michael P.; DOYLE, Michael P; HU, Wen-Hao(胡文浩); 胡文浩

    2001-01-01

    The development of catalytic metal carbene transformations for the construction of macrocyclic lactones has dramatically increased their synthetic advantages.This is the first review of this developing methodology.

  10. Determination of Catalytic Coefficient for a First-Order Reaction

    Science.gov (United States)

    Fraga, E. R.; And Others

    1975-01-01

    Describes an undergraduate physical chemistry experiment in which the acid catalyzed hydrolysis of sucrose is used to determine the catalytic coefficient of the hydronium ion, the catalyst in this reaction. (MLH)

  11. Catalytic pyrolysis of waste mandarin over nanoporous materials.

    Science.gov (United States)

    Park, Young-Kwon; Kim, Jeong Wook; Park, Sung Hoon; Kim, Seong-Soo; Jeon, Jong-Ki; Lee, See Hoon

    2013-01-01

    Catalytic pyrolysis of waste mandarin was performed using nanoporous catalysts. AI-MCM-41 and Meso-MFI, which had different acid characteristics, were used. In addition, the characteristics of Pt/Meso-MFI were compared with those of Meso-MFI. To analyze the characteristics of the catalyst samples, Brunauer-Emmett-Teller surface area, temperature programmed desorption of NH3, and N2 adsorption-desorption analyses were performed. In addition, pyrolysis gas chromatography/mass spectrometry was used to facilitate the direct analysis of the pyrolytic products. The products obtained from catalytic pyrolysis contained a greater amount of valuable components than did those obtained from non-catalytic pyrolysis, indicating that catalytic pyrolysis improved the quality of the bio-oil. Additionally, valuable products such as furan and aromatic compounds were produced in greater quantities when Meso-MFI was used. When Pt/Meso-MFI was used, the amounts of furan and aromatic compounds produced increased even further.

  12. Protein composition of catalytically active human telomerase from immortal cells

    DEFF Research Database (Denmark)

    Cohen, Scott B; Graham, Mark E; Lovrecz, George O;

    2007-01-01

    on the enzyme's ability to catalyze nucleotide addition onto a DNA oligonucleotide of telomeric sequence, thereby providing specificity for catalytically active telomerase. Mass spectrometric sequencing of the protein components and molecular size determination indicated an enzyme composition of two molecules...

  13. Synthesis and Catalytic Activity of Two New Cyclic Tetraaza Ligands

    Directory of Open Access Journals (Sweden)

    Burkhard König

    2003-05-01

    Full Text Available Two new chiral cyclic tetraaza ligands were synthesized and characterized. Their catalytic activity was tested in the asymmetric addition of diethylzinc to benzaldehyde. The expected secondary alcohol was obtained in moderate yields, but with very low enantioselectivity.

  14. Optimized Combination of Residue Hydrodesulfurization and Residue Fluid Catalytic Cracking

    Institute of Scientific and Technical Information of China (English)

    Chen Junwu

    2003-01-01

    @@1 Introduction Combination of residue hydrodesulfurization (HDS) and resi-due fluid catalytic cracking (RFCC) is a unique technologyfor processing high-sulfur residue. This paper discusses theoptimized combination of these two processes.

  15. Porous protein crystals as catalytic vessels for organometallic complexes.

    Science.gov (United States)

    Tabe, Hiroyasu; Abe, Satoshi; Hikage, Tatsuo; Kitagawa, Susumu; Ueno, Takafumi

    2014-05-01

    Porous protein crystals, which are protein assemblies in the solid state, have been engineered to form catalytic vessels by the incorporation of organometallic complexes. Ruthenium complexes in cross-linked porous hen egg white lysozyme (HEWL) crystals catalyzed the enantioselective hydrogen-transfer reduction of acetophenone derivatives. The crystals accelerated the catalytic reaction and gave different enantiomers based on the crystal form (tetragonal or orthorhombic). This method represents a new approach for the construction of bioinorganic catalysts from protein crystals.

  16. Northwestern University Facility for Clean Catalytic Process Research

    Energy Technology Data Exchange (ETDEWEB)

    Marks, Tobin Jay [Northwestern University

    2013-05-08

    Northwestern University with DOE support created a Facility for Clean Catalytic Process Research. This facility is designed to further strengthen our already strong catalysis research capabilities and thus to address these National challenges. Thus, state-of-the art instrumentation and experimentation facility was commissioned to add far greater breadth, depth, and throughput to our ability to invent, test, and understand catalysts and catalytic processes, hence to improve them via knowledge-based design and evaluation approaches.

  17. Catalytic Upgrading of Sugars to Hydrocarbons Technology Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Biddy, M.; Jones, S.

    2013-03-01

    This technology pathway case investigates the catalytic conversion of solubilized carbohydrate streams to hydrocarbon biofuels, utilizing data from recent efforts within the National Advanced Biofuels Consortium (NABC) in collaboration with Virent, Inc. Technical barriers and key research needs that should be pursued for the catalytic conversion of sugars pathway to be competitive with petroleum-derived gasoline-, diesel-, and jet-range hydrocarbon blendstocks have been identified.

  18. Water recovery by catalytic treatment of urine vapor

    Science.gov (United States)

    Budininkas, P.; Quattrone, P. D.; Leban, M. I.

    1980-01-01

    The objective of this investigation was to demonstrate the feasibility of water recovery on a man-rated scale by the catalytic processing of untreated urine vapor. For this purpose, two catalytic systems, one capable of processing an air stream containing low urine vapor concentrations and another to process streams with high urine vapor concentrations, were designed, constructed, and tested to establish the quality of the recovered water.

  19. Hydrogen production by catalytic partial oxidation of methane

    OpenAIRE

    Enger, Bjørn Christian

    2008-01-01

    Hydrogen production by catalytic partial oxidation of natural gas was investigated using tools ranging from theoretical calculations to experimental work and sophisticated characterization techniques.Catalytic partial oxidation (CPO) was carried out in a conventional continuous flow experimental apparatus using a xed-bed reactor, and operating at 1 atm and furnace temperatures in the range from ambient to 1073 K. The feed typically consisted of a mixture of methane and air, with a CH4/O2 rati...

  20. Response reactions: equilibrium coupling.

    Science.gov (United States)

    Hoffmann, Eufrozina A; Nagypal, Istvan

    2006-06-01

    It is pointed out and illustrated in the present paper that if a homogeneous multiple equilibrium system containing k components and q species is composed of the reactants actually taken and their reactions contain only k + 1 species, then we have a unique representation with (q - k) stoichiometrically independent reactions (SIRs). We define these as coupling reactions. All the other possible combinations with k + 1 species are the coupled reactions that are in equilibrium when the (q - k) SIRs are in equilibrium. The response of the equilibrium state for perturbation is determined by the coupling and coupled equilibria. Depending on the circumstances and the actual thermodynamic data, the effect of coupled equilibria may overtake the effect of the coupling ones, leading to phenomena that are in apparent contradiction with Le Chatelier's principle.

  1. Catalytic flash pyrolysis of oil-impregnated-wood and jatropha cake using sodium based catalysts

    NARCIS (Netherlands)

    Ali Imran, A.; Bramer, E.A.; Seshan, K.; Brem, G.

    2016-01-01

    Catalytic pyrolysis of wood with impregnated vegetable oil was investigated and compared with catalytic pyrolysis of jatropha cake making use of sodium based catalysts to produce a high quality bio-oil. The catalytic pyrolysis was carried out in two modes: in-situ catalytic pyrolysis and post treatm

  2. Molecular Self-Assembly Strategy for Generating Catalytic Hybrid Polypeptides

    Science.gov (United States)

    Ikezoe, Yasuhiro; Pike, Douglas H.; Nanda, Vikas; Matsui, Hiroshi

    2016-01-01

    Recently, catalytic peptides were introduced that mimicked protease activities and showed promising selectivity of products even in organic solvents where protease cannot perform well. However, their catalytic efficiency was extremely low compared to natural enzyme counterparts presumably due to the lack of stable tertiary fold. We hypothesized that assembling these peptides along with simple hydrophobic pockets, mimicking enzyme active sites, could enhance the catalytic activity. Here we fused the sequence of catalytic peptide CP4, capable of protease and esterase-like activities, into a short amyloidogenic peptide fragment of Aβ. When the fused CP4-Aβ construct assembled into antiparallel β-sheets and amyloid fibrils, a 4.0-fold increase in the hydrolysis rate of p-nitrophenyl acetate (p-NPA) compared to neat CP4 peptide was observed. The enhanced catalytic activity of CP4-Aβ assembly could be explained both by pre-organization of a catalytically competent Ser-His-acid triad and hydrophobic stabilization of a bound substrate between the triad and p-NPA, indicating that a design strategy for self-assembled peptides is important to accomplish the desired functionality. PMID:27116246

  3. Catalytic decarboxylations of fatty acids in immature oil source rocks

    Institute of Scientific and Technical Information of China (English)

    李哲; 张再龙; 孙燕华; 劳永新; 蔺五正; 吴卫芳

    2003-01-01

    Catalytic decarboxylations of fatty acids in immature oil source rock samples were examined in this study. The rock samples were obtained from seven oil fields in China. In order to clarify the effect of each mineral matter in the rock samples, both the Fe M?ssbauer effect and the X-ray diffraction (XRD) were used to determine the relative content of each mineral in the rock samples, and the catalytic activities of several minerals like clays, carbonates and pyrite were determined. The Fe M?ssbauer effect and the XRD studies show that clays are the main mineral components in the rock samples except for the samples from Biyang and Jianghan in which the main mineral component is ankerite. The other mineral components include calcite, plagioclase, quartz, feldspar, siderite, aragonite, pyrite, analcime, pyroxene and anhydrite. The studies of the catalytic decarboxylations of fatty acids suggest that carbonates and pyrite can make much greater contributions to the catalytic activities of the rock samples than clays. It is found that the overall catalytic activities of the rock samples are well related to the relative contents and the catalytic activities of clays, carbonates and pyrite in the rock samples.

  4. Catalytic pyrolysis of waste rice husk over mesoporous materials

    Science.gov (United States)

    Jeon, Mi-Jin; Kim, Seung-Soo; Jeon, Jong-Ki; Park, Sung Hoon; Kim, Ji Man; Sohn, Jung Min; Lee, See-Hoon; Park, Young-Kwon

    2012-01-01

    Catalytic fast pyrolysis of waste rice husk was carried out using pyrolysis-gas chromatography/mass spectrometry [Py-GC/MS]. Meso-MFI zeolite [Meso-MFI] was used as the catalyst. In addition, a 0.5-wt.% platinum [Pt] was ion-exchanged into Meso-MFI to examine the effect of Pt addition. Using a catalytic upgrading method, the activities of the catalysts were evaluated in terms of product composition and deoxygenation. The structure and acid site characteristics of the catalysts were analyzed by Brunauer-Emmett-Teller surface area measurement and NH3 temperature-programmed desorption analysis. Catalytic upgrading reduced the amount of oxygenates in the product vapor due to the cracking reaction of the catalysts. Levoglucosan, a polymeric oxygenate species, was completely decomposed without being detected. While the amount of heavy phenols was reduced by catalytic upgrading, the amount of light phenols was increased because of the catalytic cracking of heavy phenols into light phenols and aromatics. The amount of aromatics increased remarkably as a result of catalytic upgrading, which is attributed to the strong Brönsted acid sites and the shape selectivity of the Meso-MFI catalyst. The addition of Pt made the Meso-MFI catalyst even more active in deoxygenation and in the production of aromatics.

  5. Catalytic pyrolysis of car tire waste using expanded perlite.

    Science.gov (United States)

    Kar, Y

    2011-08-01

    In this study, the non-catalytic and catalytic pyrolysis experiments were conducted on the sample of tire waste using expanded perlite as an additive material to determine especially the effect of temperature and catalyst-to-tire ratio on the products yields and the compositions and qualities of pyrolytic oils (NCPO and CPO). Non-catalytic studies, which were carried out under the certain conditions (a nitrogen flow of 100mL/min and a heating rate of 10°C/min), showed that the highest yield of pyrolytic oil (NCPO) was 60.02wt.% at 425°C. Then, the catalytic pyrolysis studies were carried out at catalyst-to-tire ratio range of 0.05-0.25 and the highest catalytic pyrolytic oil (CPO) yield was 65.11wt.% at the ratio of 0.10 with the yield increase of 8.48wt.% compared with the non-catalytic pyrolysis. Lastly, the pyrolytic oils were characterized with applying a various techniques such as elemental analyses and various chromatographic and spectroscopic techniques (GC-MS, (1)H NMR, FT-IR, etc.). The characterization results revealed that the pyrolytic oils which were complex mixtures of C(5)-C(15) organic compounds (predominantly aromatic compounds) and also the CPO compared to the NCPO was more similar to conventional fuels in view of the certain fuel properties.

  6. Catalytic activities of zeolite compounds for decomposing aqueous ozone.

    Science.gov (United States)

    Kusuda, Ai; Kitayama, Mikito; Ohta, Yoshio

    2013-12-01

    The advanced oxidation process (AOP), chemical oxidation using aqueous ozone in the presence of appropriate catalysts to generate highly reactive oxygen species, offers an attractive option for removing poorly biodegradable pollutants. Using the commercial zeolite powders with various Si/Al ratios and crystal structures, their catalytic activities for decomposing aqueous ozone were evaluated by continuously flowing ozone to water containing the zeolite powders. The hydrophilic zeolites (low Si/Al ratio) with alkali cations in the crystal structures were found to possess high catalytic activity for decomposing aqueous ozone. The hydrophobic zeolite compounds (high Si/Al ratio) were found to absorb ozone very well, but to have no catalytic activity for decomposing aqueous ozone. Their catalytic activities were also evaluated by using the fixed bed column method. When alkali cations were removed by acid rinsing or substituted by alkali-earth cations, the catalytic activities was significantly deteriorated. These results suggest that the metal cations on the crystal surface of the hydrophilic zeolite would play a key role for catalytic activity for decomposing aqueous ozone.

  7. Conformally Coupled Inflation

    Directory of Open Access Journals (Sweden)

    Valerio Faraoni

    2013-07-01

    Full Text Available A massive scalar field in a curved spacetime can propagate along the light cone, a causal pathology, which can, in principle, be eliminated only if the scalar couples conformally to the Ricci curvature of spacetime. This property mandates conformal coupling for the field driving inflation in the early universe. During slow-roll inflation, this coupling can cause super-acceleration and, as a signature, a blue spectrum of primordial gravitational waves.

  8. Running surface couplings

    OpenAIRE

    1995-01-01

    We discuss the renormalization group improved effective action and running surface couplings in curved spacetime with boundary. Using scalar self-interacting theory as an example, we study the influence of the boundary effects to effective equations of motion in spherical cap and the relevance of surface running couplings to quantum cosmology and symmetry breaking phenomenon. Running surface couplings in the asymptotically free SU(2) gauge theory are found.

  9. Conversation, coupling and complexity

    DEFF Research Database (Denmark)

    Fusaroli, Riccardo; Abney, Drew; Bahrami, Bahador;

    We investigate the linguistic co-construction of interpersonal synergies. By applying a measure of coupling between complex systems to an experimentally elicited corpus of joint decision dialogues, we show that interlocutors’ linguistic behavior displays increasing signature of multi-scale coupling......, known as complexity matching, over the course of interaction. Furthermore, we show that stronger coupling corresponds with more effective interaction, as measured by collective task performance....

  10. Conformally coupled inflation

    CERN Document Server

    Faraoni, Valerio

    2013-01-01

    A massive scalar field in a curved spacetime can propagate along the light cone, a causal pathology, which can, in principle, be eliminated only if the scalar couples conformally to the Ricci curvature of spacetime. This property mandates conformal coupling for the field driving inflation in the early universe. During slow-roll inflation, this coupling can cause super-acceleration and, as a signature, a blue spectrum of primordial gravitational waves.

  11. Pneumatic flexible shaft couplings

    OpenAIRE

    2007-01-01

    Main effort of every design engineer is reduction of torsional oscillation in any mechanical system. At present this problem can be solved by means of a suitable modification of dynamic properties of flexible shaft couplings according to dynamics in the given systems. But the dynamic properties of nowadays-applied flexible couplings arenot unchangeable because of aging and fatigue processes occurring in flexible coupling elements. Result of this fact causes detuning of mechanical system. Taki...

  12. Human P-glycoprotein exhibits reduced affinity for substrates during a catalytic transition state.

    Science.gov (United States)

    Ramachandra, M; Ambudkar, S V; Chen, D; Hrycyna, C A; Dey, S; Gottesman, M M; Pastan, I

    1998-04-01

    Human P-glycoprotein (Pgp), a plasma membrane protein that confers multidrug resistance, functions as an ATP-dependent drug efflux pump. Pgp contains two ATP binding/utilization sites and exhibits ATPase activity that is stimulated in the presence of substrates and modulating agents. The mechanism of coupling of ATP hydrolysis to drug transport is not known. To understand the role of ATP hydrolysis in drug binding, it is necessary to develop methods for purifying and reconstituting Pgp that retains properties including stimulation of ATPase activity by known substrates to an extent similar to that in the native membrane. In this study, (His)6-tagged Pgp was expressed in Trichoplusia ni (High Five) cells using the recombinant baculovirus system and purified by metal affinity chromatography. Upon reconstitution into phospholipid vesicles, purified Pgp exhibited specific binding to analogues of substrates and ATP in affinity labeling experiments and displayed a high level of drug-stimulated ATPase activity (specific activity ranging from 4.5 to 6.5 micromol min-1 mg-1). The ATPase activity was inhibited by ADP in a competitive manner, and by vanadate and N-ethylmaleimide at low concentrations. Vanadate which is known to inhibit ATPase activity by trapping MgADP at the catalytic site inhibited photoaffinity labeling of Pgp with substrate analogues, [125I]iodoarylazidoprazosin and [3H]azidopine, only under ATP hydrolysis conditions. Because vanadate-trapped Pgp is known to resemble the ADP and phosphate-bound catalytic transition state, our findings indicate that ATP hydrolysis results in a conformation with reduced affinity for substrates. A catalytic transition conformation with reduced affinity would essentially result in substrate dissociation and supports a model for drug transport in which an ATP hydrolysis-induced conformational change leads to drug release toward the extracellular medium.

  13. Unraveling Surface Plasmon Decay in Core-Shell Nanostructures toward Broadband Light-Driven Catalytic Organic Synthesis.

    Science.gov (United States)

    Huang, Hao; Zhang, Lei; Lv, Zhiheng; Long, Ran; Zhang, Chao; Lin, Yue; Wei, Kecheng; Wang, Chengming; Chen, Lu; Li, Zhi-Yuan; Zhang, Qun; Luo, Yi; Xiong, Yujie

    2016-06-01

    Harnessing surface plasmon of metal nanostructures to promote catalytic organic synthesis holds great promise in solar-to-chemical energy conversion. High conversion efficiency relies not only on broadening the absorption spectrum but on coupling the harvested energy into chemical reactions. Such coupling undergoes hot-electron transfer and photothermal conversion during the decay of surface plasmon; however, the two plasmonic effects are unfortunately entangled, making their individual roles still under debate. Here, we report that in a model system of bimetallic Au-Pd core-shell nanostructures the two effects can be disentangled through tailoring the shell thickness at atomic-level precision. As demonstrated by our ultrafast absorption spectroscopy characterizations, the achieved tunability of the two effects in a model reaction of Pd-catalyzed organic hydrogenation offers a knob for enhancing energy coupling. In addition, the two intrinsic plasmonic modes at 400-700 and 700-1000 nm in the bar-shaped nanostructures allow for utilizing photons to a large extent in full solar spectrum. This work establishes a paradigmatic guidance toward designing plasmonic-catalytic nanomaterials for enhanced solar-to-chemical energy conversion.

  14. Catalytic conversion of chloromethane to methanol and dimethyl ether over two catalytic beds: a study of acid strength

    Energy Technology Data Exchange (ETDEWEB)

    Fernandes, D.R.; Leite, T.C.M.; Mota, C.J.A. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Quimica], e-mail: cmota@iq.ufrj.br

    2010-07-15

    The catalytic hydrolysis of chloromethane to methanol and dimethyl ether (DME) was studied over metal-exchanged Beta and Mordenite zeolites, acidic MCM-22 and SAPO-5. The use of a second catalytic bed with HZSM-5 zeolite increased the selectivity to DME, due to methanol dehydration on the acid sites. The effect was more significant on catalysts presenting medium and weak acid site distribution, showing that dehydration of methanol to DME is accomplished over sites of higher acid strength. (author)

  15. Separation of electron-transfer and coupled chemical reaction components of biocatalytic processes using Fourier transform ac voltammetry.

    Science.gov (United States)

    Fleming, Barry D; Zhang, Jie; Bond, Alan M; Bell, Stephen G; Wong, Luet-Lok

    2005-06-01

    The underlying electron-transfer and coupled chemical processes associated with biologically important catalytic reactions can be resolved using a combination of Fourier transform ac voltammetry with an analysis of the separated dc and ac components. This outcome can be achieved because the response associated with generation of the catalytic current is essentially confined to the steady-state dc component, whereas the electron-transfer step is dominant in the fundamental and higher harmonics. For the mediated oxidation of glucose with glucose oxidase, it was found that the underlying reversible redox chemistry of the mediator, ferrocenemonocarboxylic acid, as detected in the third and higher harmonics, was totally unaffected by introduction of the catalytic process. In contrast, for the catalytic reduction of molecular oxygen by cytochrome P450, slight changes in the P450 redox process were detected when the catalytic reaction was present. Simulations of a simple catalytic reaction scheme support the fidelity of this novel FT ac voltammetric approach for examining mechanistic nuances of catalytic forms of electrochemical reaction schemes.

  16. 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.

  17. 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).

  18. Prominent catalytic activity of mesoporous molecular sieves in the vapor phase dehydration of cyclohexanol to cyclohexene

    Institute of Scientific and Technical Information of China (English)

    Azhagapillai Prabhu; Ahmed Al Shoaibi; Chandrasekar Srinivasakannan; Muthaiahpillai Palanichamy; Velayutham Murugesan

    2013-01-01

    Cerium incorporated KIT-6 mesoporous materials were synthesized through direct hydrothermal method and characterized by using X-ray diffraction (XRD),nitrogen sorption isotherm (BET),Fourier transform infrared spectroscopy (FT-IR),inductively coupled plasma-atomic emission spectroscopy (ICP-AES),diffuse reflectance ultraviolet visible spectroscopy (DRS-UV-Vis),thermogravimetric analysis (TGA),scanning electron microscopy (SEM) and transmission electron microscopy (TEM) methods.It appeared that stable cerium ions were inserted into the silica framework of KIT-6,thus generating acid properties in their host materials.The catalytic activity of Ce-KIT-6 materials was evaluated in the vapor phase dehydration of cyclohexanol to cyclohexene and dicyclohexyl ether at different temperatures with various Si/Ce molar ratios.Ce-KIT-6 (25) showed higher activity with 54% cyclohexanol conversion and 64% selectivity to cyclohexene.The catalytic results indicated that Ce-KIT-6 mesoporous materials could be used as versatile and stable acid catalysts.

  19. Catalytic pyrolysis characteristics of scrap printed circuit boards by TG-FTIR.

    Science.gov (United States)

    Zhao, Chunhu; Zhang, Xiaoping; Shi, Lin

    2017-03-01

    In the present work, pyrolysis and catalytic pyrolysis of waste printed circuit boards (WPCBs) was carried out in the coupling of Thermo Gravimetric Analysis and Fourier Transform Infrared Spectroscopy (TG-FTIR) under nitrogen atmosphere. The reaction temperature was increased from 30 to 700°C, while the heating rates were varied from 10 to 40°C/min. Experimental results show that the effect of catalyst on the WPCBs particles pyrolysis was significance. Compared with another two combustion-supporting agents (MgO, CaO), the whole pyrolysis process was optimized when the catalyst ZSM-5 was added into the WPCBs particles. The distributed activation energy model (DAEM) was used to analyze the kinetic parameters of the WPCBs pyrolysis. It was found that values of frequency factor (k0) changed with different activation energy (E) values during pyrolysis process. The activation energy values range from 129.15 to 280.53kJ/mol, and the frequency factor values range from 9.02×10(10) to 4.21×10(22)s(-1). The generated major products for the catalytic pyrolysis of WPCBs were H2, CO2, CO, H2O, phenols and aromatics.

  20. Preparation and photo-catalytic activities of FeOOH/ZnO/MMT composite

    Science.gov (United States)

    Zhou, Yao; Liu, Fusheng; Yu, Shitao

    2015-11-01

    Montmorillonite (MMT) was used as the carrier for synthesis of FeOOH and FeOOH/ZnO nano-material. FeOOH and FeOOH/ZnO were synthesized by the aqueous solutions of Fe(NO3)3-HNO3 and Zn(NO3)2-NaOH/Fe(NO3)3-HNO3 with the carrier of montmorillonite respectively. Transmission electron-microscopy (TEM) and X-ray diffraction (XRD) were used to study the morphology form and structure of the nano-materials. TEM was also used to demonstrate that FeOOH/ZnO can be formed with the appropriate interface. According to UV-vis absorption spectra, FeOOH/ZnO has a better response to visible light than FeOOH and ZnO, which indicates there is some coupling effect between FeOOH and ZnO. Pentachlorophenol (PCP) was used as a representative organic pollutant to evaluate the photo-catalytic efficiency of the FeOOH/ZnO and FeOOH catalysts in visible light (λ > 400 nm). The photo-catalytic efficiency of FeOOH/ZnO/MMT is better than FeOOH/MMT. According to FTIR, changes of pH and TOC, the degradation mechanism was also discussed. PCP was degraded to aromatic ketone and chloro-hydrocarbon compounds and then to H2O, CO2 and HCl.

  1. Palladium supported on natural phosphate: Catalyst for Suzuki coupling reactions in water

    KAUST Repository

    Hassine, Ayoub

    2013-01-01

    The Suzuki-Miyaura coupling reaction is one of the most important synthetic catalytic reactions developed in the 20th century. However, the use of toxic organic solvents for this reaction still poses a scientific challenge and is an aspect of economical and ecological relevance. The use of water as a reaction medium overcomes this issue. In the present work, we described efficient Suzuki coupling reactions in water, without any phase transfer reagents and it is possible to couple challenging substrates like aryl chlorides. Notably, this protocol also works with ultra-low loading of catalyst with high turnover numbers. © 2012 Elsevier B.V.

  2. Selective catalytic two-step process for ethylene glycol from carbon monoxide

    Science.gov (United States)

    Dong, Kaiwu; Elangovan, Saravanakumar; Sang, Rui; Spannenberg, Anke; Jackstell, Ralf; Junge, Kathrin; Li, Yuehui; Beller, Matthias

    2016-01-01

    Upgrading C1 chemicals (for example, CO, CO/H2, MeOH and CO2) with C–C bond formation is essential for the synthesis of bulk chemicals. In general, these industrially important processes (for example, Fischer Tropsch) proceed at drastic reaction conditions (>250 °C; high pressure) and suffer from low selectivity, which makes high capital investment necessary and requires additional purifications. Here, a different strategy for the preparation of ethylene glycol (EG) via initial oxidative coupling and subsequent reduction is presented. Separating coupling and reduction steps allows for a completely selective formation of EG (99%) from CO. This two-step catalytic procedure makes use of a Pd-catalysed oxycarbonylation of amines to oxamides at room temperature (RT) and subsequent Ru- or Fe-catalysed hydrogenation to EG. Notably, in the first step the required amines can be efficiently reused. The presented stepwise oxamide-mediated coupling provides the basis for a new strategy for selective upgrading of C1 chemicals. PMID:27377550

  3. Gear Spline Coupling Program

    Energy Technology Data Exchange (ETDEWEB)

    2013-08-29

    An analytical model is developed to evaluate the design of a spline coupling. For a given torque and shaft misalignment, the model calculates the number of teeth in contact, tooth loads, stiffnesses, stresses, and safety factors. The analytic model provides essential spline coupling design and modeling information and could be easily integrated into gearbox design and simulation tools.

  4. Translation-coupling systems

    Science.gov (United States)

    Pfleger, Brian; Mendez-Perez, Daniel

    2013-11-05

    Disclosed are systems and methods for coupling translation of a target gene to a detectable response gene. A version of the invention includes a translation-coupling cassette. The translation-coupling cassette includes a target gene, a response gene, a response-gene translation control element, and a secondary structure-forming sequence that reversibly forms a secondary structure masking the response-gene translation control element. Masking of the response-gene translation control element inhibits translation of the response gene. Full translation of the target gene results in unfolding of the secondary structure and consequent translation of the response gene. Translation of the target gene is determined by detecting presence of the response-gene protein product. The invention further includes RNA transcripts of the translation-coupling cassettes, vectors comprising the translation-coupling cassettes, hosts comprising the translation-coupling cassettes, methods of using the translation-coupling cassettes, and gene products produced with the translation-coupling cassettes.

  5. Bibliographic Coupling: A Review

    Science.gov (United States)

    Weinberg, Bella Hass

    1974-01-01

    The theory and practical applications of bibliographic coupling are reviewed. The reviewer takes issue with the use of bibliographic coupling for information retrieval and automatic classification on logical grounds, and for reasons relating to uncontrolled citation practices. The usefulness of the procedure for the study of the science of science…

  6. Translation-coupling systems

    Energy Technology Data Exchange (ETDEWEB)

    Pfleger, Brian; Mendez-Perez, Daniel

    2015-05-19

    Disclosed are systems and methods for coupling translation of a target gene to a detectable response gene. A version of the invention includes a translation-coupling cassette. The translation-coupling cassette includes a target gene, a response gene, a response-gene translation control element, and a secondary structure-forming sequence that reversibly forms a secondary structure masking the response-gene translation control element. Masking of the response-gene translation control element inhibits translation of the response gene. Full translation of the target gene results in unfolding of the secondary structure and consequent translation of the response gene. Translation of the target gene is determined by detecting presence of the response-gene protein product. The invention further includes RNA transcripts of the translation-coupling cassettes, vectors comprising the translation-coupling cassettes, hosts comprising the translation-coupling cassettes, methods of using the translation-coupling cassettes, and gene products produced with the translation-coupling cassettes.

  7. Catalytic synthesis of silicon carbide preceramic polymers: Polycarbosilanes. Research progress report, March 1, 1991--October 31, 1991

    Energy Technology Data Exchange (ETDEWEB)

    Berry, D.H.

    1991-11-01

    Polycarbosilanes are the most successful and widely studied class of polymer precursors for silicon carbide, but traditional methods for thier synthesis are inefficient and nonselective. This project is focused on developing transition metal catalysts for the synthesis of polycarbosilanes and other perceramic polymers. In recent work we have developed the first homogeneous transition metal catalysts for the dehydrogenative coupling of simple alkyl silanes to oligomeric and polymeric carbosilanes, H-(SiR{sub 2}CR{prime}{sub 2}){sub n}-SiR{sub 3}. Future work will help elucidate the mechanism of the catalytic process, explore the use of hydrogen acceptors as reaction accelerators, and develop new and more active catalysts.

  8. Millisecond dynamics in glutaredoxin during catalytic turnover is dependent on substrate binding and absent in the resting states

    DEFF Research Database (Denmark)

    Jensen, Kristine Steen; Winther, Jakob R; Teilum, Kaare

    2011-01-01

    on the time scale of catalytic turnover were not observed for the enzyme in the resting states, implying that alternative conformers do not accumulate to significant concentrations. These results infer that the turnover rate in glutaredoxin is governed by formation of a productive enzyme-substrate encounter...... to the glutathione exchange rate was observed for 23 residues. Binding of reduced glutathione resulted in competitive inhibition of the reduced enzyme having kinetics similar to that of the reaction. This observation couples the motions observed during catalysis directly to substrate binding. Backbone motions...

  9. Dynamic\tmodelling of catalytic three-phase reactors for hydrogenation and oxidation processes

    Directory of Open Access Journals (Sweden)

    Salmi T.

    2000-01-01

    Full Text Available The dynamic modelling principles for typical catalytic three-phase reactors, batch autoclaves and fixed (trickle beds were described. The models consist of balance equations for the catalyst particles as well as for the bulk phases of gas and liquid. Rate equations, transport models and mass balances were coupled to generalized heterogeneous models which were solved with respect to time and space with algorithms suitable for stiff differential equations. The aspects of numerical solution strategies were discussed and the procedure was illustrated with three case studies: hydrogenation of aromatics, hydrogenation of aldehydes and oxidation of ferrosulphate. The case studies revealed the importance of mass transfer resistance inside the catalyst pallets as well as the dynamics of the different phases being present in the reactor. Reliable three-phase reactor simulation and scale-up should be based on dynamic heterogeneous models.

  10. H2CAP - Hydrogen assisted catalytic biomass pyrolysis for green fuels

    DEFF Research Database (Denmark)

    Arndal, Trine Marie Hartmann; Høj, Martin; Jensen, Peter Arendt

    2014-01-01

    that can be used to upgrade the crude bio-oil to fuel-grade oil. The development of the HDO process is challenged by rapid catalyst deactivation, instability of the pyrolysis oil, poorly investigated reaction conditions and a high complexity and variability of the input oil composition. However, continuous...... catalytic hydropyrolysis coupled with downstream HDO of the pyrolysis vapors before condensation shows promise (Figure 1). A bench scale experimental setup will be constructed for the continuous conversion of solid biomass (100g /h) to low oxygen, fuel-grade bio-oil. The aim is to provide a proof......-of-concept for the proposed process(Figure 1), to understand the reaction mechanisms of HDO, to develop highly active and durable catalysts for hydropyrolysis and HDO and to optimize the operating conditions; all in order to develop a sustainable production of green transportation fuels from biomass.To support the process...

  11. Precursor type affecting surface properties and catalytic activity of sulfated zirconia

    Directory of Open Access Journals (Sweden)

    Zarubica Aleksandra R.

    2007-01-01

    Full Text Available Zirconium-hydroxide precursor samples are synthesized from Zr-hydroxide, Zr-nitrate, and Zr-alkoxide, by precipitation/impregnation, as well as by a modified sol-gel method. Precursor samples are further sulphated for the intended SO4 2- content of 4 wt.%, and calcined at 500-700oC. Differences in precursors’ origin and calcination temperature induce the incorporation of SO4 2- groups into ZrO2 matrices by various mechanisms. As a result, different amounts of residual sulphates are coupled with other structural, as well as surface properties, resulting in various catalytic activities of sulphated zirconia samples. Catalyst activity and selectivity are a complex synergistic function of tetragonal phase fraction, sulphates contents, textural and surface characteristics. Superior activity of SZ of alkoxide origin can be explained by a beneficial effect of meso-pores owing to a better accommodation of coke deposits.

  12. 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.

  13. Carbon supported trimetallic nickel-palladium-gold hollow nanoparticles with superior catalytic activity for methanol electrooxidation

    Science.gov (United States)

    Shang, Changshuai; Hong, Wei; Wang, Jin; Wang, Erkang

    2015-07-01

    In this paper, Ni nanoparticles (NPs) are prepared in an aqueous solution by using sodium borohydride as reducing agent. With Ni NPs as the sacrificial template, hollow NiPdAu NPs are successfully prepared via partly galvanic displacement reaction between suitable metal precursors and Ni NPs. The as-synthesized hollow NiPdAu NPs can well dispersed on the carbon substrate. Transmission electron microscopy, X-ray diffraction and inductively coupled plasma mass spectrometry are taken to analyze the morphology, structure and composition of the as-synthesized catalysts. The prepared catalysts show superior catalytic activity and stability for methanol electrooxidation in alkaline media compared with commercial Pd/C and Pt/C. Catalysts prepared in this work show great potential to be anode catalysts in direct methanol fuel cells.

  14. 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

  15. Reductive Catalytic Fractionation of Corn Stover Lignin

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Eric M.; Katahira, Rui; Reed, Michelle; Resch, Michael G.; Karp, Eric M.; Beckham, Gregg T.; Román-Leshkov, Yuriy

    2016-12-05

    Reductive catalytic fractionation (RCF) has emerged as an effective biomass pretreatment strategy to depolymerize lignin into tractable fragments in high yields. We investigate the RCF of corn stover, a highly abundant herbaceous feedstock, using carbon-supported Ru and Ni catalysts at 200 and 250 degrees C in methanol and, in the presence or absence of an acid cocatalyst (H3PO4 or an acidified carbon support). Three key performance variables were studied: (1) the effectiveness of lignin extraction as measured by the yield of lignin oil, (2) the yield of monomers in the lignin oil, and (3) the carbohydrate retention in the residual solids after RCF. The monomers included methyl coumarate/ferulate, propyl guaiacol/syringol, and ethyl guaiacol/syringol. The Ru and Ni catalysts performed similarly in terms of product distribution and monomer yields. The monomer yields increased monotonically as a function of time for both temperatures. At 6 h, monomer yields of 27.2 and 28.3% were obtained at 250 and 200 degrees C, respectively, with Ni/C. The addition of an acid cocatalysts to the Ni/C system increased monomer yields to 32% for acidified carbon and 38% for phosphoric acid at 200 degrees C. The monomer product distribution was dominated by methyl coumarate regardless of the use of the acid cocatalysts. The use of phosphoric acid at 200 degrees C or the high temperature condition without acid resulted in complete lignin extraction and partial sugar solubilization (up to 50%) thereby generating lignin oil yields that exceeded the theoretical limit. In contrast, using either Ni/C or Ni on acidified carbon at 200 degrees C resulted in moderate lignin oil yields of ca. 55%, with sugar retention values >90%. Notably, these sugars were amenable to enzymatic digestion, reaching conversions >90% at 96 h. Characterization studies on the lignin oils using two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance and gel permeation chromatrography revealed

  16. OXIDATIVE COUPLING OF METHANE USING INORGANIC MEMBRANE REACTORS

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Y.H. Ma; Dr. W.R. Moser; Dr. A.G. Dixon; Dr. A.M. Ramachandra; Dr. Y. Lu; C. Binkerd

    1998-04-01

    The objective of this research is to study the oxidative coupling of methane in catalytic inorganic membrane reactors. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and higher yields than in conventional non-porous, co-feed, fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for the formation of CO{sub x} products. Such gas phase reactions are a cause of decreased selectivity in the oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Membrane reactor technology also offers the potential for modifying the membranes both to improve catalytic properties as well as to regulate the rate of the permeation/diffusion of reactants through the membrane to minimize by-product generation. Other benefits also exist with membrane reactors, such as the mitigation of thermal hot-spots for highly exothermic reactions such as the oxidative coupling of methane. The application of catalytically active inorganic membranes has potential for drastically increasing the yield of reactions which are currently limited by either thermodynamic equilibria, product inhibition, or kinetic selectivity.

  17. Role for threonine 201 in the catalytic cycle of the soluble diiron hydroxylase toluene 4-monooxygenase.

    Science.gov (United States)

    Elsen, Nathaniel L; Bailey, Lucas J; Hauser, Andrew D; Fox, Brian G

    2009-05-12

    The active site residue Thr-201 in toluene 4-monooxygenase hydroxylase (T4moH) has a structural counterpart in the active sites of all diiron monooxygenases. Thus, our previous finding that mutation of this residue to Ala, Gly, or Ser had no impact on steady-state catalysis or coupling was surprising. In this work, we provide kinetic, biochemical, and structural evidence that one role of Thr-201 may be to stabilize a peroxo-level intermediate during enzyme catalysis. During reactions in the absence of substrate, T201 T4moH slowly consumed O(2) but only a negligible amount of H(2)O(2) was released. In contrast, T201A T4moH gave stoichometric release of H(2)O(2) during reaction in the absence of substrate. Both enzyme isoforms were tightly coupled during steady-state catalysis with saturating toluene and other optimal substrates and exhibited near-identical kinetic parameters. However, rapid mix single-turnover studies showed that T201A T4moH had a faster first-order rate constant for product formation than T201 T4moH did. Comparison of X-ray crystal structures of resting and reduced T201A T4moH in complex with T4moD with comparable structures of T201 T4moHD revealed changes in the positions of several key active site residues relative to the comparable structures of T201 T4moH with T4moD. This combination of catalytic and structural studies offers important new insight into the role of the role of conserved Thr-201, and its contributions to the catalytic reaction cycle.

  18. The influence of copper in dealloyed binary platinum–copper electrocatalysts on methanol electroxidation catalytic activities

    Energy Technology Data Exchange (ETDEWEB)

    Poochai, Chatwarin [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Veerasai, Waret, E-mail: waret.vee@mahidol.ac.th [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Somsook, Ekasith [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Dangtip, Somsak [Department of Physics, and NANOTEC COE at Mahidol University, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand)

    2015-08-01

    In this study, we prepared and characterized carbon paper-supported dealloyed binary Pt–Cu core–shell electrocatalysts (denoted as Pt{sub x}Cu{sub (100−x)/}CP) by cyclic co-electrodeposition and selective copper dealloying in an acidic medium, and we investigated the effect of the copper content in the samples on the catalytic activities toward methanol electroxidation reaction (MOR). X-ray photo-emission spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES) indicated that the structure of dealloyed binary Pt–Cu catalysts possessed a Pt-rich shell and a Cu rich core. X-ray absorption near edge spectroscopy (XANES) displayed that the oxidation states of Pt and Cu were zero and one, respectively, implying the formation of metallic Pt and Cu{sub 2}O, respectively. X-ray diffraction spectroscopy (XRD) confirmed that Cu was inserted into a face-centered cubic Pt structure forming Pt–Cu alloys. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) displayed a cubic shape of Pt/CP and a spherical shape of Pt{sub x}Cu{sub (100−x)/}CP with several hundred nanometer sizes of agglomeration that depended on the Cu content. Cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy were performed to confirm that the sample of Pt{sub 70}Cu{sub 30}/CP exhibited the best catalytic activities in terms of the specific current, current density, catalytic poisoning tolerance, and stability. - Graphical abstract: Display Omitted - Highlights: • Binary electrocatalysts of Pt{sub x}Cu{sub (100−x)}/CP were prepared by cyclic co-electrodeposition and selective copper dealloying. • The structures of Pt{sub x}Cu{sub (100−x)}/CP were a Pt rich shell and a Cu rich core. • The Pt{sub 70}Cu{sub 30}/CP was the excellent catalytic activity towards methanol electrooxidation and CO{sub ads} tolerance.

  19. Depression: The Differing Narratives of Couples in Couple Therapy

    Science.gov (United States)

    Rautiainen, Eija-Liisa; Aaltonen, Jukka

    2010-01-01

    How does the spouse of a person with depression take part in constructing narratives of depression in couple therapy? In this study we examined couples' ways of co-constructing narratives of depression in couple therapy. Three couple therapy processes were chosen for the study, one spouse in each couple having been referred to an outpatient clinic…

  20. A compact process for the treatment of olive mill wastewater by combining wet hydrogen peroxide catalytic oxidation and biological techniques.

    Science.gov (United States)

    Azabou, Samia; Najjar, Wahiba; Bouaziz, Mohamed; Ghorbel, Abdelhamid; Sayadi, Sami

    2010-11-15

    A system based on combined actions of catalytic wet oxidation and microbial technologies for the treatment of highly polluted OMW containing polyphenols was studied. The wet hydrogen peroxide catalytic oxidation (WHPCO) process has been investigated in the semi-batch mode at atmospheric pressure, using aluminium-iron-pillared inter layer clay ((Al-Fe)PILC), under two different catalytic processes: ((Al-Fe)PILC/H(2)O(2)/ultraviolet radiations) at 25°C and ((Al-Fe)PILC/H(2)O(2)) at 50°C. The results show that raw OMW was resistant to the photocatalytic process. However ((Al-Fe)PILC/H(2)O(2)), system operating at 50°C reduced considerably the COD, colour and total phenolic contents, and thus decreased the inhibition of the marine photobacteria Vibrio fischeri luminescence by 70%. This study also examined the feasibility of coupling WHPCO and anaerobic digestion treatment. Biomethanisation experiments performed with raw OMW or pre-treated OMW proved that pre-treatments with ((Al-Fe)PILC/H(2)O(2)) system, for more than 2 h, resulted in higher methane production. Both untreated OMW as well as 2-h pre-treated OMW revealed as toxic to anaerobic bacteria.

  1. Effects of support acidity on the reaction mechanisms of selective catalytic reduction of NO by CH4 in excess oxygen

    Institute of Scientific and Technical Information of China (English)

    Shicheng XU; Junhua LI; Dong YANG; Jiming HAO

    2009-01-01

    The reaction mechanisms of selective catalytic reduction (SCR) of nitric oxide (NO) by methane (CH4)over solid superacid-based catalysts were proposed and testified by DRIFTS studies on transient reaction as well as by kinetic models. Catalysts derived from different supports would lead to different reaction pathways, and the acidity of solid superacid played an important role in determining the reaction mechanisms and the catalytic activities. Higher ratios of Bronsted acid sites to Lewis acid sites would lead to stronger oxidation of methane and then could facilitate the step of methane activation. Strong Bronsted acid sites would not necessarily lead to better catalytic performance, however, since the active surface NOy species and the corresponding reaction routes were determined by the overall acidity strength of the support.The reaction routes where NO2 moiety was engaged as an important intermediate involved moderate oxidation of methane, the rate of which could determine the overall activity. The reaction involving NO moiety was likely to be determined by the step of reduction of NO. Therefore, to enhance the SCR activity of solid superacid catalysts,reactions between appropriate couples of active NOy species and activated hydrocarbon intermediates should be realized by modification of the support acidity.

  2. Photo-catalytic Activities of Plant Hormones on Semiconductor Nanoparticles by Laser-Activated Electron Tunneling and Emitting

    Science.gov (United States)

    Tang, Xuemei; Huang, Lulu; Zhang, Wenyang; Jiang, Ruowei; Zhong, Hongying

    2015-03-01

    Understanding of the dynamic process of laser-induced ultrafast electron tunneling is still very limited. It has been thought that the photo-catalytic reaction of adsorbents on the surface is either dependent on the number of resultant electron-hole pairs where excess energy is lost to the lattice through coupling with phonon modes, or dependent on irradiation photon wavelength. We used UV (355 nm) laser pulses to excite electrons from the valence band to the conduction band of titanium dioxide (TiO2), zinc oxide (ZnO) and bismuth cobalt zinc oxide (Bi2O3)0.07(CoO)0.03(ZnO)0.9 semiconductor nanoparticles with different photo catalytic properties. Photoelectrons are extracted, accelerated in a static electric field and eventually captured by charge deficient atoms of adsorbed organic molecules. A time-of-flight mass spectrometer was used to detect negative molecules and fragment ions generated by un-paired electron directed bond cleavages. We show that the probability of electron tunneling is determined by the strength of the static electric field and intrinsic electron mobility of semiconductors. Photo-catalytic dissociation or polymerization reactions of adsorbents are highly dependent on the kinetic energy of tunneling electrons as well as the strength of laser influx. By using this approach, photo-activities of phytohormones have been investigated.

  3. Preconversion catalytic deoxygenation of phenolic functional groups. Quarterly technical progress report, April 1, 1991--June 30, 1991

    Energy Technology Data Exchange (ETDEWEB)

    Kubiak, C.P.

    1991-12-31

    The deoxygenation of phenols is a conceptually simple, but unusually difficult chemical transformation to achieve. Aryl carbon-oxygen bond cleavage is a chemical transformation of importance in coal liquefaction and the upgrading of coal liquids as well as in the synthesis of natural products. This proposed research offers the possibility of effecting the selective catalytic deoxygenation of phenolic functional groups using CO. A program of research for the catalytic deoxygenation of phenols, via a low energy mechanistic pathway that is based on the use of the CO/CO{sub 2} couple to remove phenolic oxygen atoms, is underway. We are focusing on systems which have significant promise as catalysts: Ir(triphos)OPh, [Pt(triphos)OPh]{sup +} and Rh(triphos)OPh. Our studies of phenol deoxygenation focus on monitoring the reactions for the elementary processes upon which catalytic activity will depend: CO insertion into M-OPh bonds, CO{sub 2} elimination from aryloxy carbonyls {l_brace}M-C(O)-O-Ph{r_brace}, followed by formation of a coordinated benzyne intermediate.

  4. Spectroscopic characterization of the catalytically competent ferrous site of the resting, activated, and substrate-bound forms of phenylalanine hydroxylase

    Energy Technology Data Exchange (ETDEWEB)

    Loeb, K.E.; Westre, T.E.; Hedman, B.; Hodgson, K.O.; Solomon, E.I. [Stanford Univ., CA (United States); Kappock, T.J.; Mitic, N.; Glasfeld, E.; Caradonna, J.P. [Yale Univ., New Haven, CT (United States)

    1997-02-26

    The geometric structure of the catalytically relevant ferrous active site of phenylalanine hydroxylase (PAH) has been investigated using magnetic circular dichroism (MCD) and X-ray absorption (XAS) spectroscopies. From the excited state ligand field transitions in the MCD spectrum, the temperature and field dependence of these transitions, and the XAS pre-edge shapes and intensities, the resting ferrous site of the `tense` from PAH is six-coordinate distorted octahedral. The low ligand field strength observed in the MCD spectrum results from significant oxygen ligation and longer Fe-O/N bond distances relative to model complexes as determined from an EXAFS analysis. Substrate-induced allosteric activation ({approx}34 kcal/mol) does not alter the structure of the iron site in the `relaxed` form of PAH compared to the substrate-bound `tense` state. Thus, while activation is necessary for the enzyme to achieve complete catalytic competence, it does not appear to affect the geometry of the catalytically relevent six-coordinate ferrous active site and only directly influences the surrounding protein conformation. In contrast, substrate addition results in a geometric and electronic structural change at the iron center which may help orient the substrate for completely coupled hydroxylation. 106 refs., 10 figs., 6 tabs.

  5. Photo-catalytic activities of plant hormones on semiconductor nanoparticles by laser-activated electron tunneling and emitting.

    Science.gov (United States)

    Tang, Xuemei; Huang, Lulu; Zhang, Wenyang; Jiang, Ruowei; Zhong, Hongying

    2015-01-01

    Understanding of the dynamic process of laser-induced ultrafast electron tunneling is still very limited. It has been thought that the photo-catalytic reaction of adsorbents on the surface is either dependent on the number of resultant electron-hole pairs where excess energy is lost to the lattice through coupling with phonon modes, or dependent on irradiation photon wavelength. We used UV (355 nm) laser pulses to excite electrons from the valence band to the conduction band of titanium dioxide (TiO₂), zinc oxide (ZnO) and bismuth cobalt zinc oxide (Bi₂O₃)₀.₀₇(CoO)₀.₀₃(ZnO)₀.₉ semiconductor nanoparticles with different photo catalytic properties. Photoelectrons are extracted, accelerated in a static electric field and eventually captured by charge deficient atoms of adsorbed organic molecules. A time-of-flight mass spectrometer was used to detect negative molecules and fragment ions generated by un-paired electron directed bond cleavages. We show that the probability of electron tunneling is determined by the strength of the static electric field and intrinsic electron mobility of semiconductors. Photo-catalytic dissociation or polymerization reactions of adsorbents are highly dependent on the kinetic energy of tunneling electrons as well as the strength of laser influx. By using this approach, photo-activities of phytohormones have been investigated.

  6. Catalytic conversion of biomass to fuels. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Garten, R. L.; Ushiba, K. K.; Cooper, M.; Mahawili, I.

    1978-01-01

    This report presents an assessment and perspective concerning the application of catalytic technologies to the thermochemical conversion of biomass resources to fuels. The major objectives of the study are: to provide a systematic assessment of the role of catalysis in the direct thermochemical conversion of biomass into gaseous and liquid fuels; to establish the relationship between potential biomass conversion processes and catalytic processes currently under development in other areas, with particular emphasis on coal conversion processes; and to identify promising catalytic systems which could be utilized to reduce the overall costs of fuels production from biomass materials. The report is divided into five major parts which address the above objectives. In Part III the physical and chemical properties of biomass and coal are compared, and the implications for catalytic conversion processes are discussed. With respect to chemical properties, biomass is shown to have significant advantages over coal in catalytic conversion processes because of its uniformly high H/C ratio and low concentrations of potential catalyst poisons. The physical properties of biomass can vary widely, however, and preprocessing by grinding is difficult and costly. Conversion technologies that require little preprocessing and accept a wide range of feed geometries, densities, and particle sizes appear desirable. Part IV provides a comprehensive review of existing and emerging thermochemical conversion technologies for biomass and coal. The underlying science and technology for gasification and liquefaction processes are presented.

  7. Catalytic conversion of ethanol on H-Y zeolite

    Directory of Open Access Journals (Sweden)

    Čegar Nedeljko

    2005-01-01

    Full Text Available The catalytic activity of the H-form of synthetic zeolite NaY was examined in this study. The catalytic activity was determined according to the rate of ethanol conversion in a gas phase in the static system. In the conversion of ethanol on synthetic NaY zeolite at 585, 595, and 610 K, on which the reaction develops at an optimal rate, ethene and diethyl ether are evolved in approximately the same quantity. After transforming the NaY zeolite into the H-form, its catalytic activity was extremely increases so, the reaction develops at a significantly lower temperature with a very large increase in the reaction rate. The distribution of the products also changes, so that at lower temperatures diethyl ether is elvolved in most cases, and the development of ethene is favored at higher ones, and after a certain period of time there is almost complete conversion of ethanol into ethene. The increase in catalytic activity, as well as the change of selectivity of conversion of ethanol on the H-form of zeolite, is the result of removing Na+ cations in the NaY zeolite, so that more acidic catalyst is obtained which contains a number of acidic catalytically active centers, as well as a more powerful one compared to the original NaY zeolite.

  8. Reduction of nitrate from groundwater: powder catalysts and catalytic membrane.

    Science.gov (United States)

    Chen, Ying-Xu; Zhang, Yan; Liu, Hong-Yuan

    2003-09-01

    The reduction of nitrate contaminant in groundwater has gained renewed and intensive attention due to the environmental problems and health risks. Catalytic denetrification presents one of the most promising approaches for the removal of nitrate from water. Catalytic nitrate reduction from water by powder catalysts and catalytic membrane in a batch reactor was studied. And the effects of the initial concentration, the amounts of catalyst, and the flux H2 on the nitrate reduction were also discussed. The results demonstrated that nitrate reduction activity and the selectivity to nitrogen gas were mainly controlled by diffusion limitations and the mass transfer of the reactants. The selectivity can improved while retaining a high catalytic activity under controlled diffusion condition or the intensification of the mass transfer, and a good reaction condition. The total nitrogen removal efficiency reached above 80%. Moreover, catalytic membrane can create a high effective gas/liquid/solid interface, and show a good selectivity to nitrogen in comparative with the powder catalyst, the selectivity to nitrogen was improved from 73.4% to 89.4%.

  9. Reduction of nitrate from groundwater: powder catalysts and catalytic membrane

    Institute of Scientific and Technical Information of China (English)

    CHEN Ying-xu; ZHANG Yan; LIU Hong-yuan

    2003-01-01

    The reduction of nitrate contaminant in groundwater has gained renewed and intensive attention due to the environmental problems and health risks. Catalytic denetrification presents one of the most promising approaches for the removal of nitrate from water. Catalytic nitrate reduction from water by powder catalysts and catalytic membrane in a batch reactor was studied. And the effects of the initial concentration, the amounts of catalyst, and the flux H2 on the nitrate reduction were also discussed. The results demonstrated that nitrate reduction activity and the selectivity to nitrogen gas were mainly controlled by diffusion limitations and the mass transfer of the reactants. The selectivity can improved while retaining a high catalytic activity under controlled diffusion condition or the intensification of the mass transfer, and a good reaction condition. The total nitrogen removal efficiency reached above 80%. Moreover, catalytic membrane can create a high effective gas/liquid/solid interface, and show a good selectivity to nitrogen in comparative with the powder catalyst, the selectivity to nitrogen was improved from 73.4% to 89.4%.

  10. Poisoning of bubble propelled catalytic micromotors: the chemical environment matters

    Science.gov (United States)

    Zhao, Guanjia; Sanchez, Samuel; Schmidt, Oliver G.; Pumera, Martin

    2013-03-01

    Self-propelled catalytic microjets have attracted considerable attention in recent years and these devices have exhibited the ability to move in complex media. The mechanism of propulsion is via the Pt catalysed decomposition of H2O2 and it is understood that the Pt surface is highly susceptible to poisoning by sulphur-containing molecules. Here, we show that important extracellular thiols as well as basic organic molecules can significantly hamper the motion of catalytic microjet engines. This is due to two different mechanisms: (i) molecules such as dimethyl sulfoxide can quench the hydroxyl radicals produced at Pt surfaces and reduce the amount of oxygen gas generated and (ii) molecules containing -SH, -SSR, and -SCH3 moieties can poison the catalytically active platinum surface, inhibiting the motion of the jet engines. It is essential that the presence of such molecules in the environment be taken into consideration for future design and operation of catalytic microjet engines. We show this effect on catalytic micromotors prepared by both rolled-up and electrodeposition approaches, demonstrating that such poisoning is universal for Pt catalyzed micromotors. We believe that our findings will contribute significantly to this field to develop alternative systems or catalysts for self-propulsion when practical applications in the real environment are considered.

  11. Bite angle effects of diphosphines in C-C and C-X bond forming cross coupling reactions

    NARCIS (Netherlands)

    Birkholz, M.N.; Freixa, Z.; van Leeuwen, P.W.N.M.

    2009-01-01

    Catalytic reactions of C-C and C-X bond formation are discussed in this critical review with particular emphasis on cross coupling reactions catalyzed by palladium and wide bite angle bidentate diphosphine ligands. Especially those studies have been collected that allow comparison of the ligand bite

  12. Application of bisphosphomide-palladium(II) pincer complex in Suzuki-Miyaura cross-coupling reaction under microwave irradiation

    Indian Academy of Sciences (India)

    Maruthai Kumaravel; Pawan Kumar; Maravanji S Balakrishna

    2014-05-01

    The bisphosphomide-based pincer complex [PdBr{2,6-{Ph2PC(O)}2(C6H3)}] (2) has shown very high catalytic activity in Suzuki-Miyaura cross coupling reaction under microwave irradiation for a variety of aryl bromides and aryl boronic acids. The complex showed the same efficiency for gram scale reactions.

  13. 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.

  14. Hydrogen production via catalytic processing of renewable feedstocks

    Energy Technology Data Exchange (ETDEWEB)

    Nazim Muradov; Franklyn Smith; Ali T-Raissi [Florida Solar Energy Center, University of Central Florida, Cocoa, Florida, (United States)

    2006-07-01

    Landfill gas (LFG) and biogas can potentially become important feedstocks for renewable hydrogen production. The objectives of this work were: (1) to develop a catalytic process for direct reforming of CH{sub 4}-CO{sub 2} gaseous mixture mimicking LFG, (2) perform thermodynamic analysis of the reforming process using AspenPlus chemical process simulator, (3) determine operational conditions for auto-thermal (or thermo-neutral) reforming of a model CH{sub 4}-CO{sub 2} feedstock, and (4) fabricate and test a bench-scale hydrogen production unit. Experimental data obtained from catalytic reformation of the CH{sub 4}-CO{sub 2} and CH{sub 4}-CO{sub 2}-O{sub 2} gaseous mixtures using Ni-catalyst were in a good agreement with the simulation results. It was demonstrated that catalytic reforming of LFG-mimicking gas produced hydrogen with the purity of 99.9 vol.%. (authors)

  15. Catalytic enantioselective addition of Grignard reagents to aromatic silyl ketimines

    Science.gov (United States)

    Rong, Jiawei; Collados, Juan F.; Ortiz, Pablo; Jumde, Ravindra P.; Otten, Edwin; Harutyunyan, Syuzanna R.

    2016-12-01

    α-Chiral amines are of significant importance in medicinal chemistry, asymmetric synthesis and material science, but methods for their efficient synthesis are scarce. In particular, the synthesis of α-chiral amines with the challenging tetrasubstituted carbon stereocentre is a long-standing problem and catalytic asymmetric additions of organometallic reagents to ketimines that would give direct access to these molecules are underdeveloped. Here we report a highly enantioselective catalytic synthesis of N-sulfonyl protected α-chiral silyl amines via the addition of inexpensive, easy to handle and readily available Grignard reagents to silyl ketimines. The key to this success was our ability to suppress any unselective background addition reactions and side reduction pathway, through the identification of an inexpensive, chiral Cu-complex as the catalytically active structure.

  16. 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.

  17. Photolytic AND Catalytic Destruction of Organic Waste Water Pollutants

    Science.gov (United States)

    Torosyan, V. F.; Torosyan, E. S.; Kryuchkova, S. O.; Gromov, V. E.

    2017-01-01

    The system: water supply source - potable and industrial water - wastewater - sewage treatment - water supply source is necessary for water supply and efficient utilization of water resources. Up-to-date technologies of waste water biological treatment require for special microorganisms, which are technologically complex and expensive but unable to solve all the problems. Application of photolytic and catalytically-oxidizing destruction is quite promising. However, the most reagents are strong oxidizers in catalytic oxidation of organic substances and can initiate toxic substance generation. Methodic and scientific approaches to assess bread making industry influence on the environment have been developed in this paper in order to support forecasting and taking technological decisions concerning reduction of this influence. Destructive methods have been tested: ultra violet irradiation and catalytic oxidation for extraction of organic compounds from waste water by natural reagents.

  18. Catalytically and noncatalytically treated automobile exhaust: biological effects in rats

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, G.P. (Univ. of Cincinnati); Lewkowski, J.P.; Hastings, L.; Malanchuk, M.

    1977-12-01

    Chronic exposure to catalytically treated or noncatalytically treated automobile exhaust significantly depressed the spontaneous locomotor activity (SLA) of rats. Exposure to H/sub 2/SO/sub 4/ alone or CO at comparable levels did not alter the SLA. Exposure to noncatalytically treated exhaust resulted in significant reductions in growth rate and food and water intake. However, these effects were not evident in the exposure to catalytically treated exhaust or in the control H/sub 2/SO/sub 4/ and CO exposures. Blood acid-base analyses indicated that exposure to either catalytically treated exhaust or H/sub 2/SO/sub 4/ elicits a metabolic alkalosis, while exposure to CO alone results in a metabolic acidosis. All acid-base parameters were within the normal range several weeks after the termination of exposure.

  19. Catalytic Desulfurization of Benzothiophene Using Keggin Type Polyoxometalates as Catalyst

    Directory of Open Access Journals (Sweden)

    Aldes Lesbani

    2015-01-01

    Full Text Available Performance of catalytic desulfurization of benzothiophen (BT was studied using polyoxometalates as catalyst. Polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40], have different heteroatom in Keggin structure and catalytic activities. Polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] have high crystallinity with homogeneous distribution particles. Desulfurization of BT using polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] resulted % conversion up to 99% for 3 h reaction time and at temperature 40 oC. Application of polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] for crude oil desulfurization showed % conversion of 4-88%. The main functional groups of polyoxometalates still retained after catalytic desulfurization indicated the stability of polyoxometalate compounds

  20. Catalytically highly active top gold atom on palladium nanocluster.

    Science.gov (United States)

    Zhang, Haijun; Watanabe, Tatsuya; Okumura, Mitsutaka; Haruta, Masatake; Toshima, Naoki

    2011-10-23

    Catalysis using gold is emerging as an important field of research in connection with 'green' chemistry. Several hypotheses have been presented to explain the markedly high activities of Au catalysts. So far, the origin of the catalytic activities of supported Au catalysts can be assigned to the perimeter interfaces between Au nanoclusters and the support. However, the genesis of the catalytic activities of colloidal Au-based bimetallic nanoclusters is unclear. Moreover, it is still a challenge to synthesize Au-based colloidal catalysts with high activity. Here we now present the 'crown-jewel' concept (Supplementary Fig. S1) for preparation of catalytically highly Au-based colloidal catalysts. Au-Pd colloidal catalysts containing an abundance of top (vertex or corner) Au atoms were synthesized according to the strategy on a large scale. Our results indicate that the genesis of the high activity of the catalysts could be ascribed to the presence of negatively charged top Au atoms.

  1. Electro-catalytic degradation of sulfisoxazole by using graphene anode.

    Science.gov (United States)

    Wang, Yanyan; Liu, Shuan; Li, Ruiping; Huang, Yingping; Chen, Chuncheng

    2016-05-01

    Graphite and graphene electrodes were prepared by using pure graphite as precursor. The electrode materials were characterized by a scanning electron microscope (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV) measurements. The electro-catalytic activity for degradation of sulfisoxazole (SIZ) was investigated by using prepared graphene or graphite anode. The results showed that the degradation of SIZ was much more rapid on the graphene than that on the graphite electrode. Moreover, the graphene electrode exhibited good stability and recyclability. The analysis on the intermediate products and the measurement of active species during the SIZ degradation demonstrated that indirect oxidation is the dominant mechanism, involving the electro-catalytic generation of OH and O2(-) as the main active oxygen species. This study implies that graphene is a promising potential electrode material for long-term application to electro-catalytic degradation of organic pollutants.

  2. A catalytic distillation process for light gas oil hydrodesulfurization

    Energy Technology Data Exchange (ETDEWEB)

    Vargas-Villamil, F.D.; Marroquin, J.O.; Paz, C. de la; Rodriguez, E. [Prog. de Matematicas Aplicadas y Computacion, Prog. de Tratamiento de Crudo Maya, Instituto Mexicano del Petroleo, Mexico City, DF (Mexico)

    2004-07-01

    A light gas oil hydrodesulfurization process via catalytic distillation is developed and compared to a conventional process. By integrating the separation and reaction into a single unit, the catalytic distillation may produce a diesel with low concentration of sulfur compounds at a lower cost than the traditional reaction/separation process. The process proposed in this work is compared to an optimised conventional hydrodesulfurization unit which represents fairly well a plant that belongs to the National System of Refineries. During the optimisation of the conventional process, a compromise is established among the production of diesel and naphtha and the operating costs. The results show that the light gas oil hydrodesulfurization via catalytic distillation is as or more efficient than the conventional process. However, the removal of the sulfur compounds is carried out under less rigorous conditions. This design reduces the fix and operational costs. (author)

  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. The subfertile couple.

    Science.gov (United States)

    McCusker, M P

    1982-01-01

    When pregnancy is achieved through fertility awareness, there are further long-range benefits to the couple: information which will permit them the choice to avoid, delay or achieve subsequent pregnancies. Thus, the opportunity for responsible parenthood continues. The goal of nursing in subfertility care is to identify factors which may contribute to lowered fertility, and to teach and/or refer appropriately. The most comprehensive single intervention may be to teach the couple awareness of their own fertility through the Billings Method of natural family planning. If conception does not occur, the couple may progress to infertility investigation, knowing that the expense, inconvenience, and possible trauma are justified. Whether pregnancy occurs or not, it is likely that the couple will have had the benefit of clarifying their relationship, further understanding their bodies, and generally growing toward fuller personhood.

  5. Disformally coupled inflation

    CERN Document Server

    van de Bruck, Carsten; Longden, Chris

    2015-01-01

    A disformal coupling between two scalar fields is considered in the context of cosmological inflation. The coupling introduces novel derivative interactions mixing the kinetic terms of the fields but without introducing superluminal or unstable propagation of the two scalar fluctuation modes. Though the typical effect of the disformal coupling is to inhibit one of the fields from inflating the universe, the energy density of the other field can drive viable near Sitter -inflation in the presence of nontrivial disformal dynamics, in particular when one assumes exponential instead of power-law form for the couplings. The linear perturbation equations are written for the two-field system, its canonical degrees of freedom are quantised, their spectra are derived and the inflationary predictions are reported for numerically solved exponential models. A generic prediction is low tensor-to-scalar ratio.

  6. Pneumatic flexible shaft couplings

    Directory of Open Access Journals (Sweden)

    Jaroslav HOMIŠIN

    2007-01-01

    Full Text Available Main effort of every design engineer is reduction of torsional oscillation in any mechanical system. At present this problem can be solved by means of a suitable modification of dynamic properties of flexible shaft couplings according to dynamics in the given systems. But the dynamic properties of nowadays-applied flexible couplings arenot unchangeable because of aging and fatigue processes occurring in flexible coupling elements. Result of this fact causes detuning of mechanical system. Taking into consideration the above-mentioned situation, we suggest for mechanical systems application of a newly developed pneumatic couplings that have constant characteristicfeatures during the whole current operation and thus they have a positive influence on the system running.

  7. Site-specific growth of Au-Pd alloy horns on Au nanorods: A platform for highly sensitive monitoring of catalytic reactions by surface enhancement raman spectroscopy

    KAUST Repository

    Huang, Jianfeng

    2013-06-12

    Surface-enhanced Raman scattering (SERS) is a highly sensitive probe for molecular detection. The aim of this study was to develop an efficient platform for investigating the kinetics of catalytic reactions with SERS. To achieve this, we synthesized a novel Au-Pd bimetallic nanostructure (HIF-AuNR@AuPd) through site-specific epitaxial growth of Au-Pd alloy horns as catalytic sites at the ends of Au nanorods. Using high-resolution electron microscopy and tomography, we successfully reconstructed the complex three-dimensional morphology of HIF-AuNR@AuPd and identified that the horns are bound with high-index {11l} (0.25 < l < 0.43) facets. With an electron beam probe, we visualized the distribution of surface plasmon over the HIF-AuNR@AuPd nanorods, finding that strong longitudinal surface plasmon resonance concentrated at the rod ends. This unique crystal morphology led to the coupling of high catalytic activity with a strong SERS effect at the rod ends, making HIF-AuNR@AuPd an excellent bifunctional platform for in situ monitoring of surface catalytic reactions. Using the hydrogenation of 4-nitrothiophenol as a model reaction, we demonstrated that its first-order reaction kinetics could be accurately determined from this platform. Moreover, we clearly identified the superior catalytic activity of the rod ends relative to that of the rod bodies, owing to the different SERS activities at the two positions. In comparison with other reported Au-Pd bimetallic nanostructures, HIF-AuNR@AuPd offered both higher catalytic activity and greater detection sensitivity. © 2013 American Chemical Society.

  8. OPERATING SPECIFICATIONS OF CATALYTIC CLEANING OF GAS FROM BIOMASS GASIFICATION

    Directory of Open Access Journals (Sweden)

    Martin Lisý

    2015-12-01

    Full Text Available The paper focuses on the theoretical description of the cleaning of syngas from biomass and waste gasification using catalytic methods, and on the verification of the theory through experiments. The main obstruction to using syngas from fluid gasification of organic matter is the presence of various high-boiling point hydrocarbons (i.e., tar in the gas. The elimination of tar from the gas is a key factor in subsequent use of the gas in other technologies for cogeneration of electrical energy and heat. The application of a natural or artificial catalyst for catalytic destruction of tar is one of the methods of secondary elimination of tar from syngas. In our experiments, we used a natural catalyst (dolomite or calcium magnesium carbonate from Horní Lánov with great mechanical and catalytic properties, suitable for our purposes. The advantages of natural catalysts in contrast to artificial catalysts include their availability, low purchase prices and higher resilience to the so-called catalyst poison. Natural calcium catalysts may also capture undesired compounds of sulphure and chlorine. Our paper presents a theoretical description and analysis of catalytic destruction of tar into combustible gas components, and of the impact of dolomite calcination on its efficiency. The efficiency of the technology is verified in laboratories. The facility used for verification was a 150 kW pilot gasification unit with a laboratory catalytic filter. The efficiency of tar elimination reached 99.5%, the tar concentration complied with limits for use of the gas in combustion engines, and the tar content reached approximately 35 mg/mn3. The results of the measurements conducted in laboratories helped us design a pilot technology for catalytic gas cleaning.

  9. Fuel Flexible, Low Emission Catalytic Combustor for Opportunity Fuel Applications

    Energy Technology Data Exchange (ETDEWEB)

    Eteman, Shahrokh

    2013-06-30

    Limited fuel resources, increasing energy demand and stringent emission regulations are drivers to evaluate process off-gases or process waste streams as fuels for power generation. Often these process waste streams have low energy content and/or highly reactive components. Operability of low energy content fuels in gas turbines leads to issues such as unstable and incomplete combustion. On the other hand, fuels containing higher-order hydrocarbons lead to flashback and auto-ignition issues. Due to above reasons, these fuels cannot be used directly without modifications or efficiency penalties in gas turbine engines. To enable the use of these wide variety of fuels in gas turbine engines a rich catalytic lean burn (RCL®) combustion system was developed and tested in a subscale high pressure (10 atm.) rig. The RCL® injector provided stability and extended turndown to low Btu fuels due to catalytic pre-reaction. Previous work has shown promise with fuels such as blast furnace gas (BFG) with LHV of 85 Btu/ft3 successfully combusted. This program extends on this work by further modifying the combustor to achieve greater catalytic stability enhancement. Fuels containing low energy content such as weak natural gas with a Lower Heating Value (LHV) of 6.5 MJ/m3 (180 Btu/ft3 to natural gas fuels containing higher hydrocarbon (e.g ethane) with LHV of 37.6 MJ/m3 (1010 Btu/ft3) were demonstrated with improved combustion stability; an extended turndown (defined as the difference between catalytic and non-catalytic lean blow out) of greater than 250oF was achieved with CO and NOx emissions lower than 5 ppm corrected to 15% O2. In addition, for highly reactive fuels the catalytic region preferentially pre-reacted the higher order hydrocarbons with no events of flashback or auto-ignition allowing a stable and safe operation with low NOx and CO emissions.

  10. Coupled transverse motion

    Energy Technology Data Exchange (ETDEWEB)

    Teng, L.C.

    1989-01-01

    The magnetic field in an accelerator or a storage ring is usually so designed that the horizontal (x) and the vertical (y) motions of an ion are uncoupled. However, because of imperfections in construction and alignment, some small coupling is unavoidable. In this lecture, we discuss in a general way what is known about the behaviors of coupled motions in two degrees-of-freedom. 11 refs., 6 figs.

  11. Evidence for the formation of a covalent thiosulfinate intermediate with peroxiredoxin in the catalytic mechanism of sulfiredoxin.

    Science.gov (United States)

    Roussel, Xavier; Béchade, Guillaume; Kriznik, Alexandre; Van Dorsselaer, Alain; Sanglier-Cianferani, Sarah; Branlant, Guy; Rahuel-Clermont, Sophie

    2008-08-15

    The typical 2-Cys peroxiredoxins are thiol-peroxidases involved in the physiology of hydrogen peroxide not only as a toxic but also as a signaling molecule. Coordination of these functions depends on the sulfinylation of the catalytic Cys, a modification reversed by ATP-dependent sulfiredoxin, which specifically reduces the sulfinic acid group of overoxidized 2-Cys peroxiredoxins into a sulfenic acid. Sulfiredoxin was originally proposed to operate by covalent catalysis, with formation of a peroxiredoxin-sulfiredoxin intermediate linked by a thiosulfinate bond between the catalytic Cys of both partners, a hypothesis rejected by a study of the human enzyme. To settle the argument, we investigated the catalytic mechanism of Saccharomyces cerevisiae sulfiredoxin, by the characterization of the nature and kinetics of formation of the protein species formed between sulfiredoxin and its substrate in the presence of ATP, using mutants of the non-essential Cys residues of both proteins. We observed the formation of a dithiothreitol-reducible peroxiredoxin-sulfiredoxin species using SDS-PAGE and Western blot analysis, and its mass was shown to correspond to a thiosulfinate complex by high resolution mass spectrometry coupled to liquid chromatography. We next measured indirectly and directly a rate constant of formation of the thiosulfinate species of approximately 2 min(-1), for both wild-type and mutant sulfiredoxins, at least equal to the steady-state rate constant of the reaction, with a stoichiometry of 1:1 relative to peroxiredoxin. Taken altogether, our results strongly argue in favor of the formation of a covalent thiosulfinate peroxiredoxin-sulfiredoxin species as an intermediate on the catalytic pathway.

  12. STUDY ON THE CATALYTIC ABILITY OF BIOACTIVE FIBERS

    Institute of Scientific and Technical Information of China (English)

    YAO Yuyuan; CHEN Wenxing

    2006-01-01

    Two kinds of water-soluble metallophthalocyanines (Mt2Pc2), binuclear cobalt phthalocyanine (Co2Pc2) and binuclear ferric phthalocyanine (Fe2Pc2), were supported on silk fibers and modified viscose fibers to construct bioactive fibers of mimic enzyme, Mt2Pc2 used as the active center of bioactive fibers, viscose and silk fibers as the microenvironments. The catalytic oxidation ability of bioactive fibers on the malodors of methanthiol and hydrogen sulfide was investigated at room temperature. The experimental results demonstrated that the catalytic activity of such bioactive fibers was tightly correlative to the types of bioactive fibers and substrates.

  13. Degradation of Organic Pollutants in Water by Catalytic Ozonation

    Institute of Scientific and Technical Information of China (English)

    LI Xin; YAO Jun-hai; QI Jing-yao

    2007-01-01

    Different series of transition metal catalysts supported on Al2O3 were prepared by the impregnation method. The catalytic activity was measured in a batch reactor with ozone as the oxidizing reagent. The experimental results indicate that Cu/Al2O3 has a very effective catalytic activity during the ozonation of organic pollutants in water. The optimum conditions for preparing Cu/Al2O3 were systematically investigated with the orthogonal testing method. Furthermore, the results also show that the surface properties of catalyst are not compulsory for effective oxidation.

  14. Heterogeneous catalytic hydrogenation reactions in continuous-flow reactors.

    Science.gov (United States)

    Irfan, Muhammad; Glasnov, Toma N; Kappe, C Oliver

    2011-03-21

    Microreactor technology and continuous flow processing in general are key features in making organic synthesis both more economical and environmentally friendly. Heterogeneous catalytic hydrogenation reactions under continuous flow conditions offer significant benefits compared to batch processes which are related to the unique gas-liquid-solid triphasic reaction conditions present in these transformations. In this review article recent developments in continuous flow heterogeneous catalytic hydrogenation reactions using molecular hydrogen are summarized. Available flow hydrogenation techniques, reactors, commonly used catalysts and examples of synthetic applications with an emphasis on laboratory-scale flow hydrogenation reactions are presented.

  15. Effect of praseodymium on catalytic graphitization of furan resin carbon

    Institute of Scientific and Technical Information of China (English)

    易守军; 陈金华; 肖雄; 刘露; 樊桢

    2010-01-01

    We introduced a new catalyst,rare earth element praseodymium,for the catalytic graphitization of furan resin carbon.The extent of graphitization of the furan resin carbon was examined by X-ray diffraction and Raman spectroscopy.The morphology of furan resin carbon was characterized by scanning electron microscopy.The effects of the praseodymium content and the heat-treatment temperature on the catalytic graphitization of furan resin carbon were also investigated.The results indicated that the praseodymium c...

  16. Catalytic hydrogen evolution by polyaminoacids using mercury electrode

    Directory of Open Access Journals (Sweden)

    Marko Živanovič

    2010-12-01

    Full Text Available It was shown that using constant current chronopotentiometricstripping (CPS peptides and proteins at nanomolar concentrations produce protein structure–sensitive peak H at mercury electrodes. This peak is due to the catalytic hydrogen evolution reaction (HER. Polyamino acids can be considered as an intermediate model system between peptides and macromolecular proteins. Here we used polyamino acids (poly(aa such as polylysine (polyLys and polyarginine (polyArg and cyclic voltammetry or CPS in combination with hanging mercury drop electrode to explore how different amino acid residues in proteins contribute to the catalyticHER.

  17. Study on Synthesis and Catalytic Performance of Hierarchical Zeolite

    Institute of Scientific and Technical Information of China (English)

    Zhang Lingling; Li Fengyan; ZhaoTianbo; Sun Guida

    2007-01-01

    A kind of hierarchical zeolite catalyst was synthesized by hydrothermal method.X-ray diffraction (XRD)and nitrogen adsorption-desorption method were used to study the phase and aperture structure of the prepared catalyst.Infrared(IR)spectra of pyridine adsorbed on the sample showed that the hierarchical zeolite really had much more Bronsted and Lewis acidic sites than the HZSM-5 zeolite.The catalytic cracking of large hydrocarbon molecules showed that the hierarchical zeolite had a higher catalytic activity than the HZSM-5 zeolite.

  18. Simulation of Suspension Catalytic Distillation for Synthesis of Linear Alkylbenzene

    Institute of Scientific and Technical Information of China (English)

    王二强; 李成岳

    2003-01-01

    Suspension catalytic distillation (SCD) has been developed recently as an innovative technology in catalytic distillation. In this paper, a brief introduction to SCD is given and an equilibrium stage (EQ) model is developed to simulate this new process for synthesis of linear alkylbenzene (LAB) from benzene and 1-dodecene.Since non-ideality of this reaction system is not strong, EQ model developed could be applied to it successfully.Simulation results agree well with experimental data, and indicate some characteristics of SCD process as an advanced technology for the production of LAB: 100% conversion of olefins, low temperature (90-100℃) and low benzene/olefin mole ratio.

  19. Upgrading of Intermediate Bio-Oil Produced by Catalytic Pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Abdullah, Zia [Battelle Memorial Inst., Columbus, OH (United States); Chadwell, Brad [Battelle Memorial Inst., Columbus, OH (United States); Taha, Rachid [Battelle Memorial Inst., Columbus, OH (United States); Hindin, Barry [Battelle Memorial Inst., Columbus, OH (United States); Ralston, Kevin [Battelle Memorial Inst., Columbus, OH (United States)

    2015-06-30

    The objectives of this project were to (1) develop a process to upgrade catalytic pyrolysis bio-oil, (2) investigate new upgrading catalysts suited for upgrading catalytic pyrolysis bio-oil, (3) demonstrate upgrading system operation for more than 1,000 hours using a single catalyst charge, and (4) produce a final upgraded product that can be blended to 30 percent by weight with petroleum fuels or that is compatible with existing petroleum refining operations. This project has, to the best of our knowledge, for the first time enabled a commercially viable bio-oil hydrotreatment process to produce renewable blend stock for transportation fuels.

  20. Solid catalytic growth mechanism of micro-coiled carbon fibers

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Micro-coiled carbon fibers were prepared by catalytic pyrolysisof acetylene with nano-sized nickel powder catalyst using the substrate method. The morphology of micro-coiled carbon fibers was observed through field emission scanning electron microscopy. It was found that the fiber and coil diameter of the obtained micro-coiled carbon fibers is about 500—600 nm and 4—5 μm, respectively. Most of the micro-coiled carbon fibers obtained were regular double carbon coils, but a few irregular ones were also observed. On the basis of the experimental observation, a solid catalytic growth mechanism of micro-coiled carbon fibers was proposed.

  1. Catalytic Preparation of Methyl Formate from Methanol over Silver

    Institute of Scientific and Technical Information of China (English)

    YANG Zhi; LI Jing; YANG Xiang-guang; WU Yue

    2005-01-01

    A catalytic reaction over a silver catalyst performed in an unregarded temperature region(473-873 K) with a long catalytic lifetime for the production of methyl formate from methanol was provided as a potential preparing route. The optimal yield of methyl formate(ca. 14.8%) with a selectivity >90% was obtained at about 573 K. Because α-oxygen species and bulk oxygen species coexist in the unregarded temperature region, a synergistic process concerning α-oxygen species and bulk oxygen species was proved over Oα -rich and Oγ-rich samples.

  2. Bubble driven quasioscillatory translational motion of catalytic micromotors.

    Science.gov (United States)

    Manjare, Manoj; Yang, Bo; Zhao, Y-P

    2012-09-21

    A new quasioscillatory translational motion has been observed for big Janus catalytic micromotors with a fast CCD camera. Such motional behavior is found to coincide with both the bubble growth and burst processes resulting from the catalytic reaction, and the competition of the two processes generates a net forward motion. Detailed physical models have been proposed to describe the above processes. It is suggested that the bubble growth process imposes a growth force moving the micromotor forward, while the burst process induces an instantaneous local pressure depression pulling the micromotor backward. The theoretic predictions are consistent with the experimental data.

  3. Catalytically active nanomaterials: a promising candidate for artificial enzymes.

    Science.gov (United States)

    Lin, Youhui; Ren, Jinsong; Qu, Xiaogang

    2014-04-15

    Natural enzymes, exquisite biocatalysts mediating every biological process in living organisms, are able to accelerate the rate of chemical reactions up to 10(19) times for specific substrates and reactions. However, the practical application of enzymes is often hampered by their intrinsic drawbacks, such as low operational stability, sensitivity of catalytic activity to environmental conditions, and high costs in preparation and purification. Therefore, the discovery and development of artificial enzymes is highly desired. Recently, the merging of nanotechnology with biology has ignited extensive research efforts for designing functional nanomaterials that exhibit various properties intrinsic to enzymes. As a promising candidate for artificial enzymes, catalytically active nanomaterials (nanozymes) show several advantages over natural enzymes, such as controlled synthesis in low cost, tunability in catalytic activities, as well as high stability against stringent conditions. In this Account, we focus on our recent progress in exploring and constructing such nanoparticulate artificial enzymes, including graphene oxide, graphene-hemin nanocomposites, carbon nanotubes, carbon nanodots, mesoporous silica-encapsulated gold nanoparticles, gold nanoclusters, and nanoceria. According to their structural characteristics, these enzyme mimics are categorized into three classes: carbon-, metal-, and metal-oxide-based nanomaterials. We aim to highlight the important role of catalytic nanomaterials in the fields of biomimetics. First, we provide a practical introduction to the identification of these nanozymes, the source of the enzyme-like activities, and the enhancement of activities via rational design and engineering. Then we briefly describe new or enhanced applications of certain nanozymes in biomedical diagnosis, environmental monitoring, and therapeutics. For instance, we have successfully used these biomimetic catalysts as colorimetric probes for the detection of

  4. Catalytic synthesis of silicon carbide preceramic polymers: Polycarbosilanes. Technical research progress report, October 1, 1991--September 30, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Berry, D.H.

    1992-10-01

    Polycarbosilanes are the most successful and widely studied class of polymer precursors for silicon carbide, but traditional methods for their synthesis are inefficient and nonselective. This project is focused on developing transition metal catalysts for the synthesis of polycarbosilanes and other preceramic polymers. In recent work we have developed the first homogeneous transition metal catalysts for the dehydrogenative coupling of simple alkyl silanes to oligomeric and polymeric carbosilanes, H-(SiR{sub 2}CR{prime}{sub 2})n-SiR{sub 3}. The coupling of alkylgermanes, however, yields the corresponding oligomeric poly(germanes) (Ge-Ge). Future work will help elucidate the mechanisms of these catalytic process, explore the use of hydrogen acceptors as reaction accelerators, and develop new and more active catalysts.

  5. Diffusion effects on the determination of surface catalysis in Inductively Coupled Plasma facility

    Science.gov (United States)

    Viladegut, Alan; Düzel, Ümran; Chazot, Olivier

    2017-03-01

    Atomic recombination is an important process to consider when computing the heat flux transferred to the wall of a re-entry vehicle. Two chemical processes are influencing the species diffusion in the boundary layer surrounding a re-usable Thermal Protection System: gas phase reactions and catalytic recombination at the surface. The coupling between them is not normally taken into account when determining the catalytic recombination coefficient (γ) in plasma facilities. This work aims to provide evidence of such coupling based on both a theoretical analysis and an experimental campaign in the VKI-Plasmatron facility. Recombination coefficient measurements at off-stagnation point configuration on a linear copper calorimeter are provided. An evolution from a high-catalytic to a low-catalytic condition due to the boundary layer growth along the probe is observed. This result is consistent with a parametric analysis carried out using the in-house non-equilibrium boundary layer solver, which shows how the experimentally determined catalysis could be influenced by the amount of gas-phase recombination inside the boundary layer.

  6. Identification of a Catalytic Iron-Hydride at the H-Cluster of [FeFe]-Hydrogenase

    Energy Technology Data Exchange (ETDEWEB)

    Mulder, David W.; Guo, Yisong; Ratzloff, Michael W.; King, Paul W.

    2017-01-11

    Hydrogenases couple electrochemical potential to the reversible chemical transformation of H2 and protons, yet the reaction mechanism and composition of intermediates are not fully understood. In this Communication we describe the biophysical properties of a hydride-bound state (Hhyd) of the [FeFe]-hydrogenase from Chlamydomonas reinhardtii. The catalytic H-cluster of [FeFe]-hydrogenase consists of a [4Fe-4S] subcluster ([4Fe-4S]H) linked by a cysteine thiol to an azadithiolate-bridged 2Fe subcluster ([2Fe]H) with CO and CN- ligands. Mossbauer analysis and density functional theory (DFT) calculations show that Hhyd consists of a reduced [4Fe-4S]H+ coupled to a diferrous [2Fe]H with a terminally bound Fe-hydride. The existence of the Fe-hydride in Hhyd was demonstrated by an unusually low Mossbauer isomer shift of the distal Fe of the [2Fe]H subcluster. A DFT model of Hhyd shows that the Fe-hydride is part of a H-bonding network with the nearby bridging azadithiolate to facilitate fast proton exchange and catalytic turnover.

  7. Moving waves and spatiotemporal patterns due to weak thermal effects in models of catalytic oxidation

    Science.gov (United States)

    Nekhamkina, Olga; Sheintuch, Moshe

    2005-05-01

    We analyze the behavior of a microkinetic model of a catalytic reaction coupled with weak enthalpy effects to show that under fixed gas-phase concentrations it can produce moving waves with an intrinsic length scale, when the underlying kinetics is oscillatory. The kinetic model incorporates dissociative oxygen adsorption, reactant adsorption and desorption, and surface reaction. Three typical patterns may emerge in a one-dimensional system (a long wire or a ring): homogeneous oscillations, a family of moving waves propagating with constant velocities, and patterns with multiple source/sink points. Pattern selection depends on the ratio of the system length to the intrinsic wave length and the governing parameters. We complement these analysis with simulations that revealed a plethora of patterned states on one- and two-dimensional systems (a disk or a cylinder). This work shows that weak long-range coupling due to high feed rates maintains such patterns, while low feed rates or strong long-range interaction can gradually suppress the emerging patterns.

  8. Catalytic properties of carbon materials for wet oxidation of aniline.

    Science.gov (United States)

    Gomes, Helder T; Machado, Bruno F; Ribeiro, Andreia; Moreira, Ivo; Rosário, Márcio; Silva, Adrián M T; Figueiredo, José L; Faria, Joaquim L

    2008-11-30

    A mesoporous carbon xerogel with a significant amount of oxygen functional groups and a commercial activated carbon, were tested in the catalytic wet air oxidation of aniline at 200 degrees C and 6.9 bar of oxygen partial pressure. Both carbon materials showed high activity in aniline and total organic carbon removal, a clear increase in the removal efficiency relatively to non-catalytic wet air oxidation being observed. The best results in terms of aniline removal were obtained with carbon xerogel, an almost complete aniline conversion after 1h oxidation with high selectivity to non-organic compounds being achieved. The materials were characterized by thermogravimetric analysis, temperature programmed desorption, N(2) adsorption and scanning electron microscopy, in order to relate their performances to the chemical and textural characteristics. It was concluded that the removal efficiency, attributed to both adsorption and catalytic activity, is related to the mesoporous character of the materials and to the presence of specific oxygen containing functional groups at their surface. The effect of catalytic activity was found to be more important in the removal of aniline than the effect of adsorption at the materials surface. The results obtained indicate that mesoporous carbon xerogels are promising catalysts for CWAO processes.

  9. Integrated approach for the intensification of heterogeneous catalytic processes.

    Science.gov (United States)

    Kiwi-Minsker, Lioubov; Crespo-Quesada, Micaela

    2011-01-01

    The integrated approach for the design of solid catalysts for process intensification is presented addressing simultaneously different levels of scale and complexity involved in the development starting from the molecular/nano-scale of the active phase optimization up to the macro-scale of the catalytic reactor design. The feasibility of this approach is demonstrated through case studies carried out in our group.

  10. Catalytic properties of carbon materials for wet oxidation of aniline

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, Helder T. [Laboratorio de Catalise e Materiais (LCM), Laboratorio Associado LSRE/LCM, Departamento de Engenharia Quimica, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Departamento de Tecnologia Quimica e Biologica, Escola Superior de Tecnologia e de Gestao, Instituto Politecnico de Braganca, Campus de Santa Apolonia, 5300-857 Braganca (Portugal); Machado, Bruno F.; Ribeiro, Andreia; Moreira, Ivo; Rosario, Marcio; Silva, Adrian M.T.; Figueiredo, Jose L. [Laboratorio de Catalise e Materiais (LCM), Laboratorio Associado LSRE/LCM, Departamento de Engenharia Quimica, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Faria, Joaquim L. [Laboratorio de Catalise e Materiais (LCM), Laboratorio Associado LSRE/LCM, Departamento de Engenharia Quimica, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal)], E-mail: jlfaria@fe.up.pt

    2008-11-30

    A mesoporous carbon xerogel with a significant amount of oxygen functional groups and a commercial activated carbon, were tested in the catalytic wet air oxidation of aniline at 200 deg. C and 6.9 bar of oxygen partial pressure. Both carbon materials showed high activity in aniline and total organic carbon removal, a clear increase in the removal efficiency relatively to non-catalytic wet air oxidation being observed. The best results in terms of aniline removal were obtained with carbon xerogel, an almost complete aniline conversion after 1 h oxidation with high selectivity to non-organic compounds being achieved. The materials were characterized by thermogravimetric analysis, temperature programmed desorption, N{sub 2} adsorption and scanning electron microscopy, in order to relate their performances to the chemical and textural characteristics. It was concluded that the removal efficiency, attributed to both adsorption and catalytic activity, is related to the mesoporous character of the materials and to the presence of specific oxygen containing functional groups at their surface. The effect of catalytic activity was found to be more important in the removal of aniline than the effect of adsorption at the materials surface. The results obtained indicate that mesoporous carbon xerogels are promising catalysts for CWAO processes.

  11. Biodiesel by catalytic reactive distillation powered by metal oxides

    NARCIS (Netherlands)

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

    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

  12. Mechanism of Ribonuclease III Catalytic Regulation by Serine Phosphorylation

    Science.gov (United States)

    Gone, Swapna; Alfonso-Prieto, Mercedes; Paudyal, Samridhdi; Nicholson, Allen W.

    2016-05-01

    Ribonuclease III (RNase III) is a conserved, gene-regulatory bacterial endonuclease that cleaves double-helical structures in diverse coding and noncoding RNAs. RNase III is subject to multiple levels of control, reflective of its global regulatory functions. Escherichia coli (Ec) RNase III catalytic activity is known to increase during bacteriophage T7 infection, reflecting the expression of the phage-encoded protein kinase, T7PK. However, the mechanism of catalytic enhancement is unknown. This study shows that Ec-RNase III is phosphorylated on serine in vitro by purified T7PK, and identifies the targets as Ser33 and Ser34 in the N-terminal catalytic domain. Kinetic experiments reveal a 5-fold increase in kcat and a 1.4-fold decrease in Km following phosphorylation, providing a 7.4–fold increase in catalytic efficiency. Phosphorylation does not change the rate of substrate cleavage under single-turnover conditions, indicating that phosphorylation enhances product release, which also is the rate-limiting step in the steady-state. Molecular dynamics simulations provide a mechanism for facilitated product release, in which the Ser33 phosphomonoester forms a salt bridge with the Arg95 guanidinium group, thereby weakening RNase III engagement of product. The simulations also show why glutamic acid substitution at either serine does not confer enhancement, thus underscoring the specific requirement for a phosphomonoester.

  13. Note on “Electrochemical promotion of catalytic reactions”

    Science.gov (United States)

    Vernoux, Philippe; Vayenas, Constantinos G.

    2011-05-01

    A recent review published in this Journal of the electrochemical promotion of catalysis (EPOC or NEMCA effect) is discussed. Some key aspects of the effect’s phenomenology and physicochemical origin are reviewed and clarified and the interplay of catalytic kinetics and mass transfer limitations in EPOC studies under high vacuum is discussed.

  14. Raman Nanospectroscopy of a Photo-Catalytic Reaction

    NARCIS (Netherlands)

    van Schrojenstein Lantman, E.M.

    2014-01-01

    A chemical reaction between molecules requires a certain amount of energy to occur. A catalyst can lower this activation energy, resulting in a faster, greener and more sustainable chemical process. Ideally, one would like to follow a reaction over a single catalytic nanoparticle, to fully understan

  15. Assessing the reliability of calculated catalytic ammonia synthesis rates

    DEFF Research Database (Denmark)

    Medford, Andrew James; Wellendorff, Jess; Vojvodic, Aleksandra

    2014-01-01

    We introduce a general method for estimating the uncertainty in calculated materials properties based on density functional theory calculations. We illustrate the approach for a calculation of the catalytic rate of ammonia synthesis over a range of transition-metal catalysts. The correlation...

  16. Catalytic behavior of Cu, Ag and Au nanoparticles. A comparison

    NARCIS (Netherlands)

    Lippits, Meindert Jan

    2010-01-01

    Clearly gold deposited as nanoparticles on a support is a very active catalyst in contrast to bulk gold which does not show any catalytic activity. The question arises if this particle size effect is exclusively valid for gold catalysis or can a similar effect be found in other metals? In the resear

  17. 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 to a...

  18. Advanced Catalytic Converter in Gasoline Enginer Emission Control: A Review

    Directory of Open Access Journals (Sweden)

    Leman A.M.

    2017-01-01

    Full Text Available Exhaust emission from automobile source has become a major contributor to the air pollution and environmental problem. Catalytic converter is found to be one of the most effective tools to reduce the overwhelming exhaust pollutants in our environment. The development of sustainable catalytic converter still remains a critical issue due to the stringent exhaust emission regulations. Another issue such as price and availability of the precious metal were also forced the automotive industry to investigate the alternatives for producing a better replacement for the material used in catalytic converter. This paper aims at reviewing the present development and improvement on the catalytic converter used on the reduction of exhaust emission in order to meet the regulations and market demand. The use of new catalyst such as to replace the noble metal material of Platinum (Pt, Palladium (Pd and Rhodium (Rh has been reviewed. Material such as zeolite, nickel oxide and metal oxide has been found to effectively reduce the emission than the commercial converter. The preparation method of the catalyst has also evolved through the years as it is to ensure a good characteristic of a good monolith catalyst. Ultrasonic treatment with combination of electroplating technique, citrate method and Plasma Electrolytic Oxidation (PEO has been found as the latest novel preparation method on producing an effective catalyst in reducing the exhaust emission.

  19. Enhanced Heterogeneous Catalytic Conversion of Furfuryl Alcohol into Butyl Levulinate

    NARCIS (Netherlands)

    Carà, P.D..; Ciriminna, R.; Shiju, N.R.; Rothenberg, G.; Pagliaro, M.

    2014-01-01

    We study the catalytic condensation of furfuryl alcohol with 1-butanol to butyl levulinate. A screening of several commercial and as-synthesized solid acid catalysts shows that propylsulfonic acid-functionalized mesoporous silica outperforms the state-of-the-art phosphotungstate acid catalysts. The

  20. Ex-Situ Catalytic Fast Pyrolysis Technology Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Biddy, M.; Dutta, A.; Jones, S.; Meyer, A.

    2013-03-01

    This technology pathway case investigates converting woody biomass using ex-situ catalytic fast pyrolysis followed by upgrading to gasoline-, diesel-, and jet-range hydrocarbon blendstocks. Technical barriers and key research needs that should be pursued for this pathway to be competitive with petroleum-derived blendstocks have been identified.

  1. In-Situ Catalytic Fast Pyrolysis Technology Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Biddy, M.; Dutta, A.; Jones, S.; Meyer, A.

    2013-03-01

    This technology pathway case investigates converting woody biomass using in-situ catalytic fast pyrolysis followed by upgrading to gasoline-, diesel-, and jet-range hydrocarbon blendstocks. Technical barriers and key research needs that should be pursued for this pathway to be competitive with petroleum-derived blendstocks have been identified.

  2. Simulation for Synthesis of TAME with Catalytic Distillation Process

    Institute of Scientific and Technical Information of China (English)

    Liu Boxue; Deng Zhengyong; Weng Huixin; Gao Buliang

    2008-01-01

    The triangular matrixing modified relaxation model equation was established for the synthesis of TAME with catalytic distillation process, and a new accelerated convergence technique was adopted. The simulation on the synthesis of TAME showed that the calculated data agreed well with the experimental results.

  3. Catalytic carbonization of wood charcoal : graphite or diamond?

    NARCIS (Netherlands)

    Hata, T; Vystavel, T; Bronsveld, P; DeHosson, J; Kikuchi, H; Nishimiya, K; Imamura, Y

    2004-01-01

    We report on the process of making graphite out of wood by catalytic carbonization. Two different types of microstructure were observed. One type being typical for graphitization of wood without the effect of a catalyst, the main characteristic being the typical fibrillar microstructure related back

  4. Catalytic control over the formation of supramolecular materials

    NARCIS (Netherlands)

    Eelkema, R; Esch, van J.H.

    2014-01-01

    In this Perspective, we will discuss how the rate of formation of supramolecular materials can be drastically enhanced by catalytically controlling the rate of formation of their molecular building blocks, resulting in the formation of out-of-equilibrium soft materials with enhanced mechanical prope

  5. Catalytic domain surface residues mediating catecholamine inhibition in tyrosine hydroxylase.

    Science.gov (United States)

    Briggs, Gabrielle D; Bulley, Jesse; Dickson, Phillip W

    2014-03-01

    Tyrosine hydroxylase (TH) performs the rate-limiting step in catecholamine (CA) synthesis and is a tetramer composed of regulatory, catalytic and tetramerization domains. CAs inhibit TH by binding two sites in the active site; one with high affinity and one with low affinity. Only high affinity CA binding requires the regulatory domain, believed to interact with the catalytic domain in the presence of CA. Without a crystal structure of the regulatory domain, the specific areas involved in this process are largely undefined. It is not clear whether the regulatory domain-catalytic domain interaction is asymmetrical across the tetramer to produce the high and low affinity sites. To investigate this, pure dimeric TH was generated through double substitution of residues at the tetramerization interface and dimerization salt bridge (K170E/L480A). This was shown to be the core regulatory unit of TH for CA inhibition, possessing both high and low affinity CA binding sites, indicating that there is symmetry between dimers of the tetramer. We also examined possible regulatory domain-interacting regions on the catalytic domain that mediate high affinity CA binding. Using site-directed mutagenesis, A297, E362/E365 and S368 were shown to mediate high affinity dopamine inhibition through V(max) reduction and increasing the K(M) for the cofactor.

  6. Short hydrogen bonds in the catalytic mechanism of serine proteases

    Directory of Open Access Journals (Sweden)

    VLADIMIR LESKOVAC

    2008-04-01

    Full Text Available The survey of crystallographic data from the Protein Data Bank for 37 structures of trypsin and other serine proteases at a resolution of 0.78–1.28 Å revealed the presence of hydrogen bonds in the active site of the enzymes, which are formed between the catalytic histidine and aspartate residues and are on average 2.7 Å long. This is the typical bond length for normal hydrogen bonds. The geometric properties of the hydrogen bonds in the active site indicate that the H atom is not centered between the heteroatoms of the catalytic histidine and aspartate residues in the active site. Taken together, these findings exclude the possibility that short “low-barrier” hydrogen bonds are formed in the ground state structure of the active sites examined in this work. Some time ago, it was suggested by Cleland that the “low-barrier hydrogen bond” hypothesis is operative in the catalytic mechanism of serine proteases, and requires the presence of short hydrogen bonds around 2.4 Å long in the active site, with the H atom centered between the catalytic heteroatoms. The conclusions drawn from this work do not exclude the validity of the “low-barrier hydrogen bond” hypothesis at all, but they merely do not support it in this particular case, with this particular class of enzymes.

  7. Mg2+ coordination in catalytic sites of F1-ATPase.

    Science.gov (United States)

    Weber, J; Hammond, S T; Wilke-Mounts, S; Senior, A E

    1998-01-13

    Coordination of the Mg2+ ion in Mg-nucleotide substrates by amino acid residue side chains in the catalytic site of Escherichia coli F1-ATPase was investigated. From the X-ray structure of the mitochondrial enzyme [Abrahams, J. P., Leslie, A. G. W., Lutter, R., and Walker, J. E. (1994) Nature 370, 621-628], it may be inferred that the hydroxyl of betaThr-156 is a direct ligand of Mg2+, whereas the carboxyls of betaGlu-181, betaGlu-185, and betaAsp-242 might contribute via intervening water molecules. Elimination of each respective functional group by site-directed mutagenesis, followed by determination of Mg-nucleotide and uncomplexed nucleotide binding affinities using a tryptophan probe, showed that betaThr-156, betaGlu-185, and betaAsp-242 are all involved in Mg2+ coordination, whereas betaGlu-181 is not. A derived structural model for the octahedral coordination around the Mg2+ ion is presented. The results indicate that the ADP-containing site in the X-ray structure is the catalytic site of highest affinity. Correct Mg2+ coordination is required for catalytic activity at physiological rates. Elimination of any one of the Mg2+-coordinating residues led to complete loss of Mg2+-dependent nucleotide binding cooperativity of the catalytic sites.

  8. Asymmetric catalytic synthesis of the proposed structure of trocheliophorolide B.

    Science.gov (United States)

    Trost, Barry M; Quintard, Adrien

    2012-09-01

    A concise catalytic asymmetric synthesis of the proposed structure of trocheliophorolide B is reported. The synthetic sequence notably features an asymmetric acetaldehyde alkynylation, a Ru-catalyzed alder-ene reaction, and a Zn-ProPhenol ynone aldol condensation. Comparison with the reported data suggests a misassignment of the natural product structure.

  9. Clay Minerals as Solid Acids and Their Catalytic Properties.

    Science.gov (United States)

    Helsen, J.

    1982-01-01

    Discusses catalytic properties of clays, attributed to acidity of the clay surface. The formation of carbonium ions on montmorillonite is used as a demonstration of the presence of surface acidity, the enhanced dissociation of water molecules when polarized by cations, and the way the surface can interact with organic substances. (Author/JN)

  10. 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.

  11. Development of catalytic hydrogenation reactors for the fine chemicals industry

    NARCIS (Netherlands)

    Westerterp, K.R.; Gelder, van K.B.; Janssen, H.J.; Oyevaar, M.H.

    1988-01-01

    A survey is given of the problems to be solved before catalytic hydrogenation reactors can be applied in a multiproduct plant in which selectivity problems are experienced. Some results are reported on work done on the reaction kinetics of two multistep model reactions and on mathematical modelling

  12. 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

  13. Catalytic upgrading of biomass pyrolysis vapours using Faujasite zeolite catalysts

    NARCIS (Netherlands)

    Nguyen, T.S.; Zabeti, M.; Lefferts, L.; Brem, G.; Seshan, K.

    2012-01-01

    Bio-oil produced via fast pyrolysis of biomass has the potential to be processed in a FCC (fluid catalytic cracking) unit to generate liquid fuel. However, this oil requires a significant upgrade to become an acceptable feedstock for refinery plants due to its high oxygen content. One promising rout

  14. Well-defined transition metal hydrides in catalytic isomerizations.

    Science.gov (United States)

    Larionov, Evgeny; Li, Houhua; Mazet, Clément

    2014-09-07

    This Feature Article intends to provide an overview of a variety of catalytic isomerization reactions that have been performed using well-defined transition metal hydride precatalysts. A particular emphasis is placed on the underlying mechanistic features of the transformations discussed. These have been categorized depending upon the nature of the substrate and in most cases discussed following a chronological order.

  15. Design parameters for measurements of local catalytic activity on surfaces

    DEFF Research Database (Denmark)

    Johansson, Martin; Johannessen, Tue; Jørgensen, Jan Hoffmann;

    2006-01-01

    Computational fluid dynamics in combination with experiments is used to characterize a gas sampling device for measurements of the local catalytic activity on surfaces. The device basically consists of a quartz capillary mounted concentrically inside an aluminum tube. Reactant gas is blown toward...

  16. Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons

    Science.gov (United States)

    Rollins, Harry W.; Petkovic, Lucia M.; Ginosar, Daniel M.

    2011-02-01

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

  17. Heterogeneous kinetic modeling of the catalytic conversion of cycloparaffins

    Science.gov (United States)

    Al-Sabawi, Mustafa N.

    The limited availability of high value light hydrocarbon feedstocks along with the rise in crude prices has resulted in the international recognition of the vast potential of Canada's oil sands. With the recent expansion of Canadian bitumen production come, however, many technical challenges, one of which is the significant presence of aromatics and cycloparaffins in bitumen-derived feedstocks. In addition to their negative environmental impact, aromatics limit fluid catalytic cracking (FCC) feedstock conversion, decrease the yield and quality of valuable products such as gasoline and middle distillates, increase levels of polyaromatic hydrocarbons prone to form coke on the catalyst, and ultimately compromise the FCC unit performance. Although cycloparaffins do not have such negative impacts, they are precursors of aromatics as they frequently undergo hydrogen transfer reactions. However, cycloparaffin cracking chemistry involves other competing reactions that are complex and need much investigation. This dissertation provides insights and understanding of the fundamentals of the catalytic cracking of cycloparaffins using carefully selected model compounds such as methylcyclohexane (MCH) and decalin. Thermal and catalytic cracking of these cycloparaffins on FCC-type catalysts are carried out using the CREC Riser Simulator under operating conditions similar to those of the industrial FCC units in terms of temperature, reaction time, reactant partial pressure and catalyst-to-hydrocarbon ratio. The crystallite size of the supported zeolites is varied between 0.4 and 0.9 microns, with both activity and selectivity being monitored. Catalytic conversions ranged between 4 to 16 wt% for MCH and between 8 to 27 wt% for decalin. Reaction pathways of cycloparaffins are determined, and these include ring-opening, protolytic cracking, isomerization, hydrogen transfer and transalkylation. The yields and selectivities of over 60 and 140 products, formed during MCH and decalin

  18. Industrial Gas Turbine Engine Catalytic Pilot Combustor-Prototype Testing

    Energy Technology Data Exchange (ETDEWEB)

    Etemad, Shahrokh [Precision Combustion, Inc., North Haven, CT (United States); Baird, Benjamin [Precision Combustion, Inc., North Haven, CT (United States); Alavandi, Sandeep [Precision Combustion, Inc., North Haven, CT (United States); Pfefferle, William [Precision Combustion, Inc., North Haven, CT (United States)

    2010-04-01

    PCI has developed and demonstrated its Rich Catalytic Lean-burn (RCL®) technology for industrial and utility gas turbines to meet DOE's goals of low single digit emissions. The technology offers stable combustion with extended turndown allowing ultra-low emissions without the cost of exhaust after-treatment and further increasing overall efficiency (avoidance of after-treatment losses). The objective of the work was to develop and demonstrate emission benefits of the catalytic technology to meet strict emissions regulations. Two different applications of the RCL® concept were demonstrated: RCL® catalytic pilot and Full RCL®. The RCL® catalytic pilot was designed to replace the existing pilot (a typical source of high NOx production) in the existing Dry Low NOx (DLN) injector, providing benefit of catalytic combustion while minimizing engine modification. This report discusses the development and single injector and engine testing of a set of T70 injectors equipped with RCL® pilots for natural gas applications. The overall (catalytic pilot plus main injector) program NOx target of less than 5 ppm (corrected to 15% oxygen) was achieved in the T70 engine for the complete set of conditions with engine CO emissions less than 10 ppm. Combustor acoustics were low (at or below 0.1 psi RMS) during testing. The RCL® catalytic pilot supported engine startup and shutdown process without major modification of existing engine controls. During high pressure testing, the catalytic pilot showed no incidence of flashback or autoignition while operating over a wide range of flame temperatures. In applications where lower NOx production is required (i.e. less than 3 ppm), in parallel, a Full RCL® combustor was developed that replaces the existing DLN injector providing potential for maximum emissions reduction. This concept was tested at industrial gas turbine conditions in a Solar Turbines, Incorporated high-pressure (17 atm.) combustion rig and in a modified Solar

  19. Theoretical Study on the Mechanism of Sonogashira Coupling Reaction

    Institute of Scientific and Technical Information of China (English)

    CHEN Li-Ping; HONG San-Guo; HOU Hao-Qing

    2008-01-01

    The mechanism of palladium-catalyzed Sonogashira cross-coupling reaction has been studied theoretically by DFT (density functional theory) calculations. The model system studied consists of Pd(PH3)2 as the starting catalyst complex, phenyl bromide as the substrate and acetylene as the terminal alkyne, without regarding to the co-catalyst and base. Mechanistically and energetically plausible catalytic cycles for the cross-coupling have been identified. The DFT analysis shows that the catalytic cycle occurs in three stages: oxidative addition of phenyl bromide to the palladium center, alkynylation of palladium(II) intermediate, and reductive elimination to phenylacetylene. In the oxidative addition, the neutral and anionic pathways have been investigated, which could both give rise to cis-configured palladium(II) diphosphine intermediate. Starting from the palladium(II) diphosphine intermediate, the only identifiable pathway in alkynylation involves the dissociation of Br group and the formation of square-planar palladium(II) intermediate, in which the phenyl and alkynyl groups are oriented cis to each other. Due to the close proximity of phenyl and alkynyl groups, the reductive elimination of phenylacetylene proceeds smoothly.

  20. Selenium utilization in thioredoxin and catalytic advantage provided by selenocysteine

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Moon-Jung [Department of Biochemistry and Molecular Biology, Yeungnam University College of Medicine, Daegu 705-717 (Korea, Republic of); Lee, Byung Cheon [Division of Genetics, Department of Medicine, Brigham and Women' s Hospital, Harvard Medical School, Boston, MA 02115 (United States); Division of Biotechnology, College of Life Sciences & Biotechnology, Korea University, Seoul 136-701 (Korea, Republic of); Hwang, Kwang Yeon [Division of Biotechnology, College of Life Sciences & Biotechnology, Korea University, Seoul 136-701 (Korea, Republic of); Gladyshev, Vadim N. [Division of Genetics, Department of Medicine, Brigham and Women' s Hospital, Harvard Medical School, Boston, MA 02115 (United States); Kim, Hwa-Young, E-mail: hykim@ynu.ac.kr [Department of Biochemistry and Molecular Biology, Yeungnam University College of Medicine, Daegu 705-717 (Korea, Republic of)

    2015-06-12

    Thioredoxin (Trx) is a major thiol-disulfide reductase that plays a role in many biological processes, including DNA replication and redox signaling. Although selenocysteine (Sec)-containing Trxs have been identified in certain bacteria, their enzymatic properties have not been characterized. In this study, we expressed a selenoprotein Trx from Treponema denticola, an oral spirochete, in Escherichia coli and characterized this selenoenzyme and its natural cysteine (Cys) homologue using E. coli Trx1 as a positive control. {sup 75}Se metabolic labeling and mutation analyses showed that the SECIS (Sec insertion sequence) of T. denticola selenoprotein Trx is functional in the E. coli Sec insertion system with specific selenium incorporation into the Sec residue. The selenoprotein Trx exhibited approximately 10-fold higher catalytic activity than the Sec-to-Cys version and natural Cys homologue and E. coli Trx1, suggesting that Sec confers higher catalytic activity on this thiol-disulfide reductase. Kinetic analysis also showed that the selenoprotein Trx had a 30-fold higher K{sub m} than Cys-containing homologues, suggesting that this selenoenzyme is adapted to work efficiently with high concentrations of substrate. Collectively, the results of this study support the hypothesis that selenium utilization in oxidoreductase systems is primarily due to the catalytic advantage provided by the rare amino acid, Sec. - Highlights: • The first characterization of a selenoprotein Trx is presented. • The selenoenzyme Trx exhibits 10-fold higher catalytic activity than Cys homologues. • Se utilization in Trx is primarily due to the catalytic advantage provided by Sec residue.

  1. Activity of catalytic silver nanoparticles modulated by capping agent hydrophobicity.

    Science.gov (United States)

    Janani, Seralathan; Stevenson, Priscilla; Veerappan, Anbazhagan

    2014-05-01

    In this paper, a facile in situ method is reported for the preparation of catalytic silver nanoparticles (AgNPs) using N-acyl tyramine (NATA) with variable hydrophobic acyl length. Scanning electron microscopic analysis shows that NATA exists initially as larger aggregates in alkaline aqueous solution. The addition of AgNO3 dissociates these larger aggregate and subsequently promotes the formation of self-assembled NATA and AgNPs. Characterization of AgNPs using UV-vis spectroscopy, scanning electron microscope and transmission electron microscope revealed that the hydrophobic acyl chain length of NATA does not influence the particle size, shape and morphology. All NATA-AgNPs yielded relatively identical values in full width at half-maximum (FWHM) analysis, indicating that the AgNPs prepared with NATA are relatively polydispersed at all tested acyl chain lengths. These nanoparticles are able to efficiently catalyze the reduction of 4-nitro phenol to 4-amino phenol, 2-nitro aniline to 1,2-diamino benzene, 2,4,6-trinitro phenol to 2,4,6-triamino phenol by NaBH4 in an aqueous environment. The reduction reaction rate is determined to be pseudo-first order and the apparent rate constant is linearly dependent on the hydrophobic acyl chain length of the NATA. All reaction kinetics presented an induction period, which is dependent on the N-acyl chain length, indicating that the hydrophobic effects play a critical role in bringing the substrate to the metal nanoparticle surface to induce the catalytic reaction. In this study, however, the five catalytic systems have similar size and polydispersity, differing only in terms of capping agent hydrophobicity, and shows different catalytic activity with respect to the alkyl chain length of the capping agent. As discussed, the ability to modulate the metal nanoparticles catalytic property, by modifying the capping agent hydrophobicity represents a promising future for developing an efficient nanocatalyst without altering the size

  2. Catalytic combustion in environmental protection and energy production

    Energy Technology Data Exchange (ETDEWEB)

    Ahlstroem-Silversand, F.

    1996-12-01

    This thesis is focused on three different areas of catalytic combustion: -Catalytic combustion of diesel soot, -Development of catalytically active wire meshes through thermal spraying, -Stabilisation and activation of {gamma}-alumina for methane combustion. Emissions of diesel soot may be trapped and combusted in a particulate trap coated with catalytically active materials. The soot particles must be combusted at temperatures prevailing in diesel exhausts, generally between 150 and 400 deg C. To facilitate effective combustion at these temperatures, the particulate trap should be coated with an oxide catalyst consisting of V{sub 2}O{sub 5}/CuO (V:Cu=0.9 on molar basis). Catalytically active wire meshes offer a number of advantages over pellets and monolith catalysts. They combine geometric flexibility with excellent mass- and heat- transfer characteristics and a low pressure drop. By using a modified thermal spray technique, it is possible to produce porous adhesive ceramic coatings on metal surfaces. The specific surface area can be increased through deposition of a high-surface-area material into the macro-porosity of the as-sprayed layer. The ceramic layer is finally activated through a conventional impregnation technique. Palladium dispersed onto a Si-stabilised {gamma}-alumina is an appropriate combustion catalyst at temperatures below 1000 deg C. Adding small amounts of rhodium or platinum to the palladium increases the catalyst activity but decreases the catalyst`s stability to thermal deactivation. The addition of rare-earth-metal oxides will lead to increased thermal stability but to a decreased activity. Long-term deactivation tests show that the activity for combustion of methane decreases to the same extent as the value of the specific surface area, thus indicating that the alumina surface may play an important role during the activation of adsorbed methane molecules. 29 refs, 14 figs

  3. Component Development to Accelerate Commercial Implementation of Ultra-Low Emissions Catalytic Combustion

    Energy Technology Data Exchange (ETDEWEB)

    McCarty, Jon; Berry, Brian; Lundberg, Kare; Anson, Orris

    2003-03-31

    This final report describes a 2000-2003 program for the development of components and processes to enhance the commercialization of ultra-low emissions catalytic combustion in industrial gas turbines. The range of project tasks includes: development of more durable, lower-cost catalysts and catalytic combustor components; development and design of a catalytic pre-burner and a catalytic pilot burner for gas turbines, and on-site fuel conversion processing for utilization of liquid fuel.

  4. Two-step synthesis of Ag@GQD hybrid with enhanced photothermal effect and catalytic performance

    Science.gov (United States)

    Wu, Cong; Yuan, Yali; He, Qian; Song, Rui

    2016-12-01

    A novel Ag@GQD (graphene quantum dot) hybrid fabricated by a facile two-step strategy is presented: the GQDs are prepared by citrate acid and AgNO3 is reduced. Catalytic studies showed that the Ag@GQD hybrid exhibited excellent photothermal effect and catalytic performance for 4-nitrophenol (4-NP) reduction, suggesting that the GQDs enhanced the catalytic activity via a synergistic effect and the Ag NPs boosted the catalytic efficiency through SPR-mediated photothermal local heating.

  5. Actively coupled optical waveguides

    OpenAIRE

    Alexeeva, N. V.; Barashenkov, I. V.; Rayanov, K.; Flach, S.

    2013-01-01

    We consider light propagation through a pair of nonlinear optical waveguides with absorption, placed in a medium with power gain. The active medium boosts the in-phase component of the overlapping evanescent fields of the guides, while the nonlinearity of the guides couples it to the damped out-of-phase component creating a feedback loop. As a result, the structure exhibits stable stationary and oscillatory regimes in a wide range of gain-loss ratios. We show that the pair of actively-coupled...

  6. Actively coupled optical waveguides

    Science.gov (United States)

    Alexeeva, N. V.; Barashenkov, I. V.; Rayanov, K.; Flach, S.

    2014-01-01

    We consider light propagation through a pair of nonlinear optical waveguides with absorption, placed in a medium with power gain. The active medium boosts the in-phase component of the overlapping evanescent fields of the guides, while the nonlinearity of the guides couples it to the damped out-of-phase component creating a feedback loop. As a result, the structure exhibits stable stationary and oscillatory regimes in a wide range of gain-loss ratios. We show that the pair of actively coupled (AC) waveguides can act as a stationary or integrate-and-fire comparator sensitive to tiny differences in their input powers.

  7. [Couples counseling with Latinos].

    Science.gov (United States)

    Zumaya, Mario

    2011-01-01

    Intimate ties and emotional relationship gain the function to confirm, to stabilize and, afterwards, to structure the coherency's model of the structured self-organization up to that moment. When the couple perceives the bond of the relationship such as a sole and exclusive for a person, they take a leading role to be able to deduce a sense of individuality and uniqueness in the way to feel himself in the world. Based on these considerations, in this paper I propose a brief description of a counselling method, which characterises the work I am carrying out since several years in the counselling and therapy with couples.

  8. Wakefields and coupling impedances

    Energy Technology Data Exchange (ETDEWEB)

    Kurennoy, S. (Superconducting Super Collider Laboratory, 2550 Beckleymeade Ave., Dallas, Texas 75237 (United States))

    1995-02-01

    After a short introduction of the wake potentials and coupling impedances, a few new results in impedance calculations are discussed. The first example is a new analytical method for calculating impedances of axisymmetric structures in the low frequency range, below the cutoff frequency of the vacuum chamber. The second example demonstrates that even very small discontinuities on a smooth waveguide can result in appearance of trapped modes, with frequencies slightly below the waveguide cutoff frequency. The high-frequency (above the cutoff) behavior of the coupling impedance of many small discontinuities is discussed in the third example. [copyright] 1995 [ital American] [ital Institute] [ital of] [ital Physics

  9. Wakefields and coupling impedances

    Science.gov (United States)

    Kurennoy, Sergey

    1995-02-01

    After a short introduction of the wake potentials and coupling impedances, a few new results in impedance calculations are discussed. The first example is a new analytical method for calculating impedances of axisymmetric structures in the low frequency range, below the cutoff frequency of the vacuum chamber. The second example demonstrates that even very small discontinuities on a smooth waveguide can result in appearance of trapped modes, with frequencies slightly below the waveguide cutoff frequency. The high-frequency (above the cutoff) behavior of the coupling impedance of many small discontinuities is discussed in the third example.

  10. [Bmim]PF6-promoted ligandless Suzuki-Miyaura coupling reaction of potassium aryltrifluoroborates in water.

    Science.gov (United States)

    Liu, Leifang; Dong, Yan; Pang, Bo; Ma, Jiahai

    2014-08-01

    The Suzuki-Miyaura coupling reactions of potassium aryltrifluoroborates with aryl bromides in water are promoted by the addition of [bmim]PF6 using Pd(OAc)2 as a catalyst and Na2CO3 as a base under air. The quantity of [bmim]PF6 used is crucial to the efficiency of the catalytic system. A wide range of biaryls and polyaryls can be easily prepared in good to excellent yields.

  11. Robust acenaphthoimidazolylidene palladium complexes: highly efficient catalysts for Suzuki-Miyaura couplings with sterically hindered substrates.

    Science.gov (United States)

    Tu, Tao; Sun, Zheming; Fang, Weiwei; Xu, Mizhi; Zhou, Yunfei

    2012-08-17

    Robust acenaphthoimidazolylidene palladium complexes have been demonstrated as highly efficient and general catalysts for the sterically hindered Suzuki-Miyaura cross-coupling reactions in excellent yields even with low catalyst loadings under mild reaction conditions. The high catalytic activity of these complexes highlights that, besides the "flexible steric bulky" concept, σ-donor properties of the NHC ligands are also crucial to accelerate the transformations.

  12. Catalytic routes to fuels from C1 and oxygenate molecules.

    Science.gov (United States)

    Wang, Shuai; Agirrezabal-Telleria, Iker; Bhan, Aditya; Simonetti, Dante; Takanabe, Kazuhiro; Iglesia, Enrique

    2017-03-16

    This account illustrates concepts in chemical kinetics underpinned by the formalism of transition state theory using catalytic processes that enable the synthesis of molecules suitable as fuels from C1 and oxygenate reactants. Such feedstocks provide an essential bridge towards a carbon-free energy future, but their volatility and low energy density require the formation of new C-C bonds and the removal of oxygen. These transformations are described here through recent advances in our understanding of the mechanisms and site requirements in catalysis by surfaces, with emphasis on enabling concepts that tackle ubiquitous reactivity and selectivity challenges. The hurdles in forming the first C-C bond from C1 molecules are illustrated by the oxidative coupling of methane, in which surface O-atoms form OH radicals from O2 and H2O molecules. These gaseous OH species act as strong H-abstractors and activate C-H bonds with earlier transition states than oxide surfaces, thus rendering activation rates less sensitive to the weaker C-H bonds in larger alkane products than in CH4 reactants. Anhydrous carbonylation of dimethyl ether forms a single C-C bond on protons residing within inorganic voids that preferentially stabilize the kinetically-relevant transition state through van der Waals interactions that compensate for the weak CO nucleophile. Similar solvation effects, but by intrapore liquids instead of inorganic hosts, also become evident as alkenes condense within MCM-41 channels containing isolated Ni(2+) active sites during dimerization reactions. Intrapore liquids preferentially stabilize transition states for C-C bond formation and product desorption, leading to unprecedented reactivity and site stability at sub-ambient temperatures and to 1-alkene dimer selectivities previously achieved only on organometallic systems with co-catalysts or activators. C1 homologation selectively forms C4 and C7 chains with a specific backbone (isobutane, triptane) on solid acids

  13. Catalytic and non-catalytic roles for the mono-ADP-ribosyltransferase Arr in the mycobacterial DNA damage response.

    Science.gov (United States)

    Stallings, Christina L; Chu, Linda; Li, Lucy X; Glickman, Michael S

    2011-01-01

    Recent evidence indicates that the mycobacterial response to DNA double strand breaks (DSBs) differs substantially from previously characterized bacteria. These differences include the use of three DSB repair pathways (HR, NHEJ, SSA), and the CarD pathway, which integrates DNA damage with transcription. Here we identify a role for the mono-ADP-ribosyltransferase Arr in the mycobacterial DNA damage response. Arr is transcriptionally induced following DNA damage and cellular stress. Although Arr is not required for induction of a core set of DNA repair genes, Arr is necessary for suppression of a set of ribosomal protein genes and rRNA during DNA damage, placing Arr in a similar pathway as CarD. Surprisingly, the catalytic activity of Arr is not required for this function, as catalytically inactive Arr was still able to suppress ribosomal protein and rRNA expression during DNA damage. In contrast, Arr substrate binding and catalytic activities were required for regulation of a small subset of other DNA damage responsive genes, indicating that Arr has both catalytic and noncatalytic roles in the DNA damage response. Our findings establish an endogenous cellular function for a mono-ADP-ribosyltransferase apart from its role in mediating Rifampin resistance.

  14. Catalytic and non-catalytic roles for the mono-ADP-ribosyltransferase Arr in the mycobacterial DNA damage response.

    Directory of Open Access Journals (Sweden)

    Christina L Stallings

    Full Text Available Recent evidence indicates that the mycobacterial response to DNA double strand breaks (DSBs differs substantially from previously characterized bacteria. These differences include the use of three DSB repair pathways (HR, NHEJ, SSA, and the CarD pathway, which integrates DNA damage with transcription. Here we identify a role for the mono-ADP-ribosyltransferase Arr in the mycobacterial DNA damage response. Arr is transcriptionally induced following DNA damage and cellular stress. Although Arr is not required for induction of a core set of DNA repair genes, Arr is necessary for suppression of a set of ribosomal protein genes and rRNA during DNA damage, placing Arr in a similar pathway as CarD. Surprisingly, the catalytic activity of Arr is not required for this function, as catalytically inactive Arr was still able to suppress ribosomal protein and rRNA expression during DNA damage. In contrast, Arr substrate binding and catalytic activities were required for regulation of a small subset of other DNA damage responsive genes, indicating that Arr has both catalytic and noncatalytic roles in the DNA damage response. Our findings establish an endogenous cellular function for a mono-ADP-ribosyltransferase apart from its role in mediating Rifampin resistance.

  15. Catalytic liquid marbles: Ag nanowire-based miniature reactors for highly efficient degradation of methylene blue.

    Science.gov (United States)

    Miao, Yue-E; Lee, Hiang Kwee; Chew, Wee Shern; Phang, In Yee; Liu, Tianxi; Ling, Xing Yi

    2014-06-04

    Ag nanowire-based catalytic liquid marbles are fabricated as miniature reactors, which demonstrate highly efficient, support-free and rate-controllable heterogeneous degradation of methylene blue, with catalytic efficiency close to 100%. Our miniature catalytic liquid marbles are essential for reactions involving highly toxic/hazardous or costly reactants, where small volume preliminary reactions are preferred.

  16. Investigation on CO catalytic oxidation reaction kinetics of faceted perovskite nanostructures loaded with Pt

    KAUST Repository

    Yin, S. M.

    2017-01-18

    Perovskite lead titanate nanostructures with specific {111}, {100} and {001} facets exposed, have been employed as supports to investigate the crystal facet effect on the growth and CO catalytic activity of Pt nanoparticles. The size, distribution and surface chemical states of Pt on the perovskite supports have been significantly modified, leading to a tailored conversion temperature and catalytic kinetics towards CO catalytic oxidation.

  17. ElectroWeak Bosons Couplings

    CERN Document Server

    Ouraou, Ahmimed; The ATLAS collaboration

    2016-01-01

    Latest results on the measurement of gauge boson couplings, from ATLAS and CMS at the LHC, are presented. This review starts with an introduction to boson couplings, then the measurements of Triple and Quartic Couplings are described. And finally, limits on anomalous couplings are summarized.

  18. The different catalytic roles of the metal-binding ligands in human 4-hydroxyphenylpyruvate dioxygenase.

    Science.gov (United States)

    Huang, Chih-Wei; Liu, Hsiu-Chen; Shen, Chia-Pei; Chen, Yi-Tong; Lee, Sung-Jai; Lloyd, Matthew D; Lee, Hwei-Jen

    2016-05-01

    4-Hydroxyphenylpyruvate dioxygenase (HPPD) is a non-haem iron(II)-dependent oxygenase that catalyses the conversion of 4-hydroxyphenylpyruvate (HPP) to homogentisate (HG). In the active site, a strictly conserved 2-His-1-Glu facial triad co-ordinates the iron ready for catalysis. Substitution of these residues resulted in about a 10-fold decrease in the metal binding affinity, as measured by isothermal titration calorimetry, and a large reduction in enzyme catalytic efficiencies. The present study revealed the vital role of the ligand Glu(349) in enzyme function. Replacing this residue with alanine resulted in loss of activity. The E349G variant retained 5% activity for the coupled reaction, suggesting that co-ordinating water may be able to support activation of the trans-bound dioxygen upon substrate binding. The reaction catalysed by the H183A variant was fully uncoupled. H183A variant catalytic activity resulted in protein cleavage between Ile(267) and Ala(268) and the production of an N-terminal fragment. The H266A variant was able to produce 4-hydroxyphenylacetate (HPA), demonstrating that decarboxylation had occurred but that there was no subsequent product formation. Structural modelling of the variant enzyme with bound dioxygen revealed the rearrangement of the co-ordination environment and the dynamic behaviour of bound dioxygen in the H266A and H183A variants respectively. These models suggest that the residues regulate the geometry of the reactive oxygen intermediate during the oxidation reaction. The mutagenesis and structural simulation studies demonstrate the critical and unique role of each ligand in the function of HPPD, and which correlates with their respective co-ordination position.

  19. Microlith-Based Catalytic Reactor for Air Quality and Trace Contaminant Control Applications

    Science.gov (United States)

    Vilekar, Saurabh; Hawley, Kyle; Junaedi, Christian; Crowder, Bruce; Prada, Julian; Mastanduno, Richard; Perry, Jay L.; Kayatin, Matthew J.

    2015-01-01

    Traditionally, gaseous compounds such as methane, carbon monoxide, and trace contaminants have posed challenges for maintaining clean air in enclosed spaces such as crewed spacecraft cabins as they are hazardous to humans and are often difficult to remove by conventional adsorption technology. Catalytic oxidizers have provided a reliable and robust means of disposing of even trace levels of these compounds by converting them into carbon dioxide and water. Precision Combustion, Inc. (PCI) and NASA - Marshall (MSFC) have been developing, characterizing, and optimizing high temperature catalytic oxidizers (HTCO) based on PCI's patented Microlith® technology to meet the requirements of future extended human spaceflight explorations. Current efforts have focused on integrating the HTCO unit with a compact, simple recuperative heat exchanger to reduce the overall system size and weight while also reducing its energy requirements. Previous efforts relied on external heat exchangers to recover the waste heat and recycle it to the oxidizer to minimize the system's power requirements; however, these units contribute weight and volume burdens to the overall system. They also result in excess heat loss due to the separation of the HTCO and the heat recuperator, resulting in lower overall efficiency. Improvements in the recuperative efficiency and close coupling of HTCO and heat recuperator lead to reductions in system energy requirements and startup time. Results from testing HTCO units integrated with heat recuperators at a variety of scales for cabin air quality control and heat melt compactor applications are reported and their benefits over previous iterations of the HTCO and heat recuperator assembly are quantified in this paper.

  20. Efficient photothermal catalytic hydrogen production over nonplasmonic Pt metal supported on TiO2

    Science.gov (United States)

    Song, Rui; Luo, Bing; Jing, Dengwei

    2016-10-01

    Most of the traditional photocatalytic hydrogen productions were conducted under room temperature. In this work, we selected nonplasmonic Pt metal anchored on TiO2 nanoparticles with photothermal activity to explore more efficient hydrogen production technology over the whole solar spectrum. Photothermal experiments were carried out in a carefully designed top irradiated photocatalytic reactor that can withstand high temperature and relatively higher pressure. Four typical organic materials, i.e., methyl alcohol (MeOH), trielthanolamne (TEOA), formic acid (HCOOH) and glucose, were investigated. Formic acid, a typical hydrogen carrier, was found to show the best activity. In addition, the effects of different basic parameters such as sacrificial agent concentration and the temperature on the activity of hydrogen generation were systematically investigated for understanding the qualitative and quantitative effects of the photothermal catalytic reaction process. The hydrogen yields at 90 °C of the photothermal catalytic reaction with Pt/TiO2 are around 8.1 and 4.2 times higher than those of reactions carried out under photo or thermal conditions alone. We can see that the photothermal hydrogen yield is not the simple sum of the photo and thermal effects. This result indicated that the Pt/TiO2 nanoparticles can efficiently couple photo and thermal energy to more effectively drive hydrogen production. As a result, the excellent ability makes it superior to other conventional semiconductor photocatalysts and thermal catalysts. Future works could concentrate on exploring photothermal catalysis as well as the potential synergism between photo and thermal effects to find more efficient hydrogen production technology using the whole solar spectrum.

  1. DISCUSSIONS ON STRUCTURAL COUPLING

    Institute of Scientific and Technical Information of China (English)

    ZHU Wenbin; GUO Lingzhi; MA Ruishi; SUN Yan; WANG Feng

    2004-01-01

    The structural coupling is a common geological phenomenon. The structural differences between eastern and western active continental margins of modern Pacific and between paleo-Pacific and modern-Pacific continental margins are related to the characteristics and status of the subducting oceanic plate, namely, 1. subducting angle; 2. change in subducting angle; 3. subducting velocity; 4. change in subducting velocity; 5. subduction depth; 6. horizontal distance between the leading edge of the subducting plate and the trench; 7. the structural form of the subducting plate at the 670km boundary between the upper and lower mantle; 8. the displacement and the direction of displacement of subducting plate. The control and influence toward the shallow-level structures by the deep-level structural activities is a detailed representation of the structural coupling on active continental margin.The basin-maintain coupling phenomenon is an intracontinental structural coupling. The far field effect of collision between Indian plate and Eurasian plate results in the occurrence of intracontinental A-type subduction in central Asia, and the A-type subduction is the key factor that results in the atrophy of basins and the formation of mountain systems.

  2. Generic flux coupling analysis

    NARCIS (Netherlands)

    Reimers, A.C.; Goldstein, Y.; Bockmayr, A.

    2015-01-01

    Flux coupling analysis (FCA) has become a useful tool for aiding metabolic reconstructions and guiding genetic manipulations. Originally, it was introduced for constraint-based models of metabolic networks that are based on the steady-state assumption. Recently, we have shown that the steady-state a

  3. International Migration of Couples

    DEFF Research Database (Denmark)

    Junge, Martin; Munk, Martin D.; Poutvaara, Panu

    2017-01-01

    Migrant self-selection is important to both origin and destination countries. We develop a theoretical model regarding the migration of dual-earner couples and test it in the context of international migration, using population-wide administrative data from Denmark. Our model predicts...

  4. Coupling in reflector arrays

    DEFF Research Database (Denmark)

    Appel-Hansen, Jørgen

    1968-01-01

    In order to reduce the space occupied by a reflector array, it is desirable to arrange the array antennas as close to each other as possible; however, in this case coupling between the array antennas will reduce the reflecting properties of the reflector array. The purpose of the present communic...

  5. Coupling Gammasphere and ORRUBA

    Energy Technology Data Exchange (ETDEWEB)

    Ratkiewicz, A.; Cizewski, J. A.; Manning, B. [Department of Physics and Astronomy, Rutgers University, New Brunswick, NJ 08903 (United States); Pain, S. D.; Bardayan, D. W. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Blackmon, J. C.; Matos, M. [Department of Physics and Astronomy, Louisiana State University, Baton Rouge, LA 70803 (United States); Chipps, K. A. [Department of Physics, Colorado School of Mines, Golden, CO 80401 (United States); Hardy, S.; Shand, C. [Department of Physics and Astronomy, Rutgers University, New Brunswick, NJ 08903 and Department of Physics, University of Surrey, Guildford, Surrey, GU2 7XH (United Kingdom); Jones, K. L. [Department of Physics and Astronomy, University of Tennessee, Knoxville, TN 37996 (United States); Kozub, R. L. [Physics Department, Tennessee Technological University, Cookeville, TN 38505 (United States); Lister, C. J. [Physics Division, Argonne National Laboratory, Argonne, IL 60439 and Department of Physics and Applied Physics, University of Massachusetts Lowell, Lowell, MA 01854 (United States); Peters, W. A. [Oak Ridge Associated Universities, Oak Ridge, TN 37830 (United States); Seweryniak, D. [Physics Division, Argonne National Laboratory, Argonne, IL 60439 (United States)

    2013-04-19

    The coincident detection of particles and gamma rays allows the study of the structure of exotic nuclei via inverse kinematics reactions using radioactive ion beams and thick targets. We report on the status of the project to couple the highresolution charged-particle detector ORRUBA to Gammasphere, a high-efficiency, high-resolution gamma ray detector.

  6. Chemical Reactions and Kinetics of the Carbon Monoxide Coupling in the Presence of Hydrogen

    Institute of Scientific and Technical Information of China (English)

    Fandong Meng; Genhui Xu; Zhenhua Li; Pa Du

    2002-01-01

    The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence.

  7. Study on Catalytic Oxidation Treatment of Coking Wastewater%催化氧化法处理焦化废水研究

    Institute of Scientific and Technical Information of China (English)

    邹琳琳; 黄冲; 潘一; 杨双春

    2013-01-01

    As high concentration organic wastewater, coking wastewater is poisonous, harmful and difficult biodegradable. Catalytic oxidation process can decompose organic macromolecular material and reduce coking wastewater toxicity. In this article, research status of catalytic oxidation treatment of coking wastewater was mainly introduced, including electrode catalytic method, electrochemical catalysis method, wet catalytic oxidation, supercritical water oxidation method, catalytic coupling method, titanium dioxide photo catalysis method and ultrasonic collaborative light catalysis, and so on. Various methods were summarized and evaluated. Then, some suggestions of research direction in the future were put forward.%  焦化废水是一种有毒有害、难生物降解的高浓度有机废水,催化氧化法能够分解有机大分子物质、降低焦化废水毒性,近年来国内外学者对其研究较多。介绍了催化氧化法处理焦化废水的研究现状,包括电极催化法、电解催化法、湿式催化氧化法,超临界水氧化法、催化耦合法、二氧化钛光催化法和超声协同光催化等。对各种方法进行了综述和评价,同时对催化氧化法处理焦化废水今后的研究方向提出了建议。

  8. Green synthesis and catalytic application of curcumin stabilized silver nanoparticles

    Indian Academy of Sciences (India)

    A D VERMA; N JAIN; S K SINGHA; M A QURAISHI; I SINHA

    2016-12-01

    An ultrasonication based green synthesis approach was used to prepare curcumin-stabilized silver nanoparticles (c-AgNPs). Nanoparticles thus obtained were characterized by UV-Visible spectroscopy, X-ray diffraction (XRD), Transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). Two different size distributions of c-AgNPs were obtained by changing the ratio of curcumin to silver salt precursor. These c-AgNPs were used as catalysts in the catalytic reduction of p-nitrophenol to p-aminophenol. The c-AgNPs with narrower size distribution exhibited better catalytic activity as well as lower activation energy. Variation of apparent rate constant with the reactant concentration agreed with the Langmuir- Hinshelwood (LH) model. Consequently, the surface rate constant related to the rate-determining step and the respective adsorption constants of p-nitrophenol and of borohydride were determined as per this model.

  9. Catalytic conversion of alcohols to hydrocarbons with low benzene content

    Energy Technology Data Exchange (ETDEWEB)

    Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

    2016-09-06

    A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

  10. Effect of Novel Supporter on Catalytic Combustion of Methane

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A new catalyst support, Ce-Mg-O, was prepared in a novel way macromolecule surfactant modified method and was used as a catalyst support for low-temperature methane combustion. The results indicate that the new type of FeOx/Ce-Mg-O catalyst exhibits high activity in low-temperature methane combustion, such that the T90 at which 90% conversion of methane occurs can be obtained at 560 ℃. The structure of the catalyst and the effect of the supporter on catalytic activity were characterized by transmission electronic microscopy (TEM), X-ray diffraction (XRD), and temperature-programmed reduction (TPR). The results indicate that the high catalytic activity of FeOx/Ce-Mg-O over methane combustion is strongly dependent on the particle size, typical crystal phase of the Ce-Mg-O, and the interaction of FeOx and Ce-Mg-O.

  11. Catalytic Autoxidation of Fatty Acid Methyl Esters from Jatropha Oil

    Directory of Open Access Journals (Sweden)

    Abebe K. Endalew

    2014-01-01

    Full Text Available Metal catalysts for transesterification of vegetable oils can cause autoxidation side reactions which reduces the fuel quality of the biodiesel. On the other side, oxidation of highly unsaturated oils can open opportunities for the synthesis of other important renewable chemical products. This study reports catalytic oxidation of fatty acids of Jatropha curcas oil (JCO by Li-CaO/Fe2(SO43 catalyst during transesterification at mild reaction conditions. The catalytic oxidation of the triglycerides was shown to be enhanced by the presence of lithium incorporated in the otherwise active catalyst combination of CaO/Fe2(SO43 used for high conversion into FAME. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS was used to assess the reaction products.

  12. Ultraviolet laser deposition of graphene thin films without catalytic layers

    KAUST Repository

    Sarath Kumar, S. R.

    2013-01-09

    In this letter, the formation of nanostructured graphene by ultraviolet laser ablation of a highly ordered pyrolytic graphite target under optimized conditions is demonstrated, without a catalytic layer, and a model for the growth process is proposed. Previously, graphene film deposition by low-energy laser (2.3 eV) was explained by photo-thermal models, which implied that graphene films cannot be deposited by laser energies higher than the C-C bond energy in highly ordered pyrolytic graphite (3.7 eV). Here, we show that nanostructured graphene films can in fact be deposited using ultraviolet laser (5 eV) directly over different substrates, without a catalytic layer. The formation of graphene is explained by bond-breaking assisted by photoelectronic excitation leading to formation of carbon clusters at the target and annealing out of defects at the substrate.

  13. Hierarchical zeolites and their catalytic performance in selective oxidative processes.

    Science.gov (United States)

    Ojeda, Manuel; Grau-Atienza, Aida; Campos, Rafael; Romero, Antonio A; Serrano, Elena; Maria Marinas, Jose; García Martínez, Javier; Luque, Rafael

    2015-04-24

    Hierarchical ZSM-5 zeolites prepared using a simple alkali treatment and subsequent HCl washing are found to exhibit unprecedented catalytic activities in selective oxidation of benzyl alcohol under microwave irradiation. The metal-free zeolites promote the microwave-assisted oxidation of benzyl alcohol with hydrogen peroxide in yields ranging from 45-35 % after 5 min of reaction under mild reaction conditions as well as the epoxidation of cyclohexene to valuable products (40-60 % conversion). The hierarchically porous systems also exhibited an interesting catalytic activity in the dehydration of N,N-dimethylformamide (25-30 % conversion), representing the first example of transition-metal free catalysts in this reaction.

  14. Mechanism of Transition-Metal Nanoparticle Catalytic Graphene Cutting.

    Science.gov (United States)

    Ma, Liang; Wang, Jinlan; Yip, Joanne; Ding, Feng

    2014-04-03

    Catalytic cutting by transition-metal (TM) particles is a promising method for the synthesizing of high-quality graphene quantum dots and nanoribbons with smooth edges. Experimentally, it is observed that the cutting always results in channels with zigzag (ZZ) or armchair (AC) edges. However, the driving force that is responsible for such a cutting behavior remains a puzzle. Here, by calculating the interfacial formation energies of the TM-graphene edges with ab initio method, we show that the surface of a catalyst particle tends to be aligned along either AC or ZZ direction of the graphene lattice, and thus the cutting of graphene is guided as such. The different cutting behaviors of various catalysts are well-explained based on the competition between TM-passivated graphene edges and the etching-agent-terminated ones. Furthermore, the kinetics of graphene catalytic cutting along ZZ and AC directions, respectively, are explored at the atomic level.

  15. Formaldehyde: catalytic oxidation as a promising soft way of elimination.

    Science.gov (United States)

    Quiroz Torres, Jhon; Royer, Sébastien; Bellat, Jean-Pierre; Giraudon, Jean-Marc; Lamonier, Jean-François

    2013-04-01

    Compared to other molecules such as benzene, toluene, xylene, and chlorinated compounds, the catalytic oxidation of formaldehyde has been studied rarely. However, standards for the emission level of this pollutant will become more restrictive because of its extreme toxicity even at very low concentrations in air. As a consequence, the development of a highly efficient process for its selective elimination is needed. Complete catalytic oxidation of formaldehyde into CO2 and H2 O using noble-metal-based catalysts is a promising method to convert this pollutant at room temperature, making this process energetically attractive from an industrial point of view. However, the development of a less expensive active phase is required for a large-scale industrial development. Nanomaterials based on oxides of manganese are described as the most promising catalysts. The objective of this Minireview is to present promising recent studies on the removal of formaldehyde through heterogeneous catalysis to stimulate future research in this topic.

  16. Preparation and catalytic properties of tungsten oxides with different morphologies

    Energy Technology Data Exchange (ETDEWEB)

    Bi Yunfei, E-mail: beiyf2003@yahoo.com.cn [Research Institute of Petroleum Processing, SINOPEC, 18 Xue Yuan Road, 100083 Beijing (China); Li Dadong; Nie Hong [Research Institute of Petroleum Processing, SINOPEC, 18 Xue Yuan Road, 100083 Beijing (China)

    2010-09-01

    Tungsten oxides with different morphologies including platelet-like sheets, nanobelts, and nanoparticles have been successfully prepared by changing the ions in the synthetic solution. Transmission electron microscopy, X-ray diffraction, Fourier-transform infrared analysis and N{sub 2} adsorption were employed to reveal the morphological evolution, and results show that the morphological evolution can be attributed to the alteration of coordination environment of tungstenic cations contained in the synthetic solution. Furthermore, these products have been applied into hydrodesulfurization measurement to investigate the relationship between the morphologies of tungsten oxides and their catalytic properties. It is concluded that the catalysts originating from nanobelt-like tungsten oxides have highest catalytic activity and excellent selectivity due to their scrolled character and strong metallic edges.

  17. Polyporphyrin Complexes of Some Transition Metals. Synthesis and Catalytic Properties

    Directory of Open Access Journals (Sweden)

    A.V. Shakhvorostov

    2016-10-01

    Full Text Available The paper presents the results of synthesis of polyporphyrin structures and metal complex catalyzers at their basis. Porphyrin to be derived from the addition reaction of pyrrole and formaldehyde. Metal complex catalyzers to be derived at the reaction of complex formation of ions of Mn2+, Co2+, Ni2+ and Fe3+ with porphyrin. The structure, physical and chemical properties of derived materials to be examined with IR spectroscopy, differential thermal analysis, thermogravimetric analysis, scanning electron microscopy investigation. Catalytic activity of synthesized catalytic systems to be established at the reaction of decompounding of hydrogen peroxide and alkylaromatics oxidation by hydrogen peroxide. The processes have been conducted under soft conditions, and also at different organic solvents.

  18. Catalytic asymmetric synthesis of biologically important 3-hydroxyoxindoles: an update

    Directory of Open Access Journals (Sweden)

    Bin Yu

    2016-05-01

    Full Text Available Oxindole scaffolds are prevalent in natural products and have been recognized as privileged substructures in new drug discovery. Several oxindole-containing compounds have advanced into clinical trials for the treatment of different diseases. Among these compounds, enantioenriched 3-hydroxyoxindole scaffolds also exist in natural products and have proven to possess promising biological activities. A large number of catalytic asymmetric strategies toward the construction of 3-hydroxyoxindoles based on transition metal catalysis and organocatalysis have been reported in the last decades. Additionally, 3-hydroxyoxindoles as versatile precursors have also been used in the total synthesis of natural products and for constructing structurally novel scaffolds. In this review, we aim to provide an overview about the catalytic asymmetric synthesis of biologically important 3-substituted 3-hydroxyoxindoles and 3-hydroxyoxindole-based further transformations.

  19. Catalytic conversion of alcohols to hydrocarbons with low benzene content

    Energy Technology Data Exchange (ETDEWEB)

    Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

    2016-03-08

    A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

  20. Catalytic wet air oxidation of high concentration pharmaceutical wastewater.

    Science.gov (United States)

    Zhan, Wei; Wang, Xiaocong; Li, Daosheng; Ren, Yongzheng; Liu, Dongqi; Kang, Jianxiong

    2013-01-01

    In this study, we investigated the pretreatment of a high concentration pharmaceutical wastewater by catalytic wet air oxidation (CWAO) process. Different experiments were conducted to investigate the effects of the catalyst type, operating temperature, initial system pH, and oxygen partial pressure on the oxidation of the wastewater. Results show that the catalysts prepared by the co-precipitation method have better catalytic activity compared to others. Chemical oxygen demand (COD) conversion increased with the increase in temperature from 160 to 220 °C and decreased with the increase in pH. Moreover, the effect of the oxygen partial pressure on the COD conversion was significant only during the first 20 min of the reaction. Furthermore, the biodegradability of the wastewater improved greatly after CWAO, the ratio of BOD5/COD increased less than 0.1-0.75 when treated at 220 °C (BOD: biochemical oxygen demand).