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Sample records for base metal-palladium catalytic

  1. Novel Base Metal-Palladium Catalytic Diesel Filter Coating with NO2 Reducing Properties

    DEFF Research Database (Denmark)

    Johansen, K.; Dahl, S.; Mogensen, G.

    2007-01-01

    A novel alternative base metal/palladium coat has been developed that has limited NO2 formation and which even removes NO2 in a wide temperature range.Soot combustion, HC conversion and CO conversion properties are comparable to current platinum based solutions but the coating has a more attracti...

  2. Metal Palladium Dispersed Inside Macroporous Ion-Exchange Resins: Textural Characterization and Accessibility to Gaseou Reactants

    Czech Academy of Sciences Publication Activity Database

    Biffis, A.; Jeřábek, Karel; D'Archivio, A. A.; Galantini, L.; Corain, B.

    2000-01-01

    Roč. 130, - (2000), s. 2327-2332 ISSN 0167-2991. [International Congress on Catalysis /12./. Granada, 09.07.2000-14.07.2000] Institutional research plan: CEZ:AV0Z4072921 Keywords : metal palladium * dispersed * ion-exchange resins Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.513, year: 2000

  3. Protein structure based prediction of catalytic residues

    Science.gov (United States)

    2013-01-01

    Background Worldwide structural genomics projects continue to release new protein structures at an unprecedented pace, so far nearly 6000, but only about 60% of these proteins have any sort of functional annotation. Results We explored a range of features that can be used for the prediction of functional residues given a known three-dimensional structure. These features include various centrality measures of nodes in graphs of interacting residues: closeness, betweenness and page-rank centrality. We also analyzed the distance of functional amino acids to the general center of mass (GCM) of the structure, relative solvent accessibility (RSA), and the use of relative entropy as a measure of sequence conservation. From the selected features, neural networks were trained to identify catalytic residues. We found that using distance to the GCM together with amino acid type provide a good discriminant function, when combined independently with sequence conservation. Using an independent test set of 29 annotated protein structures, the method returned 411 of the initial 9262 residues as the most likely to be involved in function. The output 411 residues contain 70 of the annotated 111 catalytic residues. This represents an approximately 14-fold enrichment of catalytic residues on the entire input set (corresponding to a sensitivity of 63% and a precision of 17%), a performance competitive with that of other state-of-the-art methods. Conclusions We found that several of the graph based measures utilize the same underlying feature of protein structures, which can be simply and more effectively captured with the distance to GCM definition. This also has the added the advantage of simplicity and easy implementation. Meanwhile sequence conservation remains by far the most influential feature in identifying functional residues. We also found that due the rapid changes in size and composition of sequence databases, conservation calculations must be recalibrated for specific

  4. Catalytic

    Directory of Open Access Journals (Sweden)

    S.A. Hanafi

    2014-03-01

    Full Text Available A series of dealuminated Y-zeolites impregnated by 0.5 wt% Pt catalysts promoted by different amounts of Ni, Pd or Cr (0.3 and 0.6 wt% were prepared and characterized as hydrocracking catalysts. The physicochemical and structural characterization of the solid catalysts were investigated and reported through N2 physisorption, XRD, TGA-DSC, FT-IR and TEM techniques. Solid catalysts surface acidities were investigated through FT-IR spectroscopy aided by pyridine adsorption. The solid catalytic activities were evaluated through hydroconversion of n-hexane and n-heptane employing micro-catalytic pulse technique directly connected to a gas chromatograph analyzer. The thermal stability of the solids was also investigated up to 800 °C. Crystallinity studies using the XRD technique of all modified samples proved analogous to the parent Y-zeolite, exhibiting nearly an amorphous and microcrystalline character of the second metal oxides. Disclosure of bimetallic catalysts crystalline characterization, through XRD, was not viable. The nitrogen adsorption–desorption isotherms for all samples concluded type I adsorption isotherms, without any hysteresis loop, indicating that the entire pore system is composed of micropores. TEM micrographs of the solid catalysts demonstrate well-dispersed Pt, Ni and Cr nanoparticles having sizes of 2–4 nm and 7–8 nm, respectively. The catalytic activity results indicate that the bimetallic (0.5Pt–0.3Cr/D18H–Y catalyst is the most active towards n-hexane and n-heptane isomerization while (0.5Pt–0.6Ni/D18H–Y catalyst can be designed as most suitable as a cracking catalyst.

  5. Highly efficient catalytic systems based on Pd-coated microbeads

    Science.gov (United States)

    Lim, Jin Hyun; Cho, Ahyoung; Lee, Seung Hwan; Park, Bumkyo; Kang, Dong Woo; Koo, Chong Min; Yu, Taekyung; Park, Bum Jun

    2018-01-01

    The efficiency of two prototype catalysis systems using palladium (Pd)-coated microparticles was investigated with regard to the recovery and recyclability of the catalytic particles. One such system was the interface-adsorption method, in which polymer particles coated with Pd nanoparticles strongly and irreversibly attach to the oil-water interface. Due to the irreversible adsorption of the catalytic particles to the interface, particle loss was completely prevented while mixing the aqueous solution and while collecting the products. The other system was based on the magnetic field-associated particle recovery method. The use of polymeric microparticles containing Pd nanoparticles and magnetite nanoparticles accelerated the sedimentation of the particles in the aqueous phase by applying a strong magnetic field, consequently suppressing drainage of the particles from the reactor along the product stream. Upon multiple runs of the catalytic reactions, it was found that conversion does not change significantly, demonstrating the excellent recyclability and performance efficiency in the catalytic processes.

  6. Catalytic Hydroisomerization Upgrading of Vegetable Oil-Based Insulating Oil

    Directory of Open Access Journals (Sweden)

    Dieu-Phuong Phan

    2018-03-01

    Full Text Available Due to its high biodegradability, high dielectric strength, and good thermal stability, vegetable oil is under consideration as an alternative transformer fluid for power system equipment, replacing traditional petroleum-based insulating oils. Its main drawbacks are its poor low-temperature properties arising from the crystallization of its long-chain normal paraffins, and its lower oxidative stability arising from its higher concentration of unsaturated fatty acids. Hydroisomerization/isomerization over bifunctional catalysts is considered to be an efficient pathway to upgrade vegetable oil-based insulating oil; this converts saturated/unsaturated long-chain fatty acids to branched isomers. The efficiency of this process depends crucially on the behavior of the catalyst system. This paper extensively reviews recent results on the influence that the metal phase and acidity, the effects of pore channels, and the balance between metal and acid sites have upon the activity and selectivity of catalytic hydroisomerization.

  7. Catalytic Transformation of Ethylbenzene over Y-Zeolite-based Catalysts

    KAUST Repository

    Al-Khattaf, Sulaiman

    2008-11-19

    Catalytic transformation of ethylbenzene (EB) has been investigated over ultrastable Y (USY)-zeolite-based catalysts in a novel riser simulator at different operating conditions. The effect of reaction conditions on EB conversion is reported. The USY catalyst (FCC-Y) was modified by steaming to form a significantly lower acidity catalyst (FCC-SY). The current study shows that the FCC-SY catalyst favors EB disproportionation more than cracking. A comparison has been made between the results of EB conversion over the lowly acidic catalyst (FCC-SY) and the highly acidic catalyst (FCC-Y) under identical conditions. It was observed that increase in catalyst acidity favored cracking of EB at the expense of disproportionation. Kinetic parameters for EB disappearance during disproportionation reaction over the FCC-SY catalyst were calculated using the catalyst activity decay function based on time on stream (TOS). © 2008 American Chemical Society.

  8. Highly sensitive methane catalytic combustion micro-sensor based on mesoporous structure and nano-catalyst.

    Science.gov (United States)

    Su, Jiacan; Cao, Liehu; Li, Liang; Wei, Jie; Li, Gengnan; Yuan, Yinyin

    2013-10-21

    In order to get a methane catalytic combustion micro-sensor, two different catalytic systems used in traditional methane catalytic combustion sensors were fabricated into a mesoporous structure and their catalytic activities were investigated. In comparison, the Rh2O3-Al2O3 system can form more a uniform mesoporous structure and has a much higher specific surface area. Even more importantly, it has relatively higher catalytic activity and stability for the methane catalytic combustion reaction. After being coated on a microelectro-mechanical system (MEMS) micro-heater, a catalytic combustion type methane micro-sensor was fabricated. The meso-structured Rh2O3-Al2O3 hybrid based MEMS sensor demonstrated a short T90 response time, relatively high signal output, high enough signal/noise ratio for practical detecting and strong anti-poison properties.

  9. MEMS-based fuel cells with integrated catalytic fuel processor and method thereof

    Science.gov (United States)

    Jankowski, Alan F [Livermore, CA; Morse, Jeffrey D [Martinez, CA; Upadhye, Ravindra S [Pleasanton, CA; Havstad, Mark A [Davis, CA

    2011-08-09

    Described herein is a means to incorporate catalytic materials into the fuel flow field structures of MEMS-based fuel cells, which enable catalytic reforming of a hydrocarbon based fuel, such as methane, methanol, or butane. Methods of fabrication are also disclosed.

  10. Geopolymer based catalysts-New group of catalytic materials

    Czech Academy of Sciences Publication Activity Database

    Sazama, Petr; Bortnovsky, O.; Dědeček, Jiří; Tvarůžková, Zdenka; Sobalík, Zdeněk

    2011-01-01

    Roč. 164, č. 1 (2011), s. 92-99 ISSN 0920-5861. [Joint International Conference /1./ of the Tokyo Conference on Advanced Catalytic Science and Technology /11./ Asia Pacific Congress on Catalysis /5./. Sapporo, 18.07.2010-23.07.2010] R&D Projects: GA MPO FT-TA4/068; GA AV ČR KAN100400702 Institutional research plan: CEZ:AV0Z40400503 Keywords : geopolymers * redox catalysis * SCR- NOx Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.407, year: 2011

  11. Cobaloxime-based photo-catalytic devices for hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Fihri, A.; Artero, V.; Razavet, M.; Baffert, C.; Fontecave, M. [CEA Grenoble, DSV, iRTSV, Lab Chim et Biol Metaux, CNRS, UMR 5249, Univ Grenoble 1, F-38054 Grenoble 9 (France); Leibl, W. [CEA, DSV, iBiTecS, Lab Photocatalyse et Biohydrogene, CNRS, URA 2096, Gif Sur Yvette (France)

    2008-07-01

    In this paper is described the synthesis and activity of a series of novel hetero-dinuclear ruthenium-cobaloxime photo-catalysts able to achieve the photochemical production of hydrogen with the highest turnover numbers so far reported for such devices. First of all, substituting cobalt for rare and expensive platinum, palladium, or rhodium metals in photo-catalysts is a first step toward economically viable hydrogen production. Cobaloximes appear to be good candidates for H{sub 2}-evolving catalysts, and they may provide a good basis for the design of photo-catalysts that function in pure water as both the solvent and the sustainable proton source. Secondly, a molecular connection between the sensitizer and the H{sub 2}-evolving catalyst seems to provide advantages regarding the photo-catalytic activity. Structural modifications of this connection should allow a better tuning of the electron transfer between the light-harvesting unit and the catalytic center and thus an increase of the efficiency of the system. (O.M.)

  12. Alkali resistivity of Cu based selective catalytic reduction catalysts

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Jensen, Anker Degn; Riisager, Anders

    2012-01-01

    The deactivation of V2O5–WO3–TiO2, Cu–HZSM5 and Cu–HMOR plate type monolithic catalysts was investigated when exposed to KCl aerosols in a bench-scale reactor. Fresh and exposed catalysts were characterized by selective catalytic reduction (SCR) activity measurements, scanning electron microscope...... and Cu–HMOR catalysts only experienced a slight loss of acidity while the V2O5–WO3–TiO2 catalyst lost most of the acidity. High alkali resistivity seems to be characteristic of the zeolite supported SCR catalysts which thus could be attractive for flue gas cleaning in biomass plants....

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

    KAUST Repository

    Imran, Ali

    2015-11-24

    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 treatment of the pyrolysis vapors. The in-situ catalytic pyrolysis was carried out in an entrained flow reactor system using a premixed feedstock of Na2CO3 and biomass and post treatment of biomass pyrolysis vapor was conducted in a downstream fixed bed reactor of Na2CO3/γ-Al2O3. Results have shown that both Na2CO3 and Na2CO3/γ-Al2O3 can be used for the production of a high quality bio-oil from catalytic pyrolysis of oil-impregnated-wood and jatropha cake. The catalytic bio-oil had very low oxygen content, water content as low as 1wt.%, a neutral pH, and a high calorific value upto 41.8MJ/kg. The bio-oil consisted of high value chemical compounds mainly hydrocarbons and undesired compounds in the bio-oil were either completely removed or considerably reduced. Increasing the triglycerides content (vegetable oil) in the wood enhanced the formation of hydrocarbons in the bio-oil. Post treatment of the pyrolysis vapor over a fixed bed of Na2CO3/γ-Al2O3 produced superior quality bio-oil compared to in-situ catalytic pyrolysis with Na2CO3. This high quality bio-oil may be used as a precursor in a fractionating process for the production of alternative fuels. © 2015 Elsevier B.V.

  14. Catalytic thermal treatment (catalytic thermolysis) of a rice grain-based biodigester effluent of an alcohol distillery plant.

    Science.gov (United States)

    Prajapati, Abhinesh Kumar; Chaudhari, Parmesh Kumar; Mazumdar, Bidyut; Choudhary, Rumi

    2015-01-01

    The catalytic thermolysis (CT) process is an effective and novel approach to treat rice grain-based biodigester effluent (BDE) of the distillery plant. CT treatment of rice grain-based distillery wastewater was carried out in a 0.5 dm(3) thermolytic batch reactor using different catalysts such as CuO, copper sulphate and ferrous sulphate. With the CuO catalyst, a temperature of 95°C, catalyst loading of 4 g/dm(3) and pH 5 were found to be optimal, obtaining a maximum chemical oxygen demand (COD) and colour removal of 80.4% and 72%, respectively. The initial pH (pHi) was an important parameter to remove COD and colour from BDE. At higher pHi (pH 9.5), less COD and colour reduction were observed. The settling characteristics of CT-treated sludge were also analysed at different temperatures. It was noted that the treated slurry at a temperature of 80°C gave best settling characteristics. Characteristics of residues are also analysed at different pH.

  15. Base-free hydrogen generation from methanol using a bi-catalytic system.

    Science.gov (United States)

    Monney, Angèle; Barsch, Enrico; Sponholz, Peter; Junge, Henrik; Ludwig, Ralf; Beller, Matthias

    2014-01-21

    A bi-catalytic system, in which Ru-MACHO-BH and Ru(H)2(dppe)2 interact in a synergistic manner, was developed for the base-free dehydrogenation of methanol. A total TON > 4200 was obtained with only trace amounts of CO contamination (<8 ppm) in the produced gas.

  16. Cross-catalytic peptide nucleic acid (PNA) replication based on templated ligation

    DEFF Research Database (Denmark)

    Singhal, Abhishek; Nielsen, Peter E

    2014-01-01

    We report the first PNA self-replicating system based on template directed cross-catalytic ligation, a process analogous to biological replication. Using two template PNAs and four pentameric precursor PNAs, all four possible carbodiimide assisted amide ligation products were detected...

  17. Selective catalytic reduction of nitrogen oxides from industrial gases by hydrogen or methane

    International Nuclear Information System (INIS)

    Engelmann Pirez, M.

    2004-12-01

    This work deals with the selective catalytic reduction of nitrogen oxides (NO x ), contained in the effluents of industrial plants, by hydrogen or methane. The aim is to replace ammonia, used as reducing agent, in the conventional process. The use of others reducing agents such as hydrogen or methane is interesting for different reasons: practical, economical and ecological. The catalyst has to convert selectively NO into N 2 , in presence of an excess of oxygen, steam and sulfur dioxide. The developed catalyst is constituted by a support such as perovskites, particularly LaCoO 3 , on which are dispersed noble metals (palladium, platinum). The interaction between the noble metal and the support, generated during the activation of the catalyst, allows to minimize the water and sulfur dioxide inhibitor phenomena on the catalytic performances, particularly in the reduction of NO by hydrogen. (O.M.)

  18. Gaseous Heterogeneous Catalytic Reactions over Mn-Based Oxides for Environmental Applications: A Critical Review.

    Science.gov (United States)

    Xu, Haomiao; Yan, Naiqiang; Qu, Zan; Liu, Wei; Mei, Jian; Huang, Wenjun; Zhao, Songjian

    2017-08-15

    Manganese oxide has been recognized as one of the most promising gaseous heterogeneous catalysts due to its low cost, environmental friendliness, and high catalytic oxidation performance. Mn-based oxides can be classified into four types: (1) single manganese oxide (MnOx), (2) supported manganese oxide (MnOx/support), (3) composite manganese oxides (MnOx-X), and (4) special crystalline manganese oxides (S-MnOx). These Mn-based oxides have been widely used as catalysts for the elimination of gaseous pollutants. This review aims to describe the environmental applications of these manganese oxides and provide perspectives. It gives detailed descriptions of environmental applications of the selective catalytic reduction of NOx with NH 3 , the catalytic combustion of volatile organic compounds, Hg 0 oxidation and adsorption, and soot oxidation, in addition to some other environmental applications. Furthermore, this review mainly focuses on the effects of structure, morphology, and modified elements and on the role of catalyst supports in gaseous heterogeneous catalytic reactions. Finally, future research directions for developing manganese oxide catalysts are proposed.

  19. Exploration of the catalytic use of alkali metal bases

    OpenAIRE

    Bao, Wei

    2017-01-01

    This PhD thesis project was concerned with the use of alkali metal amide Brønsted bases and alkali metal alkoxide Lewis bases in (asymmetric) catalysis. The first chapter deals with formal allylic C(sp3)–H bond activation of aromatic and functionalized alkenes for subsequent C–C and C–H bond formations. The second chapter is focused on C(sp3)–Si bond activation of fluorinated pro-nucleophiles in view of C–C bond formations. In the first chapter, a screening of various metal amides...

  20. Position-based quantum cryptography and catalytic computation

    NARCIS (Netherlands)

    Speelman, F.

    2016-01-01

    In this thesis, we present several results along two different lines of research. The first part concerns the study of position-based quantum cryptography, a topic in quantum cryptography. By combining quantum mechanics with special relativity theory, new cryptographic tasks can be developed that

  1. A new surface catalytic model for silica-based thermal protection material for hypersonic vehicles

    Directory of Open Access Journals (Sweden)

    Li Kai

    2015-10-01

    Full Text Available Silica-based materials are widely employed in the thermal protection system for hypersonic vehicles, and the investigation of their catalytic characteristics is crucially important for accurate aerothermal heating prediction. By analyzing the disadvantages of Norman’s high and low temperature models, this paper combines the two models and proposes an eight-reaction combined surface catalytic model to describe the catalysis between oxygen and silica surface. Given proper evaluation of the parameters according to many references, the recombination coefficient obtained shows good agreement with experimental data. The catalytic mechanisms between oxygen and silica surface are then analyzed. Results show that with the increase of the wall temperature, the dominant reaction contributing to catalytic coefficient varies from Langmuir–Hinshelwood (LH recombination (TW  1350 K. The surface coverage of chemisorption areas varies evidently with the dominant reactions in the high temperature (HT range, while the surface coverage of physisorption areas varies within quite low temperature (LT range (TW < 250 K. Recommended evaluation of partial parameters is also given.

  2. Regulation of catalytic behaviour of hydrolases through interactions with functionalized carbon-based nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Pavlidis, Ioannis V. [University of Ioannina, Laboratory of Biotechnology, Department of Biological Applications and Technologies (Greece); Vorhaben, Torge [Institute of Biochemistry, Greifswald University, Department of Biotechnology and Enzyme Catalysis (Germany); Gournis, Dimitrios [University of Ioannina, Department of Materials Science and Engineering (Greece); Papadopoulos, George K. [Epirus Institute of Technology, Laboratory of Biochemistry and Biophysics, Faculty of Agricultural Technology (Greece); Bornscheuer, Uwe T. [Institute of Biochemistry, Greifswald University, Department of Biotechnology and Enzyme Catalysis (Germany); Stamatis, Haralambos, E-mail: hstamati@cc.uoi.gr [University of Ioannina, Laboratory of Biotechnology, Department of Biological Applications and Technologies (Greece)

    2012-05-15

    The interaction of enzymes with carbon-based nanomaterials (CBNs) is crucial for the function of biomolecules and therefore for the design and development of effective nanobiocatalytic systems. In this study, the effect of functionalized CBNs, such as graphene oxide (GO) and multi-wall carbon nanotubes (CNTs), on the catalytic behaviour of various hydrolases of biotechnological interest was monitored and the interactions between CBNs and proteins were investigated. The enzyme-nanomaterial interactions significantly affect the catalytic behaviour of enzymes, resulting in an increase up to 60 % of the catalytic efficiency of lipases and a decrease up to 30 % of the esterase. Moreover, the use of CNTs and GO derivatives, especially those that are amine-functionalized, led to increased thermal stability of most the hydrolases tested. Fluorescence and circular dichroism studies indicated that the altered catalytic behaviour of enzymes in the presence of CBNs arises from specific enzyme-nanomaterial interactions, which can lead to significant conformational changes. In the case of lipases, the conformational changes led to a more active and rigid structure, while in the case of esterases this led to destabilization and unfolding. Kinetic and spectroscopic studies indicated that the extent of the interactions between CBNs and hydrolases can be mainly controlled by the functionalization of nanomaterials than by their geometry.

  3. Mono-, bi-, and tri-metallic Ni-based catalysts for the catalytic hydrotreatment of pyrolysis liquids

    NARCIS (Netherlands)

    Yin, Wang; Venderbosch, Robbie H.; He, Songbo; Bykova, Maria V.; Khromova, Sofia A.; Yakovlev, Vadim A.; Heeres, Hero J.

    Catalytic hydrotreatment is a promising technology to convert pyrolysis liquids into intermediates with improved properties. Here, we report a catalyst screening study on the catalytic hydrotreatment of pyrolysis liquids using bi- and tri-metallic nickel-based catalysts in a batch autoclave (initial

  4. Pulsed plasma sources for the production of intense ion beams based on catalytic resonance ionization

    International Nuclear Information System (INIS)

    Knyazev, B.A.; Mel'nikov, P.I.; Bluhm, H.

    1994-01-01

    In this paper we describe a technique to produce planar and volumetric ion sources of nearly every element. This technique is based on a generalization of the LIBORS-process (Laser Ionization Based On Resonant Saturation) which because of its similarity to chemical catalytic reactions has been called CATRION (CATalytic Resonance IONization). A vapor containing the desired atomic species is doped with a suitable element processing resonance transitions that can be pumped ro saturation with a laser. By superelastic collisions with the excited atoms and by simulated bremsstrahlung absorption seed electrons are heated. It is the heated electron component which then by collisional processes ionizes the desired atomic species and are multiplied. 41 refs.; 4 figs.; 3 tabs

  5. Direct catalytic transformation of carbohydrates into 5-ethoxymethylfurfural with acid–base bifunctional hybrid nanospheres

    DEFF Research Database (Denmark)

    Li, Hu; Khokarale, Santosh Govind; Kotni, Ramakrishna

    2014-01-01

    A series of acid–base bifunctional hybrid nanospheres prepared from the self-assembly of basic amino acids and phosphotungstic acid (HPA) with different molar ratios were employed as efficient and recyclable catalysts for synthesis of liquid biofuel 5-ethoxymethylfurfural (EMF) from various carbo...... glucopyranoside in good yields could be obtained from glucose in ethanol. Moreover, the nanocatalyst functionalized with acid and basic sites was able to be reused several times with no significant loss in catalytic activity...

  6. Catalytic mechanism of LENR in quasicrystals based on localized anharmonic vibrations and phasons

    OpenAIRE

    Dubinko, Volodymyr; Laptev, Denis; Irwin, Klee

    2016-01-01

    Quasicrystals (QCs) are a novel form of matter, which are neither crystalline nor amorphous. Among many surprising properties of QCs is their high catalytic activity. We propose a mechanism explaining this peculiarity based on unusual dynamics of atoms at special sites in QCs, namely, localized anharmonic vibrations (LAVs) and phasons. In the former case, one deals with a large amplitude (~ fractions of an angstrom) time-periodic oscillations of a small group of atoms around their stable posi...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-07-15

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

  8. Direct catalytic transformation of carbohydrates into 5-ethoxymethylfurfural with acid–base bifunctional hybrid nanospheres

    International Nuclear Information System (INIS)

    Li, Hu; Govind, Khokarale Santosh; Kotni, Ramakrishna; Shunmugavel, Saravanamurugan; Riisager, Anders; Yang, Song

    2014-01-01

    Graphical abstract: Catalytic conversion of carbohydrates into HMF and EMF in ethanol/DMSO with acid–base bifunctional hybrid nanospheres prepared from self-assembly of corresponding basic amino acids and HPA. - Highlights: • Acid–base bifunctional nanospheres were efficient for production of EMF from sugars. • Synthesis of EMF in a high yield of 76.6% was realized from fructose. • Fructose based biopolymers could also be converted into EMF with good yields. • Ethyl glucopyranoside was produced in good yields from glucose in ethanol. - Abstract: A series of acid–base bifunctional hybrid nanospheres prepared from the self-assembly of basic amino acids and phosphotungstic acid (HPA) with different molar ratios were employed as efficient and recyclable catalysts for synthesis of liquid biofuel 5-ethoxymethylfurfural (EMF) from various carbohydrates. A high EMF yield of 76.6%, 58.5%, 42.4%, and 36.5% could be achieved, when fructose, inulin, sorbose, and sucrose were used as starting materials, respectively. Although, the acid–base bifunctional nanocatalysts were inert for synthesis of EMF from glucose based carbohydrates, ethyl glucopyranoside in good yields could be obtained from glucose in ethanol. Moreover, the nanocatalyst functionalized with acid and basic sites was able to be reused several times with no significant loss in catalytic activity

  9. Automated Prediction of Catalytic Mechanism and Rate Law Using Graph-Based Reaction Path Sampling.

    Science.gov (United States)

    Habershon, Scott

    2016-04-12

    In a recent article [ J. Chem. Phys. 2015 , 143 , 094106 ], we introduced a novel graph-based sampling scheme which can be used to generate chemical reaction paths in many-atom systems in an efficient and highly automated manner. The main goal of this work is to demonstrate how this approach, when combined with direct kinetic modeling, can be used to determine the mechanism and phenomenological rate law of a complex catalytic cycle, namely cobalt-catalyzed hydroformylation of ethene. Our graph-based sampling scheme generates 31 unique chemical products and 32 unique chemical reaction pathways; these sampled structures and reaction paths enable automated construction of a kinetic network model of the catalytic system when combined with density functional theory (DFT) calculations of free energies and resultant transition-state theory rate constants. Direct simulations of this kinetic network across a range of initial reactant concentrations enables determination of both the reaction mechanism and the associated rate law in an automated fashion, without the need for either presupposing a mechanism or making steady-state approximations in kinetic analysis. Most importantly, we find that the reaction mechanism which emerges from these simulations is exactly that originally proposed by Heck and Breslow; furthermore, the simulated rate law is also consistent with previous experimental and computational studies, exhibiting a complex dependence on carbon monoxide pressure. While the inherent errors of using DFT simulations to model chemical reactivity limit the quantitative accuracy of our calculated rates, this work confirms that our automated simulation strategy enables direct analysis of catalytic mechanisms from first principles.

  10. New URJC-1 Material with Remarkable Stability and Acid-Base Catalytic Properties

    Directory of Open Access Journals (Sweden)

    Pedro Leo

    2016-02-01

    Full Text Available Emerging new metal-organic structures with tunable physicochemical properties is an exciting research field for diverse applications. In this work, a novel metal-organic framework Cu(HIT(DMF0.5, named URJC-1, with a three-dimensional non-interpenetrated utp topological network, has been synthesized. This material exhibits a microporous structure with unsaturated copper centers and imidazole–tetrazole linkages that provide accessible Lewis acid/base sites. These features make URJC-1 an exceptional candidate for catalytic application in acid and base reactions of interest in fine chemistry. The URJC-1 material also displays a noteworthy thermal and chemical stability in different organic solvents of different polarity and boiling water. Its catalytic activity was evaluated in acid-catalyzed Friedel–Crafts acylation of anisole with acetyl chloride and base-catalyzed Knoevenagel condensation of benzaldehyde with malononitrile. In both cases, URJC-1 material showed very good performance, better than other metal organic frameworks and conventional catalysts. In addition, a remarkable structural stability was proven after several consecutive reaction cycles.

  11. Catalytic processes towards the production of biofuels in a palm oil and oil palm biomass-based biorefinery.

    Science.gov (United States)

    Chew, Thiam Leng; Bhatia, Subhash

    2008-11-01

    In Malaysia, there has been interest in the utilization of palm oil and oil palm biomass for the production of environmental friendly biofuels. A biorefinery based on palm oil and oil palm biomass for the production of biofuels has been proposed. The catalytic technology plays major role in the different processing stages in a biorefinery for the production of liquid as well as gaseous biofuels. There are number of challenges to find suitable catalytic technology to be used in a typical biorefinery. These challenges include (1) economic barriers, (2) catalysts that facilitate highly selective conversion of substrate to desired products and (3) the issues related to design, operation and control of catalytic reactor. Therefore, the catalytic technology is one of the critical factors that control the successful operation of biorefinery. There are number of catalytic processes in a biorefinery which convert the renewable feedstocks into the desired biofuels. These include biodiesel production from palm oil, catalytic cracking of palm oil for the production of biofuels, the production of hydrogen as well as syngas from biomass gasification, Fischer-Tropsch synthesis (FTS) for the conversion of syngas into liquid fuels and upgrading of liquid/gas fuels obtained from liquefaction/pyrolysis of biomass. The selection of catalysts for these processes is essential in determining the product distribution (olefins, paraffins and oxygenated products). The integration of catalytic technology with compatible separation processes is a key challenge for biorefinery operation from the economic point of view. This paper focuses on different types of catalysts and their role in the catalytic processes for the production of biofuels in a typical palm oil and oil palm biomass-based biorefinery.

  12. Polyelectrolyte Brush-Grafted Polydopamine-Based Catalysts with Enhanced Catalytic Activity and Stability.

    Science.gov (United States)

    Kaang, Byung Kwon; Han, Nara; Lee, Ha-Jin; Choi, Won San

    2018-01-10

    Three types of surface treatments, namely, polyethyleneimine (PEI) coating, short PEI (S-PEI) grafting, and long PEI (L-PEI) grafting, were performed on polydopamine (Pdop)-based catalysts to enhance their catalytic activity and stability. Brush-grafted catalysts were prepared by the stepwise synthesis of Au and short (or long) PEI brushes on Pdop particles (PdopP/Au/S- or L-PEI grafting). PEI-coated Pdop-based catalysts (PdopP/Au/PEI coating) were also prepared as non-brush-grafted catalysts. Among the surface-treated PdopP/Au catalysts, the brush-grafted catalysts (S-PEI and L-PEI grafting) exhibited excellent and stable catalytic performance because the brush grafting enabled the protection of the catalysts against harsh conditions, effective transfer of reactants to the catalysts, and confinement of reactants around the catalysts. The brush-grafted catalysts could also more effectively decompose larger dyes than the non-brush-grafted catalysts. The process-to-effectiveness of PEI coating is the best because the release of Pdop from PdopP/Au was moderately inhibited by the presence of only one layer of PEI coating on the PdopP/Au. Thus, this approach could be an alternative method to enhance the stability of PdopP/Au catalysts.

  13. Ruthenium(II) hydrazone Schiff base complexes: Synthesis, spectral study and catalytic applications

    Science.gov (United States)

    Manikandan, R.; Viswanathamurthi, P.; Muthukumar, M.

    2011-12-01

    Ruthenium(II) hydrazone Schiff base complexes of the type [RuCl(CO)(B)(L)] (were B = PPh 3, AsPh 3 or Py; L = hydrazone Schiff base ligands) were synthesized from the reactions of hydrazone Schiff base ligand (obtained from isonicotinoylhydrazide and different hydroxy aldehydes) with [RuHCl(CO)(EPh 3) 2(B)] (where E = P or As; B = PPh 3, AsPh 3 or Py) in 1:1 molar ratio. All the new complexes have been characterized by analytical and spectral (FT-IR, electronic, 1H, 13C and 31P NMR) data. They have been tentatively assigned an octahedral structure. The synthesized complexes have exhibited catalytic activity for oxidation of benzyl alcohol to benzaldehyde and cyclohexanol to cyclohexanone in the presence of N-methyl morpholine N-oxide (NMO) as co-oxidant. They were also found to catalyze the transfer hydrogenation of aliphatic and aromatic ketones to alcohols in KOH/Isopropanol.

  14. Catalytic Graphitization of Coal-Based Carbon Materials with Light Rare Earth Elements.

    Science.gov (United States)

    Wang, Rongyan; Lu, Guimin; Qiao, Wenming; Yu, Jianguo

    2016-08-30

    The catalytic graphitization mechanism of coal-based carbon materials with light rare earth elements was investigated using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, selected-area electron diffraction, and high-resolution transmission electron microscopy. The interface between light rare earth elements and carbon materials was carefully observed, and two routes of rare earth elements catalyzing the carbon materials were found: dissolution-precipitation and carbide formation-decomposition. These two simultaneous processes certainly accelerate the catalytic graphitization of carbon materials, and light rare earth elements exert significant influence on the microstructure and thermal conductivity of graphite. Moreover, by virtue of praseodymium (Pr), it was found that a highly crystallographic orientation of graphite was induced and formed, which was reasonably attributed to the similar arrangements of the planes perpendicular to (001) in both graphite and Pr crystals. The interface between Pr and carbon was found to be an important factor for the orientation of graphite structure.

  15. Kinetic spectrophotometric determination of iron based on catalytic oxidation of p-acetylarsenazo

    Directory of Open Access Journals (Sweden)

    Qing-Zhou Zhai

    2009-12-01

    Full Text Available A novel catalytic kinetic spectrophotometric method for the determination of iron is developed based on the catalytic effect of Fe(III on the oxidation reaction of p-acetylarsenazo(ASApA by potassium periodate. Maximum absorbance of the Fe(III−ASApA−KIO4 system in 8.0 × 10-3 M sulfuric acid occurs at the wavelength of 540 nm. The change in absorbance (ΔA is linearly related with the concentration of iron(III in the range of 0.10−4.0 ng/mL and fitted the equation: ΔA = 4.91 × 10-2 C (C: ng/mL + 0.017, with a regression coefficient of 0.9966 at the wavelength. The detection limit of the method is 0.031 ng/mL. The relative standard deviation of the method was from 1.34% to 1.78% for 11 replicate determinations. The standard addition recovery of the method ranged from 95.71% to 103.3%. The method was used to determine iron in the black gingili paste, oat slice, sleeve-fish silk food samples. The determined results were in agreement with those by atomic absorption spectrometry.

  16. High performance catalytic distillation using CNTs-based holistic catalyst for production of high quality biodiesel

    Science.gov (United States)

    Zhang, Dongdong; Wei, Dali; Li, Qi; Ge, Xin; Guo, Xuefeng; Xie, Zaiku; Ding, Weiping

    2014-02-01

    For production of biodiesel from bio oils by heterogeneous catalysis, high performance catalysts of transesterification and the further utilization of glycerol have been the two points of research. The process seemed easy, however, has never been well established. Here we report a novel design of catalytic distillation using hierachically integrated CNTs-based holistic catalyst to figure out the two points in one process, which shows high performance both for the conversion of bio oils to biodiesel and, unexpectedly, for the conversion of glycerol to more valuable chemicals at the same time. The method, with integration of nano, meso to macro reactor, has overwhelming advantages over common technologies using liquid acids or bases to catalyze the reactions, which suffer from the high cost of separation and unsolved utilization of glycerol.

  17. Imidazolium- and Triazine-Based Porous Organic Polymers for Heterogeneous Catalytic Conversion of CO2 into Cyclic Carbonates.

    Science.gov (United States)

    Zhong, Hong; Su, Yanqing; Chen, Xingwei; Li, Xiaoju; Wang, Ruihu

    2017-12-22

    CO 2 adsorption and concomitant catalytic conversion into useful chemicals are promising approaches to alleviate the energy crisis and effects of global warming. This is highly desirable for developing new types of heterogeneous catalytic materials containing CO 2 -philic groups and catalytic active sites for CO 2 chemical transformation. Here, we present an imidazolium- and triazine-based porous organic polymer with counter chloride anion (IT-POP-1). The porosity and CO 2 affinity of IT-POP-1 may be modulated at the molecular level through a facile anion-exchange strategy. Compared with the post-modified polymers with iodide and hexafluorophosphate anions, IT-POP-1 possesses the highest surface area and the best CO 2 uptake capacity with excellent adsorption selectivity over N 2 . The roles of the task-specific components such as triazine, imidazolium, hydroxyl, and counter anions in CO 2 absorption and catalytic performance were illustrated. IT-POP-1 exhibits the highest catalytic activity and excellent recyclability in solvent- and additive-free cycloaddition reaction of CO 2 with epoxides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Simultaneous Elimination of Soot and NOX through Silver-Barium Based Catalytic Materials

    Directory of Open Access Journals (Sweden)

    Ganesh Chandra Dhal

    2017-04-01

    Full Text Available In this research paper, the nanometric size effect, the effects of the intrinsic factors including structure, and the redox properties of three systems of nanometric of silver-based catalysts were summarized. In this work, these catalysts were investigated for the simultaneous removal of particulate matter (diesel soot, and NOX was compared with that of a model of Pt-Ba/Al2O3 catalyst. The Silver-Barium based catalytic materials of Ag (5 wt%-Ba(10 wt%/MO (MO=Al2O3, CeO2, ZrO2, and Ag (5 wt%-Sr (10 wt%/CeO2 catalysts have been prepared by wetness impregnation method and characterized by BET, XRD, HRTEM, XPS and TPR (temperature-programmed reduction experiments. The behavior of the catalyst in the soot combustion (under tight conditions and NOX elimination has been separately analyzed by means of temperature programmed oxidation and isothermal concentration step change experiments, respectively. The results showed that all the catalysts were active in soot combustion with an indicative decrease of oxidation onset temperature compared to uncatalyzed soot oxidation. The removal of NOX in the presence and in the absence of soot was investigated under cycling conditions, i.e. alternating lean-rich phases according to the LNT approach. It has been found that the Ag-based samples were able to simultaneously remove soot and NOX. In particular, studying the behavior of the prepared catalysts, the Ba-containing systems exhibited higher NOX storage capacity than Sr-catalyst; also, the nitrogen selectivity increased even if resulted lower than the traditional LNT Pt-based catalyst. An adverse effect of soot on the NOX storage activity has been also observed. Copyright © 2017 BCREC GROUP. All rights reserved Received: 18th August 2016; Revised: 19th October 2016; Accepted: 19th October 2016 How to Cite: Dhal, G.C., Dey, S., Prasad, R., Mohan, D. (2017. Simultaneous Elimination of Soot and NOX through Silver-Barium Based Catalytic Materials. Bulletin of

  19. Industrial wastewater advanced treatment via catalytic ozonation with an Fe-based catalyst.

    Science.gov (United States)

    Li, Xufang; Chen, Weiyu; Ma, Luming; Wang, Hongwu; Fan, Jinhong

    2018-03-01

    An Fe-based catalyst was used as a heterogeneous catalyst for the ozonation of industrial wastewater, and key operational parameters (pH and catalyst dosage) were studied. The results indicated that the Fe-based catalyst significantly improved the mineralization of organic pollutants in wastewater. TOC (total organic carbon) removal was high, at 78.7%, with a catalyst concentration of 200 g/L, but only 31.6% with ozonation alone. The Fe-based catalyst significantly promoted ozone decomposition by 70% in aqueous solution. Hydroxyl radicals (·OH) were confirmed to be existed directly via EPR (electron paramagnetic resonance) experiments, and ·OH were verified to account for about 34.4% of TOC removal with NaHCO 3 as a radical scavenger. Through characterization by SEM-EDS (field emission scanning electron microscope with energy-dispersive spectrometer), XRD (X-ray powder diffraction) and XPS (X-ray photoelectron spectroscopy), it was deduced that FeOOH on the surface of the catalyst was the dominant contributor to the catalytic efficiency. The catalyst was certified as having good stability and excellent reusability based on 50 successive operations and could be used as a filler simultaneously. Thereby, it is a promising catalyst for practical industrial wastewater advanced treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Structure and acidity of individual Fluid Catalytic Cracking catalyst particles studied by synchrotron-based infrared micro-spectroscopy

    NARCIS (Netherlands)

    Buurmans, I.L.C.|info:eu-repo/dai/nl/31406592X; Soulimani, F.|info:eu-repo/dai/nl/313889449; Ruiz Martinez, J.|info:eu-repo/dai/nl/341386405; van der Bij, H.E.|info:eu-repo/dai/nl/328201294; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2013-01-01

    A synchrotron-based infrared micro-spectroscopy study has been conducted to investigate the structure as well as the Brønsted and Lewis acidity of Fluid Catalytic Cracking (FCC) catalyst particles at the individual particle level. Both fresh and laboratory-deactivated catalyst particles have been

  1. Conjugate-base-stabilized Brønsted acids: catalytic enantioselective Pictet-Spengler reactions with unmodified tryptamine.

    Science.gov (United States)

    Mittal, Nisha; Sun, Diana X; Seidel, Daniel

    2014-02-07

    A conjugate-base-stabilized Brønsted acid facilitates catalytic enantioselective Pictet-Spengler reactions with unmodified tryptamine. The chiral carboxylic acid catalyst is readily assembled in just two steps and enables the formation of β-carbolines with up to 92% ee. Achiral acid additives or in situ Boc-protection facilitate catalyst turnover.

  2. Synthesis, characterization, electrical and catalytic studies of some coordination compounds derived from unsymmetrical Schiff base ligand

    Directory of Open Access Journals (Sweden)

    G. B. Pethe

    2015-10-01

    Full Text Available New unsymmetrical tetradentate Schiff base ligand derived from 5-chloro-2-hydroxyacetophenone, 2-hydroxy-5-methyl-3-nitro acetophenone and carbohydrazide and its complexes with VO(IV, Cr(III, Mn(III, Fe(III, MoO2(VI, WO2(VI, Zr(IV and UO2(VI have been prepared. They were characterized by elemental analysis, IR and electronic spectra, magnetic susceptibility measurements and thermal analyses. The Schiff base ligand has also been characterised by 1H-NMR spectroscopy. The thermal behaviour of metal complexes shows that the hydrated complexes lose water molecules of hydration in the first and then is immediately followed by decomposition of ligand molecule in the subsequent steps. The IR spectra suggest that ligand acts as dibasic tetradentate nature and coordination takes place through azomethine nitrogen and phenolate oxygen. The crystalline nature of the VO(IV complex was conformed through the powder XRD analysis. The catalytic activity of the VO(IV and Mn(III complexes have been tested in the epoxidation reaction of styrene and conversion of styrene were 11.14-24.35% and 9.64-23.42%, respectively. The solid state electrical conductivity of ligand and its complexes were measured, which could obeyed the relation s = s0 exp (Ea/KT over the temperature range 313-413 K. DOI: http://dx.doi.org/10.4314/bcse.v29i3.6

  3. Catalytic Transfer Hydrogenation of Biomass-Derived Carbonyls over Hafnium-Based Metal-Organic Frameworks.

    Science.gov (United States)

    Rojas-Buzo, Sergio; García-García, Pilar; Corma, Avelino

    2018-01-23

    A series of highly crystalline, porous, hafnium-based metal-organic frameworks (Hf-MOFs) have been shown to catalyze the transfer hydrogenation reaction of levulinic ester to produce γ-valerolactone by using isopropanol as a hydrogen donor. The results are compared with their zirconium-based counterparts. The role of the metal center in Hf-MOFs has been identified and reaction parameters optimized. NMR studies using isotopically labeled isopropanol provide evidence that the transfer hydrogenation occurs through a direct intermolecular hydrogen transfer route. The catalyst, Hf-MOF-808, can be recycled several times with only a minor decrease in catalytic activity. The generality of the procedure has been demonstrated by accomplishing the transformation with aldehydes, ketones, and α,β-unsaturated carbonyl compounds. The combination of Hf-MOF-808 with the Brønsted-acidic Al-Beta zeolite gives the four-step one-pot transformation of furfural to γ-valerolactone in good yield of 75 %. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts.

    Science.gov (United States)

    Murahashi, Shun-Ichi

    2011-01-01

    This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. (Communicated by Ryoji Noyori, M.J.A.).

  5. Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts

    Science.gov (United States)

    MURAHASHI, Shun-Ichi

    2011-01-01

    This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. PMID:21558760

  6. Catalytic Conversion of Carbohydrates to Levulinate Ester over Heteropolyanion-Based Ionic Liquids.

    Science.gov (United States)

    Song, Changhua; Liu, Sijie; Peng, Xinwen; Long, Jinxing; Lou, Wenyong; Li, Xuehui

    2016-12-08

    An efficient one-pot approach for the production of levulinate ester from renewable carbohydrates is demonstrated over heteropolyanion-based ionic liquid (IL-POM) catalysts with alcohols as the promoters and solvents. The relationships between the structure, acidic strength, and solubility of the IL-POM in methanol and the catalytic performance were studied intensively. A cellulose conversion of 100 % could be achieved with a 71.4 % yield of methyl levulinate over the catalyst [PyPS] 3 PW 12 O 40 [PyPS=1-(3-sulfopropyl)pyridinium] at 150 °C for 5 h. This high efficiency is ascribed to the reasonably high activity of the ionic liquid (IL) catalyst and reaction coupling with rapid in situ esterification of the generated levulinic acid with the alcohol promoter, which allows the insolubility of cellulose encountered in biomass conversion to be overcome. Furthermore, the present process exhibits high feedstock adaptability for typical carbohydrates and handy catalyst recovery by a simple self-separation procedure through temperature control. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Bifunctional Porphyrin-Based Nano-Metal-Organic Frameworks: Catalytic and Chemosensing Studies.

    Science.gov (United States)

    Pereira, Carla F; Figueira, Flávio; Mendes, Ricardo F; Rocha, João; Hupp, Joseph T; Farha, Omar K; Simões, Mário M Q; Tomé, João P C; Paz, Filipe A Almeida

    2018-03-13

    The use of 5,10,15,20-tetrakis( p-phenylphosphonic acid)porphyrin (H 10 TPPA) as a linker in the preparation of porphyrin-based metal-organic frameworks (Por-MOFs) through coordination to lanthanides cations is reported. The resulting unprecedented materials, formulated as [M(H 9 TPPA)(H 2 O) x ]Cl 2 · yH 2 O [ x + y = 7; M 3+ = La 3+ (1), Yb 3+ (2), and Y 3+ (3)], prepared using hydrothermal synthesis, were extensively characterized in the solid-state, for both their structure and thermal robustness, using a myriad of solid-state advanced techniques. Materials were evaluated as heterogeneous catalysts in the oxidation of thioanisole by H 2 O 2 and as chemosensors for detection of nitroaromatic compounds (NACs). Nano-Por-MOFs 1-3 proved to be effective as heterogeneous catalysts in the sulfoxidation of thioanisole, with Por-MOF 1 exhibiting the best catalytic performance with a conversion of thioanisole of 89% in the first cycle and with a high selectivity for the sulfoxide derivative (90%). The catalyst maintained its activity roughly constant in three consecutive runs. Por-MOFs 1-3 can be employed as chemosensors because of a measured fluorescence quenching up to 70% for nitrobenzene, 1,4-dinitrobenzene, 4-nitrophenol, and phenol, with 2,4,6-trinitrophenol exhibiting a peculiar fluorescence profile.

  8. Switch in Site of Inhibition: A Strategy for Structure-Based Discovery of Human Topoisomerase IIα Catalytic Inhibitors.

    Science.gov (United States)

    Baviskar, Ashish T; Amrutkar, Suyog M; Trivedi, Neha; Chaudhary, Vikas; Nayak, Anmada; Guchhait, Sankar K; Banerjee, Uttam C; Bharatam, Prasad V; Kundu, Chanakya N

    2015-04-09

    A study of structure-based modulation of known ligands of hTopoIIα, an important enzyme involved in DNA processes, coupled with synthesis and in vitro assays led to the establishment of a strategy of rational switch in mode of inhibition of the enzyme's catalytic cycle. 6-Arylated derivatives of known imidazopyridine ligands were found to be selective inhibitors of hTopoIIα, while not showing TopoI inhibition and DNA binding. Interestingly, while the parent imidazopyridines acted as ATP-competitive inhibitors, arylated derivatives inhibited DNA cleavage similar to merbarone, indicating a switch in mode of inhibition from ATP-hydrolysis to the DNA-cleavage stage of catalytic cycle of the enzyme. The 6-aryl-imidazopyridines were relatively more cytotoxic than etoposide in cancer cells and less toxic to normal cells. Such unprecedented strategy will encourage research on "choice-based change" in target-specific mode of action for rapid drug discovery.

  9. Catalytic Performance for Hydrocarbon Production from Syngas on the Promoted Co-Based Hybrid Catalysts; Influence of Pt Contents

    Directory of Open Access Journals (Sweden)

    Suk-Hwan Kang

    2017-10-01

    How to Cite: Kang, S.H., Ryu, J.H., Kim, J.H., Kim, H.S., Yang, H.C., Chung, D.Y. (2017. Catalytic Performance for Hydrocarbon Production from Syngas on the Promoted Co-Based Hybrid Catalysts; Influence of Pt Contents. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (3: 452-459 (doi:10.9767/bcrec.12.3.592.452-459

  10. Homochiral nickel coordination polymers based on salen(Ni) metalloligands: synthesis, structure, and catalytic alkene epoxidation.

    Science.gov (United States)

    Huang, Yuanbiao; Liu, Tianfu; Lin, Jingxiang; Lü, Jian; Lin, Zujin; Cao, Rong

    2011-03-21

    One-dimensional (1D) homochiral nickel coordination polymers [Ni(3)(bpdc)(RR-L)(2)·(DMF)](n) (2R, RR-L = (R,R)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene), bpdc = 4,4'-biphenyldicarboxylic acid) and [Ni(3)(bpdc)(SS-L)(2)·(DMF)](n) (2S, SS-L = (S,S)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene) based on enantiopure pyridyl-functionalized salen(Ni) metalloligand units NiL ((1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene))Ni(II)) have been synthesized and characterized by microanalysis, IR spectroscopy, solid-state UV-vis spectroscopy, thermogravimetric analysis (TGA), circular dichroism (CD) spectroscopy, cyclic voltammetric measurement, and powder and single crystal X-ray diffraction. Each NiL as unbridging pendant metalloligand uses one terminal pyridyl group to coordinate achiral unit (nickel and bpdc(2-)) building a helical chain, while the other pyridyl group remains uncoordinated. Both 2R and 2S contain left- and right-handed helical chains made of the achiral building blocks, while the NiL as remote external chiral source is perpendicular to the backbone of the helices. The nickel coordination polymers 2R and 2S containing unsaturated active nickel center in metalloligand NiL can be used as self-supported heterogeneous catalysts. They show catalytic activity comparable with their homogeneous counterpart in alkene epoxidation and exhibit great potential as recyclable catalysts.

  11. Principles of water oxidation and O2-based hydrocarbon transformation by multinuclear catalytic sites

    Energy Technology Data Exchange (ETDEWEB)

    Musaev, Djamaladdin G [Chemistry, Emory University; Hill, Craig L [Chemistry, Emory University; Morokuma, Keiji [Chemistry, Emory University

    2014-10-28

    Abstract The central thrust of this integrated experimental and computational research program was to obtain an atomistic-level understanding of the structural and dynamic factors underlying the design of catalysts for water oxidation and selective reductant-free O2-based transformations. The focus was on oxidatively robust polyoxometalate (POM) complexes in which a catalytic active site interacts with proximal metal centers in a synergistic manner. Thirty five publications in high-impact journals arose from this grant. I. Developing an oxidatively and hydrolytically stable and fast water oxidation catalyst (WOC), a central need in the production of green fuels using water as a reductant, has proven particularly challenging. During this grant period we have designed and investigated several carbon-free, molecular (homogenous), oxidatively and hydrolytically stable WOCs, including the Rb8K2[{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2]·25H2O (1) and [Co4(H2O)2(α-PW9O34)2]10- (2). Although complex 1 is fast, oxidatively and hydrolytically stable WOC, Ru is neither abundant nor inexpensive. Therefore, development of a stable and fast carbon-free homogenous WOC, based on earth-abundant elements became our highest priority. In 2010, we reported the first such catalyst, complex 2. This complex is substantially faster than 1 and stable under homogeneous conditions. Recently, we have extended our efforts and reported a V2-analog of the complex 2, i.e. [Co4(H2O)2(α-VW9O34)2]10- (3), which shows an even greater stability and reactivity. We succeeded in: (a) immobilizing catalysts 1 and 2 on the surface of various electrodes, and (b) elucidating the mechanism of O2 formation and release from complex 1, as well as the Mn4O4L6 “cubane” cluster. We have shown that the direct O-O bond formation is the most likely pathway for O2 formation during water oxidation catalyzed by 1. II. Oxo transfer catalysts that contain two proximal and synergistically interacting redox active metal

  12. Nature inspired catalytic systems using sulfonamido-phosphorus based complexes: Increasing complexity in transition metal catalysis

    NARCIS (Netherlands)

    Terrade, F.G.

    2014-01-01

    Most industrial transformations include at least one catalytic step, as catalysis allows the reduction of waste and reduces the energy consumption. Driven by economic and environmental concerns, chemists are making constant efforts to develop ever-more efficient catalysts. Enzymes, catalysts found

  13. Catalytic Pyrolysis of Wild Reed over a Zeolite-Based Waste Catalyst

    Directory of Open Access Journals (Sweden)

    Myung Lang Yoo

    2016-03-01

    Full Text Available Fast catalytic pyrolysis of wild reed was carried out at 500 °C. Waste fluidized catalytic cracking (FCC catalyst disposed from a petroleum refinery process was activated through acetone-washing and calcination and used as catalyst for pyrolysis. In order to evaluate the catalytic activity of waste FCC catalyst, commercial HY zeolite catalyst with a SiO2/Al2O3 ratio of 5.1 was also used. The bio-oil produced from pyrolysis was analyzed using gas chromatography/mass spectrometry (GC/MS. When the biomass-to-catalyst ratio was 1:1, the production of phenolics and aromatics was promoted considerably by catalysis, whereas the content of oxygenates was affected little. Significant conversion of oxygenates to furans and aromatics was observed when the biomass-to-catalyst ratio of 1:10 was used. Activated waste FCC catalyst showed comparable catalytic activity for biomass pyrolysis to HY in terms of the promotion of valuable chemicals, such as furans, phenolics and aromatics. The results of this study imply that waste FCC catalyst can be an important economical resource for producing high-value-added chemicals from biomass.

  14. Catalytic promiscuity of a proline-based tautomerase : Aldolase activities and enzyme redesign

    NARCIS (Netherlands)

    Rahimi, Mehran

    2016-01-01

    Numerous enzymes have been found to catalyze additional and completely different types of reactions relative to the natural activity they evolved for. This interesting phenomenon, called catalytic promiscuity, has proven to be a fruitful guide for the development of novel biocatalysts for organic

  15. Catalytic enantioselective syn hydration of enones in water using a DNA-based catalyst

    NARCIS (Netherlands)

    Boersma, Arnold J.; Coquière, David; Geerdink, Danny; Rosati, Fiora; Roelfes, Gerard; Feringa, Bernard

    2010-01-01

    The enantioselective addition of water to olefins in an aqueous environment is a common transformation in biological systems, but was beyond the ability of synthetic chemists. Here, we present the first examples of a non-enzymatic catalytic enantioselective hydration of enones, for which we used a

  16. Thermo-Catalytic Methane Decomposition for Hydrogen Production: Effect of Palladium Promoter on Ni-based Catalysts

    Directory of Open Access Journals (Sweden)

    Irene Lock Sow Mei

    2016-08-01

    Full Text Available Hydrogen production from the direct thermo-catalytic decomposition of methane is a promising alternative for clean fuel production. However, thermal decomposition of methane can hardly be of any practical and empirical interest in the industry unless highly efficient and effective catalysts, in terms of both catalytic activity and operational lifetime have been developed. In this study, the effect of palladium (Pd as a promoter onto Ni supported on alumina catalyst has been investigated by using co-precipitation technique. The introduction of Pd promotes better catalytic activity, operational lifetime and thermal stability of the catalyst. As expected, highest methane conversion was achieved at reaction temperature of 800 °C while the bimetallic catalyst (1 wt.% Ni -1wt.% Pd/Al2O3 gave the highest methane conversion of 70% over 15 min of time-on-stream (TOS. Interestingly, the introduction of Pd as promoter onto Ni-based catalyst also has a positive effect on the operational lifetime and thermal stability of the catalyst as the methane conversion has improved significantly over 240 min of TOS. Copyright © 2016 BCREC GROUP. All rights reserved Received: 21st January 2016; Revised: 6th February 2016; Accepted: 6th March 2016 How to Cite: Mei, I.L.S., Lock, S.S.M., Vo, D.V.N., Abdullah, B. (2016. Thermo-Catalytic Methane Decomposition for Hydrogen Production: Effect of Palladium Promoter on Ni-based Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2: 191-199 (doi:10.9767/bcrec.11.2.550.191-199 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.2.550.191-199

  17. Production of phenolic-rich bio-oil from catalytic fast pyrolysis of biomass using magnetic solid base catalyst

    International Nuclear Information System (INIS)

    Zhang, Zhi-bo; Lu, Qiang; Ye, Xiao-ning; Li, Wen-tao; Hu, Bin; Dong, Chang-qing

    2015-01-01

    Highlights: • Phenolic-rich bio-oil was selectively produced from catalytic fast pyrolysis of biomass using magnetic solid base catalyst. • The actual yield of twelve major phenolic compounds reached 43.9 mg/g. • The peak area% of all phenolics reached 68.5% at the catalyst-to-biomass ratio of 7. • The potassium phosphate/ferroferric oxide catalyst possessed promising recycling properties. - Abstract: A magnetic solid base catalyst (potassium phosphate/ferroferric oxide) was prepared and used for catalytic fast pyrolysis of poplar wood to selectively produce phenolic-rich bio-oil. Pyrolysis–gas chromatography/mass spectrometry experiments were conducted to investigate the effects of pyrolysis temperature and catalyst-to-biomass ratio on the product distribution. The actual yields of important pyrolytic products were quantitatively determined by the external standard method. Moreover, recycling experiments were performed to determine the re-utilization abilities of the catalyst. The results showed that the catalyst exhibited promising activity to selectively produce phenolic-rich bio-oil, due to its capability of promoting the decomposition of lignin to generate phenolic compounds and meanwhile inhibiting the devolatilization of holocellulose. The maximal phenolic yield was obtained at the pyrolysis temperature of 400 °C and catalyst-to-biomass ratio of 2. The concentration of the phenolic compounds increased monotonically along with the increasing of the catalyst-to-biomass ratio, with the peak area% value increasing from 28.1% in the non-catalytic process to as high as 68.5% at the catalyst-to-biomass ratio of 7. The maximal total actual yield of twelve quantified major phenolic compounds was 43.9 mg/g, compared with the value of 29.0 mg/g in the non-catalytic process. In addition, the catalyst could be easily recovered and possessed promising recycling properties.

  18. Sulfur and Water Resistance of Mn-Based Catalysts for Low-Temperature Selective Catalytic Reduction of NOx: A Review

    Directory of Open Access Journals (Sweden)

    Chen Gao

    2018-01-01

    Full Text Available Selective catalytic reduction (SCR with NH3 is the most efficient and economic flue gas denitrification technology developed to date. Due to its high low-temperature catalytic activity, Mn-based catalysts present a great prospect for application in SCR de-NOx at low temperatures. However, overcoming the poor resistance of Mn-based catalysts to H2O and SO2 poison is still a challenge. This paper reviews the recent progress on the H2O and SO2 resistance of Mn-based catalysts for the low-temperature SCR of NOx. Firstly, the poison mechanisms of H2O and SO2 are introduced in detail, respectively. Secondly, Mn-based catalysts are divided into three categories—single MnOx catalysts, Mn-based multi-metal oxide catalysts, and Mn-based supported catalysts—to review the research progress of Mn-based catalysts for H2O and SO2 resistance. Thirdly, several strategies to reduce the poisonous effects of H2O and SO2, such as metal modification, proper support, the combination of metal modification and support, the rational design of structure and morphology, are summarized. Finally, perspectives and future directions of Mn-based catalysts for the low-temperature SCR of NOx are proposed.

  19. Support effects on adsorption and catalytic activation of O2 in single atom iron catalysts with graphene-based substrates.

    Science.gov (United States)

    Gao, Zheng-Yang; Yang, Wei-Jie; Ding, Xun-Lei; Lv, Gang; Yan, Wei-Ping

    2018-03-07

    The adsorption and catalytic activation of O 2 on single atom iron catalysts with graphene-based substrates were investigated systematically by density functional theory calculation. It is found that the support effects of graphene-based substrates have a significant influence on the stability of the single atom catalysts, the adsorption configuration, the electron transfer mechanism, the adsorption energy and the energy barrier. The differences in the stable adsorption configuration of O 2 on single atom iron catalysts with different graphene-based substrates can be well understood by the symmetrical matching principle based on frontier molecular orbital analysis. There are two different mechanisms of electron transfer, in which the Fe atom acts as the electron donor in single vacancy graphene-based substrates while the Fe atom mainly acts as the bridge for electron transfer in double vacancy graphene-based substrates. The Fermi softness and work function are good descriptors of the adsorption energy and they can well reveal the relationship between electronic structure and adsorption energy. This single atom iron catalyst with single vacancy graphene modified by three nitrogen atoms is a promising non-noble metal single atom catalyst in the adsorption and catalytic oxidation of O 2 . Furthermore, the findings can lay the foundation for the further study of graphene-based support effects and provide a guideline for the development and design of new non-noble-metal single atom catalysts.

  20. Biodiesel from waste cooking oil via base-catalytic and supercritical methanol transesterification

    International Nuclear Information System (INIS)

    Demirbas, Ayhan

    2009-01-01

    In this study, waste cooking oil has subjected to transesterification reaction by potassium hydroxide (KOH) catalytic and supercritical methanol methods obtaining for biodiesel. In catalyzed methods, the presence of water has negative effects on the yields of methyl esters. In the catalytic transesterification free fatty acids and water always produce negative effects since the presence of free fatty acids and water causes soap formation, consumes catalyst, and reduces catalyst effectiveness. Free fatty acids in the waste cooking oil are transesterified simultaneously in supercritical methanol method. Since waste cooking oil contains water and free fatty acids, supercritical transesterification offers great advantage to eliminate the pre-treatment and operating costs. The effects of methanol/waste cooking oils ratio, potassium hydroxide concentration and temperature on the biodiesel conversion were investigated

  1. Low Temperature Steam Methane Reforming Over Ni Based Catalytic Membrane Prepared by Electroless Palladium Plating.

    Science.gov (United States)

    Lee, Sang Moon; Hong, Sung Chang; Kim, Sung Su

    2018-09-01

    A Pd/Ni-YSZ porous membrane with different palladium loadings and hydrazine as a reducing reagent was prepared by electroless plating and evaluated for the steam methane reforming activity. The steam-reforming activity of a Ni-YSZ porous membrane was greatly increased by the deposition of 4 g/L palladium in the low-temperature range (600 °C). With an increasing amount of reducing reagent, the Pd clusters were well dispersed on the Ni-YSZ surface and were uniform in size (∼500 nm). The Pd/Ni-YSZ catalytic porous membrane prepared by 1 of Pd/hydrazine ratio possessed an abundant amount of metallic Pd. The optimal palladium loadings and Pd/hydrazine ratio increased the catalytic activity in both the steam-reforming reaction and the Pd dispersion.

  2. Synthesis, spectral, characterization, catalytic and biological studies of new RuII N2O Schiff base complexes

    International Nuclear Information System (INIS)

    Balasubramanian, K.P.; Manivannan, S.; Chinnusamy, V.

    2008-01-01

    Complexes of the type (RuCl(CO)(B)(L)) (B = PPh 3 , AsPh 3 , py or pip; L monobasic tridentate Schiff base) have been synthesized by the reaction of equimolar amounts of (RuHCl(CO)(EPh 3 ) 2 (B)) and Schiff bases in benzene. The resulting complexes have been characterized by analytical and spectral (IR, electronic, NMR) data. An octahedral structure has been assigned to all these complexes. The new complexes have been exhibit catalytic activity for the oxidation of benzyl alcohol and cyclohexanol in the presence of N-methylmorpholine-N-oxide as co-oxidant. (author)

  3. Engineering of Syndiotactic and Isotactic Polystyrene-Based Copolymers via Stereoselective Catalytic Polymerization

    Directory of Open Access Journals (Sweden)

    Eva Laur

    2017-04-01

    Full Text Available This contribution presents an updated overview of the different copolymers containing stereoregular polystyrene blocks. Special emphasis is placed on syndiospecific and isospecific copolymerization of styrene with co-monomers (ethylene and α-olefins, conjugated and non-conjugated dienes, styrene derivatives, etc.. The catalytic systems involved are described and the polymerization mechanisms are discussed. Alternative approaches (simultaneous, living, chain-transfer and graft copolymerization and the resulting detailed structures and characteristics of the copolymers are also reported.

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

    DEFF Research Database (Denmark)

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

    2016-01-01

    of experiments were performed to study catalytic activity and effect of sulfur poisoning: (i) CH4 and CO2 dissociation; (ii) biogas (60% CH4 and 40% CO2) temperature-programmed reactions (TPRxn); and (iii) steady-state biogas reforming reactions followed by postmortem catalyst characterization by temperature......-programmed oxidation and time-of-flight secondary ion mass spectrometry. Results showed thatNi/ScYSZ/Pd-CGO was more active for catalytic dissociation of CH4 at 750°C and subsequent reactivity of deposited carbonaceous species. Sulfur deactivated most catalytic reactions except CO2 dissociation at 750°C. The presence...... of Pd-CGO helped to mitigate sulfur deactivation effect; e.g. lowering the onset temperature (up to 190°C) for CH4 conversion during temperature-programmed reactions. Both Ni/ScYSZ and Ni/ScYSZ/Pd-CGO anode catalysts were more active for dry reforming of biogas than they were for steam reforming...

  5. Selective catalytic reduction of nitrogen oxides from industrial gases by hydrogen or methane; Reduction catalytique selective des oxydes d'azote (NO{sub x}) provenant d'effluents gazeux industriels par l'hydrogene ou le methane

    Energy Technology Data Exchange (ETDEWEB)

    Engelmann Pirez, M

    2004-12-15

    This work deals with the selective catalytic reduction of nitrogen oxides (NO{sub x}), contained in the effluents of industrial plants, by hydrogen or methane. The aim is to replace ammonia, used as reducing agent, in the conventional process. The use of others reducing agents such as hydrogen or methane is interesting for different reasons: practical, economical and ecological. The catalyst has to convert selectively NO into N{sub 2}, in presence of an excess of oxygen, steam and sulfur dioxide. The developed catalyst is constituted by a support such as perovskites, particularly LaCoO{sub 3}, on which are dispersed noble metals (palladium, platinum). The interaction between the noble metal and the support, generated during the activation of the catalyst, allows to minimize the water and sulfur dioxide inhibitor phenomena on the catalytic performances, particularly in the reduction of NO by hydrogen. (O.M.)

  6. New Element Organic Frameworks Based on Sn, Sb, and Bi, with Permanent Porosity and High Catalytic Activity

    Directory of Open Access Journals (Sweden)

    Julia Fritsch

    2010-03-01

    Full Text Available We present new element organic frameworks based on Sn, Sb and Bi atoms connected via organic linkers by element-carbon bonds. The open frameworks are characterized by specific surface areas (BET of up to 445 m2 g-1 and a good stability under ambient conditions resulting from a highly hydrophobic inner surface. They show good performance as heterogeneous catalysts in the cyanosylilation of benzaldehyde as a test reaction. Due to their catalytic activity, this class of materials might be able to replace common homogeneous element-organic and often highly toxic catalysts especially in the food industry.

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

    Science.gov (United States)

    Sun, MIn; Perry, Kevin L.

    2015-11-20

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

  8. Synthesis of New Chiral Ligands Based on Thiophene Derivatives for Use in Catalytic Asymmetric Oxidation of Sulfides

    International Nuclear Information System (INIS)

    Jeong, Yong Chul; Ahn, Dae Jun; Lee, Woo Sun; Lee, Seung Han; Ahn, Kwang Hyun

    2011-01-01

    We discovered that the vanadium complexes of new Schiff base ligands and prepared from thiophene derivatives efficiently catalyze the asymmetric oxidation of sulfides by hydrogen peroxide to provide sulfoxides with enantioselectivities up to 79% ee and in yields up to 89%. Notably, Schiff base showed better or similar enantioselectivity than the well-studied Schiff base. These results suggest possible applications of Schiff bases derived from and in other catalytic asymmetric reactions. Chiral sulfoxides are important functional groups for various applications. For example, the biological activities of sulfoxide containing drugs such as omeprazole are strongly related to the chirality of the sulfoxide group; for this reason, esomeprazole, the enantiomerically pure form of omeprazole, was later developed. There are several chiral sulfoxide based drugs that have been introduced by the pharmaceutical industry including armodafinil, aprikalim, oxisurane, and ustiloxin. Chiral sulfoxides have also been utilized as chiral auxiliaries in asymmetric syntheses of chiral intermediates

  9. Catalytic Emulsion Based on Janus Nanosheets for Ultra-Deep Desulfurization.

    Science.gov (United States)

    Xia, Lixin; Zhang, Hairan; Wei, Zhichao; Jiang, Yi; Zhang, Ling; Zhao, Jie; Zhang, Junhui; Dong, Li; Li, Erni; Ruhlmann, Laurent; Zhang, Qian

    2017-02-03

    Catalytic Janus nanosheets were synthesized by using an anion-exchange reaction between heteropolyacids (HPAs) and the modified ionic-liquid (IL) moieties of Janus nanosheets. Their morphology and surface properties were characterized by using SEM, energy-dispersive spectroscopy (EDS), FTIR spectroscopy, and X-ray photoelectron spectroscopy (XPS) studies. Because of their inherent Janus structure, the nanosheets exhibited good amphipathic character with ILs and oil to form a stable ILs-in-oil emulsion. Therefore, these Janus nanosheets can be used as both emulsifiers and catalysts to perform emulsive desulfurization. During this process, sulfur-containing compounds at the interface could be easily oxidized and efficiently removed from a model oil. Application of this Janus emulsion brings an efficient, useful, and green procedure to the desulfurization process. Compared with the desulfurization catalyzed by using HPAs in a conventional two-phase system, the sulfur removal of dibenzothiophene (DBT) achieved in a Janus emulsion system was improved from 68 to 97 % within 1.5 h. Moreover, this emulsion system could be demulsified easily by simple centrifugation to recover both the nanosheets and the ILs. Owing to the good structural stability of the Janus nanosheets, the sulfur removal efficiency of DBT could still reach 99.9 % after the catalytic nanosheets had been recycled at least six times. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Catalytic turnover-based phage selection for engineering the substrate specificity of Sfp phosphopantetheinyl transferase.

    Science.gov (United States)

    Sunbul, Murat; Marshall, Norman J; Zou, Yekui; Zhang, Keya; Yin, Jun

    2009-04-10

    We report a high-throughput phage selection method to identify mutants of Sfp phosphopantetheinyl transferase with altered substrate specificities from a large library of the Sfp enzyme. In this method, Sfp and its peptide substrates are co-displayed on the M13 phage surface as fusions to the phage capsid protein pIII. Phage-displayed Sfp mutants that are active with biotin-conjugated coenzyme A (CoA) analogues would covalently transfer biotin to the peptide substrates anchored on the same phage particle. Affinity selection for biotin-labeled phages would enrich Sfp mutants that recognize CoA analogues for carrier protein modification. We used this method to successfully change the substrate specificity of Sfp and identified mutant enzymes with more than 300-fold increase in catalytic efficiency with 3'-dephospho CoA as the substrate. The method we developed in this study provides a useful platform to display enzymes and their peptide substrates on the phage surface and directly couples phage selection with enzyme catalysis. We envision this method to be applied to engineering the catalytic activities of other protein posttranslational modification enzymes.

  11. Investigating the Synthesis, Structure, and Catalytic Properties of Versatile Gold-Based Nanocatalvsts

    Science.gov (United States)

    Pretzer, Lori A.

    Transition metal nanomaterials are used to catalyze many chemical reactions, including those key to environmental, medicinal, and petrochemical fields. Improving their catalytic properties and lifetime would have significant economic and environmental rewards. Potentially expedient options to make such advancements are to alter the shape, size, or composition of transition metal nanocatalysts. This work investigates the relationships between structure and catalytic properties of synthesized Au, Pd-on-Au, and Au-enzyme model transition metal nanocatalysts. Au and Pd-on-Au nanomaterials were studied due to their wide-spread application and structure-dependent electronic and geometric properties. The goal of this thesis is to contribute design procedures and synthesis methods that enable the preparation of more efficient transition metal nanocatalysts. The influence of the size and composition of Pd-on-Au nanoparticles (NPs) was systematically investigated and each was found to affect the catalyst's surface structure and catalytic properties. The catalytic hydrodechlorination of trichloroethene and reduction of 4-nitrophenol by Pd-on-Au nanoparticles were investigated as these reactions are useful for environmental and pharmaceutical synthesis applications, respectively. Structural characterization revealed that the dispersion and oxidation state of surface Pd atoms are controlled by the Au particle size and concentration of Pd. These structural changes are correlated with observed Pd-on-Au NP activities for both probe reactions, providing new insight into the structure-activity relationships of bimetallic nanocatalysts. Using the structure-dependent electronic properties of Au NPs, a new type of light-triggered biocatalyst was prepared and used to remotely control a model biochemical reaction. This biocatalyst consists of a model thermophilic glucokinase enzyme covalently attached to the surface of Au nanorods. The rod-like shape of the Au nanoparticles made the

  12. How accurate and statistically robust are catalytic site predictions based on closeness centrality?

    Directory of Open Access Journals (Sweden)

    Livesay Dennis R

    2007-05-01

    Full Text Available Abstract Background We examine the accuracy of enzyme catalytic residue predictions from a network representation of protein structure. In this model, amino acid α-carbons specify vertices within a graph and edges connect vertices that are proximal in structure. Closeness centrality, which has shown promise in previous investigations, is used to identify important positions within the network. Closeness centrality, a global measure of network centrality, is calculated as the reciprocal of the average distance between vertex i and all other vertices. Results We benchmark the approach against 283 structurally unique proteins within the Catalytic Site Atlas. Our results, which are inline with previous investigations of smaller datasets, indicate closeness centrality predictions are statistically significant. However, unlike previous approaches, we specifically focus on residues with the very best scores. Over the top five closeness centrality scores, we observe an average true to false positive rate ratio of 6.8 to 1. As demonstrated previously, adding a solvent accessibility filter significantly improves predictive power; the average ratio is increased to 15.3 to 1. We also demonstrate (for the first time that filtering the predictions by residue identity improves the results even more than accessibility filtering. Here, we simply eliminate residues with physiochemical properties unlikely to be compatible with catalytic requirements from consideration. Residue identity filtering improves the average true to false positive rate ratio to 26.3 to 1. Combining the two filters together has little affect on the results. Calculated p-values for the three prediction schemes range from 2.7E-9 to less than 8.8E-134. Finally, the sensitivity of the predictions to structure choice and slight perturbations is examined. Conclusion Our results resolutely confirm that closeness centrality is a viable prediction scheme whose predictions are statistically

  13. Ultrasensitive aptamer-based multiplexed electrochemical detection by coupling distinguishable signal tags with catalytic recycling of DNase I.

    Science.gov (United States)

    Tang, Dianping; Tang, Juan; Li, Qunfang; Su, Biling; Chen, Guonan

    2011-10-01

    This work reports an aptamer-based, disposable, and multiplexed sensing platform for simultaneous electrochemical determination of small molecules, employing adenosine triphosphate (ATP) and cocaine as the model target analytes. The multiplexed sensing strategy is based on target-induced release of distinguishable redox tag-conjugated aptamers from a magnetic graphene platform. The electronic signal of the aptasensors could be further amplified by coupling DNase I with catalytic recycling of self-produced reactants. The assay was based on the change in the current at the various peak potentials in the presence of the corresponding signal tags. Experimental results revealed that the multiplexed electrochemical aptasensor enabled the simultaneous monitoring of ATP and cocaine in a single run with wide working ranges and low detection limits (LODs: 0.1 pM for ATP and 1.5 pM for cocaine). This concept offers promise for rapid, simple, and cost-effective analysis of biological samples.

  14. Bactericidal and catalytic performance of green nanocomposite based-on chitosan/carbon black fiber supported monometallic and bimetallic nanoparticles.

    Science.gov (United States)

    Ali, Fayaz; Khan, Sher Bahadar; Kamal, Tahseen; Anwar, Yasir; Alamry, Khalid A; Asiri, Abdullah M

    2017-12-01

    Nanoparticles were synthesized on the surface of green nanocomposite based on carbon black dispersed in chitosan (CB-CS) fibres. The nanoparticles were monometallic Co, Ag and Cu and bimetallic Co + Cu and Co + Ag. The CB-CS fibres were prepared and introduced into separate metal salt solutions containing Co 2+ , Ag + and Cu 2+ and mixed Co 2+ +Cu 2+ and Co 2+ +Ag + ions. The metal ions immobilized on the surface of CB-CS were reduced using sodium borohydride (NaBH 4 ) as reducing agent to synthesize the corresponding zero-valent metal nanoparticles-loaded CB-CS fibres. All the nanoparticles-loaded CB-CS samples were characterized using field emission-scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction techniques. When tested as catalysts, the nanoparticles-loaded CB-CS showed excellent catalytic ability for the reduction of toxic and environmentally unwanted pollutants of para-nitrophenol, congo red and methyl orange dyes. Afterwards, the antimicrobial activities of virgin and metal-loaded CB-CS fibres were tested and the metal-loaded CB-CS fibres were found to be effective against Escherichia coli. In addition, the catalyst can be recovered easily by simply removing the fibres from the reaction mixture and can be recycled several times while maintaining high catalytic efficiency. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Catalytic devices

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ming; Zhang, Xiang

    2018-01-23

    This disclosure provides systems, methods, and apparatus related to catalytic devices. In one aspect, a device includes a substrate, an electrically insulating layer disposed on the substrate, a layer of material disposed on the electrically insulating layer, and a catalyst disposed on the layer of material. The substrate comprises an electrically conductive material. The substrate and the layer of material are electrically coupled to one another and configured to have a voltage applied across them.

  16. Structural determinants of the catalytic inhibition of human topoisomerase IIα by salicylate analogs and salicylate-based drugs.

    Science.gov (United States)

    Bau, Jason T; Kurz, Ebba U

    2014-06-15

    We previously identified salicylate as a novel catalytic inhibitor of human DNA topoisomerase II (topo II; EC 5.99.1.3) that preferentially targets the alpha isoform by interfering with topo II-mediated DNA cleavage. Many pharmaceuticals and compounds found in foods are salicylate-based. We have now investigated whether these are also catalytic inhibitors of topo II and the structural determinants modulating these effects. We have determined that a number of hydroxylated benzoic acids attenuate doxorubicin-induced DNA damage signaling mediated by the ATM protein kinase and inhibit topo II decatenation activity in vitro with varying potencies. Based on the chemical structures of these and other derivatives, we identified unique properties influencing topo II inhibition, including the importance of substitutions at the 2'- and 5'-positions. We extended our findings to a number of salicylate-based pharmaceuticals including sulfasalazine and diflunisal and found that both were effective at attenuating doxorubicin-induced DNA damage signaling, topo II DNA decatenation and they blocked stabilization of doxorubicin-induced topo II cleavable complexes in cells. In a manner similar to salicylate, we determined that these agents inhibit topo II-mediated DNA cleavage. This was accompanied by a concomitant decrease in topo II-mediated ATP-hydrolysis. Taken together, these findings reveal a novel function for the broader class of salicylate-related compounds and highlight the need for additional studies into whether they may impact the efficacy of chemotherapy regimens that include topo II poisons. Copyright © 2014 Elsevier Inc. All rights reserved.

  17. Bio-based phenols and fuel production from catalytic microwave pyrolysis of lignin by activated carbons.

    Science.gov (United States)

    Bu, Quan; Lei, Hanwu; Wang, Lu; Wei, Yi; Zhu, Lei; Zhang, Xuesong; Liu, Yupeng; Yadavalli, Gayatri; Tang, Juming

    2014-06-01

    The aim of this study is to explore catalytic microwave pyrolysis of lignin for renewable phenols and fuels using activated carbon (AC) as a catalyst. A central composite experimental design (CCD) was used to optimize the reaction condition. The effects of reaction temperature and weight hourly space velocity (WHSV, h(-1)) on product yields were investigated. GC/MS analysis showed that the main chemical compounds of bio-oils were phenols, guaiacols, hydrocarbons and esters, most of which were ranged from 71% to 87% of the bio-oils depending on different reaction conditions. Bio-oils with high concentrations of phenol (45% in the bio-oil) were obtained. The calorific value analysis revealed that the high heating values (HHV) of the lignin-derived biochars were from 20.4 to 24.5 MJ/kg in comparison with raw lignin (19 MJ/kg). The reaction mechanism of this process was analyzed. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Catalytic Characteristics of New Antibacterials Based on Hexahistidine-Containing Organophosphorus Hydrolase

    Directory of Open Access Journals (Sweden)

    Olga Maslova

    2017-09-01

    Full Text Available Catalytic characteristics of hexahistidine-containing organophosphorus hydrolase (His6-OPH and its enzyme-polyelectrolyte complexes with poly-l-glutamic acid or poly-l-aspartic acid (His6-OPH/PLD50, hydrolyzing organophosphorous compounds, and N-acyl homoserine lactones were studied in the presence of various antibiotics (ampicillin, gentamicin, kanamycin, and rifampicin. The antibiotics at concentrations below 1 g·L−1 had a negligible inhibiting effect on the His6-OPH activity. Mixed inhibition of His6-OPH was established for higher antibiotic concentrations, and rifampicin was the most potent inhibitor. Stabilization of the His6-OPH activity was observed in the presence of antibiotics at a concentration of 0.2 g·L−1 during exposure at 25–41 °C. Molecular docking of antibiotics to the surface of His6-OPH dimer revealed the antibiotics binding both to the area near active centers of the enzyme subunits and to the region of contact between subunits of the dimer. Such interactions between antibiotics and His6-OPH were verified with Fourier-transform infrared (FTIR spectroscopy. Considering all the results of the study, the combination of His6-OPH/PLD50 with β-lactam antibiotic ampicillin was established as the optimal one in terms of exhibition and persistence of maximal lactonase activity of the enzyme.

  19. A Broad Spectrum Catalytic System for Removal of Toxic Organics from Water by Deep Oxidation - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Sen, Ayusman

    2000-12-01

    A most pressing need for the DOE environmental management program is the removal of toxic organic compounds present in groundwater and soil at specific DOE sites. While several remediation procedures have been proposed, they suffer from one or more drawbacks. The objective of the present research was to develop new catalytic procedures for the removal of toxic organic compounds from the environment through their deep oxidation to harmless products. In water, metallic palladium was found to catalyze the deep oxidation of a wide variety of toxic organic compounds by dioxygen at 80-90 C in the presence of carbon monoxide or dihydrogen. Several classes of organic compounds were examined: benzene, phenol and substituted phenols, nitro and halo organics, organophosphorus, and organosulfur compounds. In every case, deep oxidation to carbon monoxide, carbon dioxide, and water occurred in high yields, resulting in up to several hundred turnovers over a 24 hour period. For substrates susceptible to hydrogenation, the conversions were generally high with dihydrogen than with carbon monoxide. It is clear from the results obtained that we have discovered an exceptionally versatile catalytic system for the deep oxidation of toxic organic compounds in water. This system possesses several attractive features not found simultaneously in other reported systems. These are (a) the ability to directly utilize dioxygen as the oxidant, (b) the ability to carry out the deep oxidation of a particularly wide range of functional organics, and (c) the ease of recovery of the catalyst by simple filtration.

  20. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

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    acetylchlorophosphonazo(CPApA) by hydrogen peroxide in 0.10 M phosphoric acid. A novel catalytic kinetic-spectrophotometric method is proposed for the determination of copper based on this principle. Copper(II) can be determined spectrophotometrically ...

  1. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

    Based on the property that in 0.12 M sulfuric acid medium titanium(IV) catalyzes the discoloring reaction of DBS-arsenazo oxidized by potassium bromate, a new catalytic kinetic spectrophotometric method for the determination of trace titanium (IV) was developed. The linear range of the determination of titanium is

  2. Synthesis, structure and catalytic activities of nickel(II) complexes bearing N4 tetradentate Schiff base ligand

    Science.gov (United States)

    Sarkar, Saikat; Nag, Sanat Kumar; Chattopadhyay, Asoke Prasun; Dey, Kamalendu; Islam, Sk. Manirul; Sarkar, Avijit; Sarkar, Sougata

    2018-05-01

    Two new nickel(II) complexes [Ni(L)Cl2] (1) and [Ni(L)(NCS)2] (2) of a neutral tetradentate mono-condensed Schiff base ligand, 3-(2-(2-aminoethylamino)ethylimino)butan-2-one oxime (L) have been synthesized and characterized using different physicochemical techniques e.g. elemental analyses, spectroscopic (IR, Electronic, NMR) methods, conductivity and molecular measurements. The crystal structure of complex (2) has been determined by using single crystal X-ray diffraction method and it suggests a distorted octahedral geometry around nickel(II) having a NiN6 coordinating atmosphere. The non-coordinated Osbnd H group on the ligand L remain engaged in H-bonding interactions with the S end of the coordinated thiocyanate moiety. These H-bonding interactions lead to Osbnd S separations of 3.132 Å and play prominent role in crystal packing. It is observed that the mononuclear units are glued together with such Osbnd H…S interactions and finally results in an 1D supramolecular sheet-like arrangement. DFT/TDDFT based theoretical calculations were also performed on the ligand and the complexes aiming at the accomplishment of idea regarding their optimized geometry, electronic transitions and the molecular energy levels. Finally the catalytic behavior of the complexes for oxidation of styrene has also been carried out. A variety of reaction conditions like the effect of solvent, effect of temperature and time as well as the effect of ratio of substrate to oxidant were thoroughly studied to judge the catalytic efficiency of the Ni(II) coordination entity.

  3. Enhanced catalytic properties of Pt-based electrode by doped Cu and Ce

    Science.gov (United States)

    Yue, Dehuai; Yang, Bin

    2017-08-01

    Novel PtCuCeO x composite membrane electrode materials were fabricated on the surface of graphite fibrous cloth by ion beam sputtering (IBS). The cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were used to analyze the influence of doped Cu and Ce on the membrane electrocatalysis performance in a tri-electrode system. The phase composition, surface structure, interfacial structure and catalytic performance of PtCuCeO x membrane were studied by x-ray diffraction (XRD) and high resolution transmission electron microscope (HR-TEM&STEM). The results indicate that surface particles of membrane electrode are made up of PtCu alloy grains and a few CeO x grains, and the interface structure of oxide metal is formed between them. The crystal plane spacing between PtCu alloy grain is reduced by about 1.11% after the corrosion, which helps increase the electron density on Pt atom. As a result, the catalysis capability of PtCu alloy is enhanced. When the content of Ce is less than or equal to 0.28 wt.%, CeO x exists in the form of amorphous. It is exciting to demonstrate that the existence of CeO x enhances the dispersion of PtCuCeO x catalyst particles. The experimental results reveal that the synthesized material possesses the best electrochemical activity surface area (ESA) and exchange current density (i 0). Compared to pure Pt catalyst, this PtCuCeO x catalyst contains much less Pt content (only 42% of Pt catalyst). However, the electrochemical performance is enhanced by 71.8% compared with pure Pt.

  4. Fast and quantitative differentiation of single-base mismatched DNA by initial reaction rate of catalytic hairpin assembly.

    Science.gov (United States)

    Li, Chenxi; Li, Yixin; Xu, Xiao; Wang, Xinyi; Chen, Yang; Yang, Xiaoda; Liu, Feng; Li, Na

    2014-10-15

    The widely used catalytic hairpin assembly (CHA) amplification strategy generally needs several hours to accomplish one measurement based on the prevailingly used maximum intensity detection mode, making it less practical for assays where high throughput or speed is desired. To make the best use of the kinetic specificity of toehold domain for circuit reaction initiation, we developed a mathematical model and proposed an initial reaction rate detection mode to quantitatively differentiate the single-base mismatch. Using the kinetic mode, assay time can be reduced substantially to 10 min for one measurement with the comparable sensitivity and single-base mismatch differentiating ability as were obtained by the maximum intensity detection mode. This initial reaction rate based approach not only provided a fast and quantitative differentiation of single-base mismatch, but also helped in-depth understanding of the CHA system, which will be beneficial to the design of highly sensitive and specific toehold-mediated hybridization reactions. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Determination of the level of DNA modification with cisplatin by catalytic hydrogen evolution at mercury-based electrodes.

    Science.gov (United States)

    Horáková, Petra; Tesnohlídková, Lucie; Havran, Ludek; Vidláková, Pavlína; Pivonková, Hana; Fojta, Miroslav

    2010-04-01

    Electrochemical methods proved useful as simple and inexpensive tools for the analysis of natural as well as chemically modified nucleic acids. In particular, covalently attached metal-containing groups usually render the DNA well-pronounced electrochemical activity related to redox processes of the metal moieties, which can in some cases be coupled to catalytic hydrogen evolution at mercury or some types of amalgam electrodes. In this paper we used voltammetry at the mercury-based electrodes for the monitoring of DNA modification with cis-diamminedichloroplatinum (cisplatin), a representative of metallodrugs used in the treatment of various types of cancer or being developed for such purpose. In cyclic voltammetry at the mercury electrode, the cisplatin-modified DNA yielded catalytic currents the intensity of which reflected DNA modification extent. In square-wave voltammetry, during anodic polarization after prereduction of the cisplatinated DNA, a well-developed, symmetrical signal (peak P) was obtained. Intensity of the peak P linearly responded to the extent of DNA modification at levels relevant for biochemical studies (rb = 0.01-0.10, where rb is the number of platinum atoms bound per DNA nucleotide). We demonstrate a correlation between the peak P intensity and a loss of sequence-specific DNA binding by tumor suppressor protein p53, as well as blockage of DNA digestion by a restriction endonuclease Msp I (both caused by the DNA cisplatination). Application of the electrochemical technique in studies of DNA reactivity with various anticancer platinum compounds, as well as for an easy determination of the extent of DNA platination in studies of its biochemical effects, is discussed.

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

    Directory of Open Access Journals (Sweden)

    Wan Azelee Wan Abu Bakar

    2015-09-01

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

  7. Radio-Frequency-Based NH3-Selective Catalytic Reduction Catalyst Control: Studies on Temperature Dependency and Humidity Influences

    Directory of Open Access Journals (Sweden)

    Markus Dietrich

    2017-07-01

    Full Text Available The upcoming more stringent automotive emission legislations and current developments have promoted new technologies for more precise and reliable catalyst control. For this purpose, radio-frequency-based (RF catalyst state determination offers the only approach for directly measuring the NH3 loading on selective catalytic reduction (SCR catalysts and the state of other catalysts and filter systems. Recently, the ability of this technique to directly control the urea dosing on a current NH3 storing zeolite catalyst has been demonstrated on an engine dynamometer for the first time and this paper continues that work. Therefore, a well-known serial-type and zeolite-based SCR catalyst (Cu-SSZ-13 was investigated under deliberately chosen high space velocities. At first, the full functionality of the RF system with Cu-SSZ-13 as sample was tested successfully. By direct RF-based NH3 storage control, the influence of the storage degree on the catalyst performance, i.e., on NOx conversion and NH3 slip, was investigated in a temperature range between 250 and 400 °C. For each operation point, an ideal and a critical NH3 storage degree was found and analyzed in the whole temperature range. Based on the data of all experimental runs, temperature dependent calibration functions were developed as a basis for upcoming tests under transient conditions. Additionally, the influence of exhaust humidity was observed with special focus on cold start water and its effects to the RF signals.

  8. Nanocrystalline Ferrihydrite-Based Catalysts for Fischer-Tropsch Synthesis: Part II. Effects of Activation Gases on the Catalytic Performance.

    Science.gov (United States)

    Rhim, Geun Bae; Hong, Seok Yong; Park, Ji Chan; Jung, Heon; Rhee, Young Woo; Chun, Dong Hyun

    2016-02-01

    Fischer-Tropsch synthesis (FTS) was carried out over nanocrystalline ferrihydrite-based (Fe9O2(OH)23) catalysts activated by different reducing agents: syngas (H2+CO), CO, and H2. The syngas activation successfully changed the ferrihydrite-based catalysts into an active and stable catalytic structure with chi-carbide (Fe2.5 C) and epsilon'-carbide (Fe2.2 C). The crystal structure of the catalysts obtained by syngas activation was similar to the structure obtained by CO activation; this similarity was probably due to the peculiar reduction behavior of the ferrihydrite-based catalysts, which exhibit much greater reducibility in CO atmosphere than in H2 atmosphere. The performance of the catalysts activated by syngas was much higher than the performance of the catalysts activated by H2 and was comparable to the performance of the catalysts activated by CO. This strongly demonstrates that the ferrihydrite-based catalysts are advantageous for industrial FTS processes because syngas can be commonly used for both activation pre-treatment and subsequent reaction.

  9. A bio-based ‘green’ process for catalytic adipic acid production from lignocellulosic biomass using cellulose and hemicellulose derived γ-valerolactone

    International Nuclear Information System (INIS)

    Han, Jeehoon

    2016-01-01

    Highlights: • A bio-based ‘green’ process for catalytic conversion of corn stover to adipic acid (ADA) is studied. • New separations for effective recovery of biomass derivatives are developed. • Separations are integrated with cellulose/hemicellulose-to-ADA conversions. • Proposed process can compete economically with the current petro-based process. - Abstract: A bio-based ‘green’ process is presented for the catalytic conversion of corn stover to adipic acid (ADA) based on experimental studies. ADA is used for biobased nylon 6.6 manufacturing from lignocellulosics as carbon and energy source. In this process, the cellulose and hemicellulose fractions are catalytically converted to γ-valerolactone (GVL), using cellulose and hemicellulose-derived GVL as a solvent, and subsequently upgrading to ADA. Experimental studies showed maximal carbon yields (biomass-to-GVL: 41% and GVL-to-ADA: 46%) at low concentrations (below 16 wt% solids) using large volumes of GVL solvents while requiring efficient interstage separations and product recovery. This work presents an integrated process, including catalytic conversion and separation subsystems for GVL and ADA production and recovery, and designs a heat exchanger network to satisfy the total energy requirements of the integrated process via combustion of biomass residues (lignin and humins). Finally, an economic analysis shows that 2000 metric tonnes (Mt) per day of corn stover feedstock processing results in a minimum selling price of $633 per Mt if using the best possible parameters.

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

    International Nuclear Information System (INIS)

    Garcia C, M.A.; Perez H, R.; Gomez C, A.; Diaz, G.

    1999-01-01

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

  11. Model-based design of low-temperature carbon nanotube synthesis via catalytic oxidation for supercapacitor application.

    Science.gov (United States)

    Vasenkov, A V; Carnahan, D L

    2010-12-01

    Novel electrochemical double layer capacitors with carbon nanotube (CNT) electrode, often referred to as supercapacitors, have a potential to bridge a power and energy gap between traditional dielectric capacitors and chemical batteries. However, their future is uncertain because current fabrication technologies involve difficult-to-control post-growth manipulations of CNTs. This paper addresses this problem by introducing model-based design of low-temperature CNT synthesis that is suitable for in-situ fabrication of CNT-based supercapacitor electrode. The insight to the surface kinetics during low-temperature CNT synthesis via catalytic oxidation was obtained via coupled Molecular Dynamics and Quantum Semiempirical Hamiltonian simulations. It was determined that the presence of oxygen on the surface of catalyst increases, by several times, the time necessary for the decomposition of hydrocarbons as well as shifts the reaction zone from the surface of catalyst to the catalyst underlayer. Theoretical trends were confirmed by CNT growth experiments. A contact between conducting CNTs and zinc oxide binding layer was analyzed in detail since its properties strongly affect the performance of CNT electrode. It was demonstrated that the formed CNT-zinc oxide interface was free from unbonded oxygen atoms and/or clusters of zinc atoms and was weakly affected by defects in CNTs.

  12. Sugar-based micro/mesoporous hypercross-linked polymers with in situ embedded silver nanoparticles for catalytic reduction

    Directory of Open Access Journals (Sweden)

    Qing Yin

    2017-06-01

    Full Text Available Porous hypercross-linked polymers based on perbenzylated monosugars (SugPOP-1–3 have been synthesized by Friedel–Crafts reaction using formaldehyde dimethyl acetal as an external cross-linker. Three perbenzylated monosugars with similar chemical structure were used as monomers in order to tune the porosity. These obtained polymers exhibit microporous and mesoporous features. The highest Brunauer–Emmett–Teller specific surface area for the resulting polymers was found to be 1220 m2 g−1, and the related carbon dioxide storage capacity was found to be 14.4 wt % at 1.0 bar and 273 K. As the prepared porous polymer SugPOP-1 is based on hemiacetal glucose, Ag nanoparticles (AgNPs can be successfully incorporated into the polymer by an in situ chemical reduction of freshly prepared Tollens’ reagent. The obtained AgNPs/SugPOP-1 composite demonstrates good catalytic activity in the reduction of 4-nitrophenol (4-NP with an activity factor ka = 51.4 s−1 g−1, which is higher than some reported AgNP-containing composite materials.

  13. Sugar-based micro/mesoporous hypercross-linked polymers with in situ embedded silver nanoparticles for catalytic reduction.

    Science.gov (United States)

    Yin, Qing; Chen, Qi; Lu, Li-Can; Han, Bao-Hang

    2017-01-01

    Porous hypercross-linked polymers based on perbenzylated monosugars ( SugPOP-1-3 ) have been synthesized by Friedel-Crafts reaction using formaldehyde dimethyl acetal as an external cross-linker. Three perbenzylated monosugars with similar chemical structure were used as monomers in order to tune the porosity. These obtained polymers exhibit microporous and mesoporous features. The highest Brunauer-Emmett-Teller specific surface area for the resulting polymers was found to be 1220 m 2 g -1 , and the related carbon dioxide storage capacity was found to be 14.4 wt % at 1.0 bar and 273 K. As the prepared porous polymer SugPOP-1 is based on hemiacetal glucose, Ag nanoparticles (AgNPs) can be successfully incorporated into the polymer by an in situ chemical reduction of freshly prepared Tollens' reagent. The obtained AgNPs/ SugPOP-1 composite demonstrates good catalytic activity in the reduction of 4-nitrophenol (4-NP) with an activity factor k a = 51.4 s -1 g -1 , which is higher than some reported AgNP-containing composite materials.

  14. Synthesis of copper/nickel nanoparticles using newly synthesized Schiff-base metals complexes and their cytotoxicity/catalytic activities.

    Science.gov (United States)

    Aazam, Elham S; El-Said, Waleed Ahmed

    2014-12-01

    Transition metal complexes compounds with Schiff bases ligand representing an important class of compounds that could be used to develop new metal-based anticancer agents and as precursors of metal NPs. Herein, 2,3-bis-[(3-ethoxy-2-hydroxybenzylidene)amino]but-2-enedinitrile Schiff base ligand and its corresponding copper/nickel complexes were synthesized. Also, we reported a facile and rapid method for synthesis nickel/copper nanoparticles based on thermal reduction of their complexes. Free ligand, its metal complexes and metals nanoparticles have been characterized based on elemental analysis, transmission electron microscopy, powder X-ray diffraction, magnetic measurements and by various spectroscopic (UV-vis, FT-IR, (1)H NMR, GC-MS) techniques. Additionally, the in vitro cytotoxic activity of free ligand and its complexes compounds were assessed against two cancer cell lines (HeLa and MCF-7 cells)and one healthy cell line (HEK293 cell). The copper complex was found to be active against these cancer cell lines at very low LD50 than the free ligand, while nickel complex did not show any anticancer activity against these cell lines. Also, the antibacterial activity of as-prepared copper nanoparticles were screened against Escherichia coli, which demonstrated minimum inhibitory concentration and minimum bactericidal concentration values lower than those values of the commercial Cu NPs as well as the previous reported values. Moreover, the synthesized nickel nanoparticles demonstrated remarkable catalytic performance toward hydrogenation of nitrobenzene that producing clean aniline with high selectivity (98%). This reactivity could be attributed to the high degree of dispersion of Ni nanoparticles. Copyright © 2014 Elsevier Inc. All rights reserved.

  15. Catalytic thermal barrier coatings

    Science.gov (United States)

    Kulkarni, Anand A.; Campbell, Christian X.; Subramanian, Ramesh

    2009-06-02

    A catalyst element (30) for high temperature applications such as a gas turbine engine. The catalyst element includes a metal substrate such as a tube (32) having a layer of ceramic thermal barrier coating material (34) disposed on the substrate for thermally insulating the metal substrate from a high temperature fuel/air mixture. The ceramic thermal barrier coating material is formed of a crystal structure populated with base elements but with selected sites of the crystal structure being populated by substitute ions selected to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a higher rate than would the base compound without the ionic substitutions. Precious metal crystallites may be disposed within the crystal structure to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a lower light-off temperature than would the ceramic thermal barrier coating material without the precious metal crystallites.

  16. Colorimetric detection of trace copper ions based on catalytic leaching of silver-coated gold nanoparticles.

    Science.gov (United States)

    Lou, Tingting; Chen, Lingxin; Chen, Zhaopeng; Wang, Yunqing; Chen, Ling; Li, Jinhua

    2011-11-01

    A colorimetric, label-free, and nonaggregation-based silver coated gold nanoparticles (Ag/Au NPs) probe has been developed for detection of trace Cu(2+) in aqueous solution, based on the fact that Cu(2+) can accelerate the leaching rate of Ag/Au NPs by thiosulfate (S(2)O(3)(2-)). The leaching of Ag/Au NPs would lead to dramatic decrease in the surface plasmon resonance (SPR) absorption as the size of Ag/Au NPs decreased. This colorimetric strategy based on size-dependence of nanoparticles during their leaching process provided a highly sensitive (1.0 nM) and selective detection toward Cu(2+), with a wide linear detection range (5-800 nM) over nearly 3 orders of magnitude. The cost-effective probe allows rapid and sensitive detection of trace Cu(2+) ions in water samples, indicating its potential applicability for the determination of copper in real samples.

  17. Lanthanide-Based Metal Organic Frameworks: Synthetic Strategies and Catalytic Applications

    NARCIS (Netherlands)

    Pagis, C.; Ferbinteanu, M.; Rothenberg, G.; Grecea, S.

    2016-01-01

    This short critical review outlines the main synthetic strategies used in the designed synthesis of lanthanide-based metal organic frameworks (Ln-MOFs). It explains the impact of the choice of organic linker on the final network topology, and it highlights the applications of Ln-MOFs in the

  18. Self-Sustained Flameless Heat Generator Based on Catalytic Oxidation of Methane or Propane-Butane Mixture for Various Object Heating Including Field Heating

    Directory of Open Access Journals (Sweden)

    Strizhak, P.Ye.

    2016-09-01

    Full Text Available An effective catalyst based on ceramic block support with honeycomb structure made of synthetic cordierite with low coefficient of temperature linear expansion has been developed. Flameless heat generator based on oxidation of methane or propane-butane mixture has been designed. Laboratory and bench testing revealed that the effectiveness of the generators is identical to foreign analogues. The production of self-sustained flameless heat catalytic generators and the catalysts have been adjusted.

  19. Citric acid induced promoted dispersion of Pt on the support and enhanced catalytic activities for a Pt-based catalyst

    Science.gov (United States)

    Cheng, Tianqiong; Wang, Jianli; Wang, Suning; Cui, Yajuan; Zhang, Hailong; Yan, Shuang; Yuan, Shandong; Chen, Yaoqiang

    2017-12-01

    Citric acid (CA), as the chelating agent, was introduced to obtain the enhanced Pt dispersion and catalytic activities for the Pt-based catalysts supported on oxygen-storage material. The role and content of CA were investigated systematically. It was found that the citric acid-assisted catalysts showed better Pt dispersion and smaller nanoparticle size of Pt. Thus, the catalyst had lower reduction temperature, preferable thermostability and possessed more oxidation state of Pt species under the oxidation atmosphere. The citric acid-induced fresh catalysts were excellent to convert CO and the corresponding aged ones exhibited higher activities for the elimination of all the target pollutants. Among the aged catalysts, P2-a (the mole ratio of Pt/CA is 2:1) presented the best performance. Particularly, compared with the reference sample (Pc-a), the light-off temperatures (T50) of NO, HC and CO for P2-a decreased by 39 °C, 42 °C and 72 °C, respectively, and the full-conversion temperatures (T90) of NO, HC and CO for P2-a decreased by 44 °C, 44 °C and 48 °C, respectively. Therefore, this work provides a facile and valid method to manufacture advanced catalysts for purification of the vehicle exhaust in the future.

  20. Development of advanced catalytic layer based on vertically aligned conductive polymer arrays for thin-film fuel cell electrodes

    Science.gov (United States)

    Jiang, Shangfeng; Yi, Baolian; Cao, Longsheng; Song, Wei; Zhao, Qing; Yu, Hongmei; Shao, Zhigang

    2016-10-01

    The degradation of carbon supports significantly influences the performance of proton exchange membrane fuel cells (PEMFCs), particularly in the cathode, which must be overcome for the wide application of fuel cells. In this study, advanced catalytic layer with electronic conductive polymer-polypyrrole (PPy) nanowire as ordered catalyst supports for PEMFCs is prepared. A platinum-palladium (PtPd) catalyst thin layer with whiskerette shapes forms along the long axis of the PPy nanowires. The resulting arrays are hot-pressed on both sides of a Nafion® membrane to construct a membrane electrode assembly (without additional ionomer). The ordered thin catalyst layer (approximately 1.1 μm) is applied in a single cell as the anode and the cathode without additional Nafion® ionomer. The single cell yields a maximum performance of 762.1 mW cm-2 with a low Pt loading (0.241 mg Pt cm-2, anode + cathode). The advanced catalyst layer indicates better mass transfer in high current density than that of commercial Pt/C-based electrode. The mass activity is 1.08-fold greater than that of DOE 2017 target. Thus, the as-prepared electrodes have the potential for application in fuel cells.

  1. Kinetic spectrophotometric determination of Bi(III based on its catalytic effect on the oxidation of phenylfluorone by hydrogen peroxide

    Directory of Open Access Journals (Sweden)

    SOFIJA M. RANČIĆ

    2009-08-01

    Full Text Available A new reaction was suggested and a new kinetic method was elaborated for determination of Bi(III in solution, based on its catalytic effect on the oxidation of phenyl-fluorone (PF by hydrogen peroxide in ammonia buffer. By application of spectrophotometric technique, a limit of quantification (LQ of 128 ng cm-3 was reached, and the limit of detection (LD of 37 ng cm-3 was obtained, where LQ was defined as the ratio signal:noise = 10:1 and LD was defined as signal 3:1 against the blank. The RSD value was found to be in the range 2.8–4.8 % for the investigated concentration range of Bi(III. The influence of some ions upon the reaction rate was tested. The method was confirmed by determining Bi(III in a stomach ulcer drug (“Bicit HP”, Hemofarm A.D.. The obtained results were compared to those obtained by AAS and good agreement of results was obtained.

  2. Application of sludge-based carbonaceous materials in a hybrid water treatment process based on adsorption and catalytic wet air oxidation.

    Science.gov (United States)

    Julcour Lebigue, Carine; Andriantsiferana, Caroline; N'Guessan Krou; Ayral, Catherine; Mohamed, Elham; Wilhelm, Anne-Marie; Delmas, Henri; Le Coq, Laurence; Gerente, Claire; Smith, Karl M; Pullket, Suangusa; Fowler, Geoffrey D; Graham, Nigel J D

    2010-12-01

    This paper describes a preliminary evaluation of the performance of carbonaceous materials prepared from sewage sludges (SBCMs) in a hybrid water treatment process based on adsorption and catalytic wet air oxidation; phenol was used as the model pollutant. Three different sewage sludges were treated by either carbonisation or steam activation, and the physico-chemical properties of the resultant carbonaceous materials (e.g. hardness, BET surface area, ash and elemental content, surface chemistry) were evaluated and compared with a commercial reference activated carbon (PICA F22). The adsorption capacity for phenol of the SBCMs was greater than suggested by their BET surface area, but less than F22; a steam activated, dewatered raw sludge (SA_DRAW) had the greatest adsorption capacity of the SBCMs in the investigated range of concentrations (<0.05 mol L(-1)). In batch oxidation tests, the SBCMs demonstrated catalytic behaviour arising from their substrate adsorptivity and metal content. Recycling of SA_DRAW in successive oxidations led to significant structural attrition and a hardened SA_DRAW was evaluated, but found to be unsatisfactory during the oxidation step. In a combined adsorption-oxidation sequence, both the PICA carbon and a selected SBCM showed deterioration in phenol adsorption after oxidative regeneration, but a steady state performance was reached after 2 or 3 cycles. Copyright © 2010 Elsevier Ltd. All rights reserved.

  3. Reduced graphene oxide wrapped Fe3O4-Co3O4 yolk-shell nanostructures for advanced catalytic oxidation based on sulfate radicals

    Science.gov (United States)

    Zhang, Lishu; Yang, Xijia; Han, Erfen; Zhao, Lijun; Lian, Jianshe

    2017-02-01

    In this work, we designed and synthesized a high performance catalyst of reduced graphene oxide (RGO) wrapped Fe3O4-Co3O4 (RGO/Fe3O4-Co3O4) yolk-shell nanostructures for advanced catalytic oxidation based on sulfate radicals. The synergistic catalytic action of the RGO/Fe3O4-Co3O4 yolk-shell nanostructures activate the peroxymonosulfate (PMS) to produce sulfate radicals (SO4rad -) for organic dyes degradation, and the Orange II can be almost completely degradated in 5 min. Meanwhile the RGO wrapping prevents the loss of cobalt in the catalytic process, and the RGO/Fe3O4-Co3O4 can be recycled after catalyzed reaction due to the presence of magnetic iron core. What's more, it can maintain almost the same high catalytic activity even after 10 cycles through repeated NaBH4 reduction treatment. Hence, RGO/Fe3O4-Co3O4 yolk-shell nanostructures possess a great opportunity to become a promising candidate for waste water treatment in industry.

  4. High performance anodes with tailored catalytic properties for La5.6WO11.4-δ based proton conducting fuel cells

    DEFF Research Database (Denmark)

    Balaguer, M.; Solis, C.; Bozza, Francesco

    2013-01-01

    A new generation of anodes for PC-SOFCs based on catalytically promoted La0.75Ce0.1Sr0.15CrO3−δ (LSCCe) is presented. LSCCe is selected as the electrode backbone structure, due to its superior total conductivity over that of LSC. The infiltration of catalytically highly active nickel nanoparticle...

  5. Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex

    Energy Technology Data Exchange (ETDEWEB)

    Song, Na [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States); Concepcion, Javier J. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Binstead, Robert A. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Rudd, Jennifer A. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Vannucci, Aaron K. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemistry and Biochemistry; Dares, Christopher J. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Coggins, Michael K. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Meyer, Thomas J. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry

    2015-04-06

    In aqueous solution above pH 2.4 with 4% (vol/vol) CH3CN, the complex [RuII(bda)(isoq)2] (bda is 2,2'-bipyridine-6,6'-dicarboxylate; isoq is isoquinoline) exists as the open-arm chelate, [RuII(CO2-bpy-CO2$-$)(isoq)2(NCCH3)], as shown by 1H and 13C-NMR, X-ray crystallography, and pH titrations. Rates of water oxidation with the open-arm chelate are remarkably enhanced by added proton acceptor bases, as measured by cyclic voltammetry (CV). In 1.0 M PO43–, the calculated half-time for water oxidation is ~7 μs. In conclusion, the key to the rate accelerations with added bases is direct involvement of the buffer base in either atom–proton transfer (APT) or concerted electron–proton transfer (EPT) pathways.

  6. Study on the mechanism of a manganese-based catalyst for catalytic NOX flue gas denitration

    Science.gov (United States)

    Zhang, Lei; Wen, Xin; Lei, Zhang; Gao, Long; Sha, Xiangling; Ma, Zhenhua; He, Huibin; Wang, Yusu; Jia, Yang; Li, Yonghui

    2018-04-01

    Manganese-based bimetallic catalysts were prepared with self-made pyrolysis coke as carrier and its denitration performance of low-temperature SCR (selective catalyst reduction) was studied. The effects of different metal species, calcination temperature, calcination time and the metal load quantity on the denitration performance of the catalyst were studied by orthogonal test. The denitration mechanism of the catalyst was analyzed by XRD (X-ray diffraction), SEM (scanning electron microscope), BET test and transient test. The experiments show that: * The denitration efficiency of Mn-based bimetallic catalysts mainly relates to the metal type, the metal load quantity and the catalyst adjuvant type. * The optimal catalyst preparation conditions are as follows: the load quantity of monometallic MnO2 is 10%, calcined at 300°C for 4h, and then loaded with 8% CeO2, calcined at 350°Cfor 3h. * The denitration mechanism of manganese-based bimetallic oxide catalysts is stated as: NH3 is firstly adsorbed by B acid center Mn-OH which nears Mn4+==O to form NH4+, NH4+ was then attacked by the gas phase NO to form N2, H2O and Mn3+-OH. Finally, Mn3+-OH was oxidized by O2 to regenerate Mn4+.

  7. Efficient and recyclable Rh-catalytic system with involvement of phosphine-functionalized phosphonium-based ionic liquids for tandem hydroformylation–acetalization

    Directory of Open Access Journals (Sweden)

    Peng Wang

    2017-10-01

    Full Text Available The phosphine-functionalized phosphonium-based ionic liquids (dppm-Q, dppe-Q, dppp-Q and dppb-Q as the bi-functional ligands enable the efficient one-pot tandem hydroformylation–acetalization. It was found that, in dppm-Q, dppe-Q, dppp-Q and dppb-Q, the incorporated phosphino-fragments were responsible for Rh-catalyzed hydroformylation and the phosphoniums were in charge of the subsequent acetalization as the Lewis acid catalysts. Moreover, the diphosphonium-based ionic liquid of dppb-DQ could be applied as a co-solvent to immobilize the Rh/dppb-Q catalytic system with the advantages of the improved catalytic performance, the available catalyst recyclability, and the wide generality for the substrates. Keywords: Phosphines, Phosphonium-based ionic liquids, Bi-functional ligands, Recyclability of homogeneous catalysts, Tandem hydroformylation–acetalization

  8. Catalytic activity of calcium-based mixed metal oxides nanocatalysts in transesterification reaction of palm oil

    Science.gov (United States)

    Hassan, Noraakinah; Ismail, Kamariah Noor; Hamid, Ku Halim Ku; Hadi, Abdul

    2017-12-01

    Nowadays, biodiesel has become the forefront development as an alternative diesel fuel derived from biological sources such as oils of plant and fats. Presently, the conventional transesterification of vegetable oil to biodiesel gives rise to some technological problem. In this sense, heterogeneous nanocatalysts of calcium-based mixed metal oxides were synthesized through sol-gel method. It was found that significant increase of biodiesel yield, 91.75 % was obtained catalyzed by CaO-NbO2 from palm oil compared to pure CaO of 53.99 % under transesterification conditions (methanol/oil ratio 10:1, reaction time 3 h, catalyst concentration 4 wt%, reaction temperature 60 °C, and mixing speed of 600 rpm). The phase structure and crystallinity as well as the texture properties of the prepared catalysts were characterized by X-ray Diffraction (XRD) and the textural properties were characterized by N2 adsorption-desorption analysis. Sol-gel method has been known as versatile method in controlling the structural and chemical properties of the catalyst. Calcium-based mixed oxide synthesized from sol-gel method was found to exist as smaller crystallite size with high surface area.

  9. High Efficiency Solar-based Catalytic Structure for CO2 Reforming

    Energy Technology Data Exchange (ETDEWEB)

    Menkara, Hisham [PhosphorTech Corporation, Kennesaw, GA (United States)

    2013-09-30

    Throughout this project, we developed and optimized various photocatalyst structures for CO2 reforming into hydrocarbon fuels and various commodity chemical products. We also built several closed-loop and continuous fixed-bed photocatalytic reactor system prototypes for a larger-scale demonstration of CO2 reforming into hydrocarbons, mainly methane and formic acid. The results achieved have indicated that with each type of reactor and structure, high reforming yields can be obtained by refining the structural and operational conditions of the reactor, as well as by using various sacrificial agents (hole scavengers). We have also demonstrated, for the first time, that an aqueous solution containing acid whey (a common bio waste) is a highly effective hole scavenger for a solar-based photocatalytic reactor system and can help reform CO2 into several products at once. The optimization tasks performed throughout the project have resulted in efficiency increase in our conventional reactors from an initial 0.02% to about 0.25%, which is 10X higher than our original project goal. When acid whey was used as a sacrificial agent, the achieved energy efficiency for formic acid alone was ~0.4%, which is 16X that of our original project goal and higher than anything ever reported for a solar-based photocatalytic reactor. Therefore, by carefully selecting sacrificial agents, it should be possible to reach energy efficiency in the range of the photosynthetic efficiency of typical crop and biofuel plants (1-3%).

  10. Catalytic destruction of PCDD/Fs over vanadium oxide-based catalysts.

    Science.gov (United States)

    Yu, Ming-Feng; Lin, Xiao-Qing; Li, Xiao-Dong; Yan, Mi; Prabowo, Bayu; Li, Wen-Wei; Chen, Tong; Yan, Jian-Hua

    2016-08-01

    Vanadium oxide-based catalysts were developed for the destruction of vapour phase PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans). A vapour phase PCDD/Fs generating system was designed to supply stable PCDD/Fs steam with initial concentration of 3.2 ng I-TEQ Nm(-3). Two kinds of titania (nano-TiO2 and conventional TiO2) and alumina were used as catalyst supports. For vanadium-based catalysts supported on nano-TiO2, catalyst activity is enhanced with operating temperature increasing from 160 to 300 °C and then reduces with temperature rising further to 350 °C. It is mainly due to the fact that high volatility of organic compounds at 350 °C suppresses adsorption of PCDD/Fs on catalysts surface and then further inhibits the reaction between catalyst and PCDD/Fs. The optimum loading of vanadium on nano-TiO2 support is 5 wt.% where vanadium oxide presents highly dispersed amorphous state according to the Raman spectra and XRD patterns. Excessive vanadium will block the pore space and form microcrystalline V2O5 on the support surface. At the vanadium loading of 5 wt.%, nano-TiO2-supported catalyst performs best on PCDD/Fs destruction compared to Al2O3 and conventional TiO2. Chemical states of vanadium in the fresh, used and reoxidized VOx(5 %)/TiO2 catalysts at different operating temperature are also analysed by XPS.

  11. Presentation of a new plant design, based on an internally circulating fluidized bed system for catalytic cracking; Fluid Catalytic Cracking: Entwicklung einer neuartigen FCC-Anlage mit intern zirkulierendem Wirbelschichtsystem

    Energy Technology Data Exchange (ETDEWEB)

    Reichhold, A.; Fimberger, W.; Hofbauer, H. [Technische Univ. Vienna (Austria). Inst. fuer Verfahrenstechnik, Brennstofftechnik und Umwelttechnik

    1998-09-01

    An internally circulating fluidized bed system was developed for use as a catalytic cracking system. The plant (hot unit) was conceived for a feed rate of 1 to 4 kg/h. The hot unit was developed based on data obtained from literature (e.g. temperature, cat to oil ratio and contact time). Important fluid dynamic parameters, such as the circulation rate and the gas separation efficiency between reaction and regeneration zone were determined in an acrylic model (cold unit) at room temperature. Scaling relationships based on the theory of Glicksman were used as much as possible to design the cold unit in order to give similitude between cold and hot unit. Important parameters influencing the catalyst circulation rate could be determined exactly. Gas separation efficiency measurements between reaction and regeneration zone proved the safety of the system. The setting of the parameters during the trials was determined based on data from the cold unit and literature (e.g. temperature, cat to oil ratio, and contact time). The trials in the hot unit were carried out with vacuum gas oil and FCC-equilibrium catalyst. The experiments ran successfully and the analysis of the cracking products matched expectations. Furthermore the new system can also be used as a plant for other reactions such as catalytic alkylation and isomerisation. (orig.) [Deutsch] Ein intern zirkulierendes Wirbelschichtsystem zur Durchfuehrung des Fluid Catalytic Cracking Verfahrens wurde entwickelt. Die Technikumsanlage wurde fuer eine Feedrate von ca. 1 bis 4 kg/h ausgelegt. Basierend auf Daten aus der Literatur (z.B. Temperatur, Kat-Oel-Verhaeltnis und Kontaktzeit) wurde das Heissmodell aus einer Spezialstahllegierung gefertigt und aufgebaut. Wichtige stroemungsmechanische Parameter, wie die Umlaufrate und Gastrenneffizienz zwischen dem Reaktor und dem Regenerator, wurden in einem Modell aus Acrylglas (sogenanntes Kaltmodell) bei Raumtemperatur bestimmt. Um die Aehnlichkeit zwischen dem Kalt- und dem

  12. Lewis base activation of Lewis acids: catalytic, enantioselective vinylogous aldol addition reactions.

    Science.gov (United States)

    Denmark, Scott E; Heemstra, John R

    2007-07-20

    The generality of Lewis base catalyzed, Lewis acid mediated, enantioselective vinylogous aldol addition reactions has been investigated. The combination of silicon tetrachloride and chiral phosphoramides is a competent catalyst for highly selective additions of a variety of alpha,beta-unsaturated ketone-, 1,3-diketone-, and alpha,beta-unsaturated amide-derived dienolates to aldehydes. These reactions provided high levels of gamma-site selectivity for a variety of substitution patterns on the dienyl unit. Both ketone- and morpholine amide-derived dienol ethers afforded high enantio- and diastereoselectivity in the addition to conjugated aldehydes. Although alpha,beta-unsaturated ketone-derived dienolate did not react with aliphatic aldehydes, alpha,beta-unsaturated amide-derived dienolates underwent addition at reasonable rates affording high yields of vinylogous aldol product. The enantioselectivities achieved with the morpholine derived-dienolate in the addition to aliphatic aldehydes was the highest afforded to date with the silicon tetrachloride-chiral phosphoramide system. Furthermore, the ability to cleanly convert the morpholine amide to a methyl ketone was demonstrated.

  13. Catalytic and peroxidase-like activity of carbon based-AuPd bimetallic nanocomposite produced using carbon dots as the reductant

    International Nuclear Information System (INIS)

    Yang, Liuqing; Liu, Xiaoying; Lu, Qiujun; Huang, Na; Liu, Meiling; Zhang, Youyu; Yao, Shouzhuo

    2016-01-01

    In this report, carbon-based AuPd bimetallic nanocomposite (AuPd/C NC) was synthesized using carbon dots (C-dots) as the reducing agent and stabilizer by a simple green sequential reduction strategy, without adding other agents. The as synthesized AuPd/C NC showed good catalytic activity and peroxidase-like property. The structure and morphology of these nanoparticles were clearly characterized by UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The AuPd/C NC catalyst exhibits noticeably higher catalytic activity than Pd and Au nanoparticles in catalysis reduction of 4-nitrophenol (4-NP). Moreover, based on the high peroxidase-like property of AuPd/C NC, a new colorimetric detection method for hydrogen peroxide (H 2 O 2 ) has been designed using 3,3′,5,5′-tetramethyl-benzidine (TMB) as the substrate, which provides a simple and sensitive means to detect H 2 O 2 in wide linear range of 5 μM–500 μM and 500 μM–4 mM with low detection limit of 1.6 μM (S/N = 3). Therefore, the facile synthesis strategy for bimetallic nanoparticles by the mild reductant of carbon dot will provide some new thoughts for preparing of carbon-based metal nanomaterials and expand their application in catalysis and analytical chemistry areas. - Highlights: • Carbon-based AuPd bimetallic nanocomposite was synthesized using carbon dots. • The green sequential reduction strategy synthesis method is simple, green, convenient and effective. • The as synthesized AuPd/C NC showed good catalytic activity and peroxidase-like activity. • The AuPd/C NC exhibits noticeably higher catalytic activity in reduction of 4-nitrophenol. • A new colorimetric detection method for hydrogen peroxide based on AuPd/C NC was proposed.

  14. Synergic catalytic effect of Ti hydride and Nb nanoparticles for improving hydrogenation and dehydrogenation kinetics of Mg-based nanocomposite

    Directory of Open Access Journals (Sweden)

    Xiujuan Ma

    2017-02-01

    Full Text Available The Mg-9.3 wt% (TiH1.971-TiH−0.7 wt% Nb nanocomposite has been synthesized by hydrogen plasma-metal reaction (HPMR approach to enhance the hydrogen sorption kinetics of Mg at moderate temperatures by providing nanosizing effect of increasing H “diffusion channels” and adding transition metallic catalysts. The Mg nanoparticles (NPs were in hexagonal shape range from 50 to 350 nm and the average size of the NPs was 177 nm. The small spherical TiH1.971, TiH and Nb NPs of about 25 nm uniformly decorated on the surface of the big Mg NPs. The Mg-TiH1.971-TiH-Nb nanocomposite could quickly absorb 5.6 wt% H2 within 5 min at 573 K and 4.5 wt% H2 within 5 min at 523 K, whereas the pure Mg prepared by HPMR could only absorb 4 and 1.5 wt% H2 at the same temperatures. TiH1.971, TiH and Nb NPs transformed into TiH2 and NbH during hydrogenation and recovered after dehydrogenation process. The apparent activation energies of the nanocomposite for hydrogenation and dehydrogenation were 45.0 and 50.7 kJ mol−1, which are much smaller than those of pure Mg NPs, 123.8 and 127.7 kJ mol−1. The improved sorption kinetics of the Mg-based nanocomposite at moderate temperatures and the small activation energy can be interpreted by the nanostructure of Mg and the synergic catalytic effects of Ti hydrides and Nb NPs.

  15. Catalytic effect of additional metallic phases on the hydrogen absorption behavior of a Zr-Based alloy

    International Nuclear Information System (INIS)

    Ruiz, F; Peretti, H; Castro, E; Real, S; Visitin, A; Triaca, W

    2005-01-01

    The electrochemical hydrogen absorption of electrodes containing Zr 0 .9Ti 0 .1(Ni 0 .5Mn 0 .25Cr 0 .20V 0 .05) 2 is studied in alkaline media by monitoring the activation and discharge capacity along charge-discharge cycling.The considered alloy is tested in both as melted and annealed condition in order to investigate the catalytic effect of small amounts of micro segregated secondary phases of the Zr-Ni system. Since these catalytic phases are only present in the as melted alloys, tests are also carried out using a composite material elaborated from powders of the annealed alloy with the addition of 18 wt.% of the suspected catalytic phases, melted separately.The hydrogen absorption-desorption behavior for the different cases is discussed and correlated with the metallurgical characterization of the materials.The catalytic effects are studied employing cyclic voltammetry and electrochemical impedance techniques. The results are analyzed in terms of a developed physicochemical model

  16. Catalytic Layer Optimization for Hydrogen Permeation Membranes Based on La5.5WO11.25-δ/La0.87Sr0.13CrO3-δComposites.

    Science.gov (United States)

    Escolástico, Sonia; Solı S, Cecilia; Kjølseth, Christian; Serra, Jose Manuel

    2017-10-18

    (LWO/LSC) composite is one of the most promising mixed ionic-electronic conducting materials for hydrogen separation at high temperature. However, these materials present limited catalytic surface activity toward H 2 activation and water splitting, which determines the overall H 2 separation rate. For the implementation of these materials as catalytic membrane reactors, effective catalytic layers have to be developed that are compatible and stable under the reaction conditions. This contribution presents the development of catalytic layers based on sputtered metals (Cu and Pd), electrochemical characterization by impendace spectroscopy, and the study of the H 2 flow obtained by coating them on 60/40-LWO/LSC membranes. Stability of the catalytic layers is also evaluated under H 2 permeation conditions and CH 4 -containing atmospheres.

  17. A review of carbon-based and non-carbon-based catalyst supports for the selective catalytic reduction of nitric oxide.

    Science.gov (United States)

    Anthonysamy, Shahreen Binti Izwan; Afandi, Syahidah Binti; Khavarian, Mehrnoush; Mohamed, Abdul Rahman Bin

    2018-01-01

    Various types of carbon-based and non-carbon-based catalyst supports for nitric oxide (NO) removal through selective catalytic reduction (SCR) with ammonia are examined in this review. A number of carbon-based materials, such as carbon nanotubes (CNTs), activated carbon (AC), and graphene (GR) and non-carbon-based materials, such as Zeolite Socony Mobil-5 (ZSM-5), TiO 2 , and Al 2 O 3 supported materials, were identified as the most up-to-date and recently used catalysts for the removal of NO gas. The main focus of this review is the study of catalyst preparation methods, as this is highly correlated to the behaviour of NO removal. The general mechanisms involved in the system, the Langmuir-Hinshelwood or Eley-Riedeal mechanism, are also discussed. Characterisation analysis affecting the surface and chemical structure of the catalyst is also detailed in this work. Finally, a few major conclusions are drawn and future directions for work on the advancement of the SCR-NH 3 catalyst are suggested.

  18. Catalytic reforming methods

    Science.gov (United States)

    Tadd, Andrew R; Schwank, Johannes

    2013-05-14

    A catalytic reforming method is disclosed herein. The method includes sequentially supplying a plurality of feedstocks of variable compositions to a reformer. The method further includes adding a respective predetermined co-reactant to each of the plurality of feedstocks to obtain a substantially constant output from the reformer for the plurality of feedstocks. The respective predetermined co-reactant is based on a C/H/O atomic composition for a respective one of the plurality of feedstocks and a predetermined C/H/O atomic composition for the substantially constant output.

  19. Production of gaseous fuel from jatropha oil by cerium oxide based catalytic fuel reactor and its utilisation on diesel engine

    Directory of Open Access Journals (Sweden)

    Mylswamy Thirunavukkarasu

    2016-01-01

    Full Text Available In this study, an attempt is made to produce a hydrocarbon fuel from jatropha vegetable oil for Diesel engine applications. The “catalytic cracking” a process recently introduced by the researchers is chosen as an alternative method to trans-esterification process to match the fuel properties to diesel. Jatropha vegetable oil was cracked into a gas using the cerium oxide catalyst in a fixed bed catalytic reactor. The produced gas is introduced at constant rate into the inlet manifold of the Diesel engine. The experimental work was carried out in single cylinder water cooled direct injection Diesel engine coupled with eddy current dynamometer. The combustion parameters are measured by AVL combustion analyser. From the experimental results, the increase in brake thermal efficiency of the engine for full load was observed to be 10% (relative compared with diesel. Notably, emissions such as HC, CO, and smoke are reduced by 18%, 61%, and 18%, respectively, when compared with diesel.

  20. Preparation, structural characterization, and catalytic performance of Pd(II) and Pt(II) complexes derived from cellulose Schiff base

    Science.gov (United States)

    Baran, Talat; Yılmaz Baran, Nuray; Menteş, Ayfer

    2018-05-01

    In this study, we reported production, characterization, and catalytic behavior of two novel heterogeneous palladium(II) and platinum(II) catalysts derived from cellulose biopolymer. In order to eliminate the use of toxic organic or inorganic solvents and to reduce the use of excess energy in the coupling reactions, we have developed a very simple, rapid, and eco-friendly microwave irradiation protocol. The developed microwave-assisted method of Suzuki cross coupling reactions produced excellent reaction yields in the presence of cellulose supported palladium and platinum (II) catalysts. Moreover, the catalysts easily regenerated after simple filtration, and they gave good reusability. This study revealed that the designed catalysts and method provide clean, simple, rapid, and impressive catalytic performance for Suzuki coupling reactions.

  1. Mononuclear Nickel(II Complexes with Schiff Base Ligands: Synthesis, Characterization, and Catalytic Activity in Norbornene Polymerization

    Directory of Open Access Journals (Sweden)

    Yi-Mei Xu

    2017-03-01

    Full Text Available The nickel(II catalyst has manifested higher catalytic activity compared to that of other late transition metal catalysts for norbornene polymerization. Therefore, several structurally similar trans-nickel(II compounds of N,O-chelate bidentate ligands were synthesized and characterized. Both the electronic effect and the steric hindrance influence polymerization. The molecular structures of 2, 4 and 5 were further confirmed by single-crystal X-ray diffraction.

  2. Binary and Ternary Catalytic Systems for Olefin Metathesis Based on MoCl5/SiO2

    Science.gov (United States)

    Bykov, Victor I.; Belyaev, Boris A.; Butenko, Tamara A.; Finkelshtein, Eugene Sh.

    Kinetics of α-olefin metathesis in the presence of binary (MoCl5/ SiO2-Me4Sn) and ternary catalytic systems (MoCl5/SiO2-Me4Sn-ECl4, E = Si or Ge) was studied. Specifically, kinetics and reactivity of 1-decene, 1-octene, and 1-hexene in the metathesis reaction at 27°C and 50°C in the presence of MoCl5/ SiO2-SnMe4 were examined and evaluated in detail. It was shown that experimental data comply well with the simple kinetic equation for the rate of formation of symmetrical olefins with allowance for the reverse reaction and catalyst deactivation: r = left( {k_1 \\cdot c_α - k_{ - 1} \\cdot c_s } right) \\cdot e^{ - k_d \\cdot tilde n_{tot} } . The coefficients for this equation were determined, and it was shown that these α-olefins had practically the same reactivity. It was found that reactivation in the course of metathesis took place due to the addition of a third component (silicon tetrachloride or germanium tetrachloride in combination with tetramethyltin) to a partially deactivated catalyst. The number of active centers was determined (5-6% of the amount of Mo) and the mechanisms of formation, deactivation, and reactivation were proposed for the binary and ternary catalytic systems. The role of individual components of the catalytic systems was revealed.

  3. Dye sensitized solar cell based on platinum decorated multiwall carbon nanotubes as catalytic layer on the counter electrode

    International Nuclear Information System (INIS)

    Mathew, Ambily; Rao, G. Mohan; Munichandraiah, N.

    2011-01-01

    Graphical abstract: I-V characteristics of the DSSCs with Pt CE and Pt/MWCNT CE measured at 100 mW/cm 2 . It shows relatively better performance with Pt/MWCNT counter electrodes. Highlights: → Synthesis of multiwalled carbon nanotubes by pyrolysis. → Synthesis of Pt/MWCNT composite by chemical reduction. → Fabrication DSSC using Pt/MWCNT as catalytic layer on the counter electrode. → Study of catalytic activity by Electrochemical Impedance Spectroscopy. -- Abstract: In this study we have employed multiwall carbon nanotubes (MWCNT), decorated with platinum as catalytic layer for the reduction of tri-iodide ions in dye sensitized solar cell (DSSC). MWCNTs have been prepared by a simple one step pyrolysis method using ferrocene as the catalyst and xylene as the carbon source. Platinum decorated MWCNTs have been prepared by chemical reduction method. The as prepared MWCNTs and Pt/MWCNTs have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In combination with a dye adsorbed TiO 2 photoanode and an organic liquid electrolyte, Pt/MWCNT composite showed an enhanced short circuit current density of 16.12 mA/cm 2 leading to a cell efficiency of 6.50% which is comparable to that of Platinum.

  4. Dye sensitized solar cell based on platinum decorated multiwall carbon nanotubes as catalytic layer on the counter electrode

    Energy Technology Data Exchange (ETDEWEB)

    Mathew, Ambily [Department of Instrumentation and Applied Physics, Indian Institute of Science, Bangalore 560012 India (India); Rao, G. Mohan, E-mail: gmrao@isu.iisc.ernet.in [Department of Instrumentation and Applied Physics, Indian Institute of Science, Bangalore 560012 India (India); Munichandraiah, N. [Department of Inorgonic and Physical Chemistry, Indian Institute of Science, Bangalore 560012 India (India)

    2011-11-15

    Graphical abstract: I-V characteristics of the DSSCs with Pt CE and Pt/MWCNT CE measured at 100 mW/cm{sup 2}. It shows relatively better performance with Pt/MWCNT counter electrodes. Highlights: {yields} Synthesis of multiwalled carbon nanotubes by pyrolysis. {yields} Synthesis of Pt/MWCNT composite by chemical reduction. {yields} Fabrication DSSC using Pt/MWCNT as catalytic layer on the counter electrode. {yields} Study of catalytic activity by Electrochemical Impedance Spectroscopy. -- Abstract: In this study we have employed multiwall carbon nanotubes (MWCNT), decorated with platinum as catalytic layer for the reduction of tri-iodide ions in dye sensitized solar cell (DSSC). MWCNTs have been prepared by a simple one step pyrolysis method using ferrocene as the catalyst and xylene as the carbon source. Platinum decorated MWCNTs have been prepared by chemical reduction method. The as prepared MWCNTs and Pt/MWCNTs have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In combination with a dye adsorbed TiO{sub 2} photoanode and an organic liquid electrolyte, Pt/MWCNT composite showed an enhanced short circuit current density of 16.12 mA/cm{sup 2} leading to a cell efficiency of 6.50% which is comparable to that of Platinum.

  5. Preparation of acid-base bifunctional mesoporous KIT-6 (KIT: Korea Advanced Institute of Science and Technology) and its catalytic performance in Knoevenagel reaction

    International Nuclear Information System (INIS)

    Xu, Ling; Wang, Chunhua; Guan, Jingqi

    2014-01-01

    Acid-base bifunctional mesoporous catalysts Al-KIT-6-NH 2 containing different aluminum content have been synthesized through post synthetic grafting method. The materials were characterized by X-ray diffraction (XRD), scanning electron micrographs (SEM), transmission electron micrographs (TEM), Fourier-transform infrared spectroscopy (FTIR), IR spectra of pyridine adsorption, NH 3 -TPD and TG analysis. The characterization results indicated that the pore structure of KIT-6 was well kept after the addition of aluminum and grafting of aminopropyl groups. The acid amount of Al-KIT-6 increased with enhancing aluminum content. Catalytic results showed that weak acid and weak base favor the Knoevenagel reaction, while catalysts with strong acid and weak base exhibited worse catalytic behavior. - Graphical abstract: The postulated steps of mechanism for the acid-base catalyzed process are as follows: (1) the aldehyde gets activated by the surface acidic sites which allow the amine undergoes nucleophilic to attack the carbonyl carbon of benzaldehyde. (2) Water is released in the formation of imine intermediate. (3) The ethyl cyanoacetate reacts with the intermediate. (4) The benzylidene ethyl cyanoacetate is formed and the amine is regenerated. - Highlights: • KIT-6 and Al-KIT-6-NH 2 with different Si/Al ratios has been successfully prepared. • 79.4% Yield was obtained over 46-Al-KIT-6-NH 2 within 20 min in Knoevenagel reaction. • Low Al-content Al-KIT-6-NH 2 shows better catalytic stability than high Al-content catalysts. • There is acid-base synergistic effect in Knoevenagel reaction

  6. Lewis base activation of Lewis acids: catalytic, enantioselective addition of glycolate-derived silyl ketene acetals to aldehydes.

    Science.gov (United States)

    Denmark, Scott E; Chung, Won-Jin

    2008-06-20

    A catalytic system involving silicon tetrachloride and a chiral, Lewis basic bisphosphoramide catalyst is effective for the addition of glycolate-derived silyl ketene acetals to aldehydes. It was found that the sense of diastereoselectivity could be modulated by changing the size of the substituents on the silyl ketene acetals. In general, the trimethylsilyl ketene acetals derived from methyl glycolates with a large protecting group on the alpha-oxygen provide enantiomerically enriched alpha,beta-dihydroxy esters with high syn-diastereoselectivity, whereas the tert-butyldimethylsilyl ketene acetals derived from bulky esters of alpha-methoxyacetic acid provide enantiomerically enriched alpha,beta-dihydroxy esters with high anti-diastereoselecitvity.

  7. Non-Catalytic and MgSO4 - Catalyst based Degradation of Glycerol in Subcritical and Supercritical Water Media

    Directory of Open Access Journals (Sweden)

    Mahfud Mahfud

    2011-02-01

    Full Text Available This research aims to study the glycerol degradation reaction in subcritical and supercritical water media. The degradation of glycerol into other products was performed both with sulphate salt catalysts and without catalyst. The reactant was made from glycerol and water with the mass ratio of 1:10. The experiments were carried out using a batch reactor at a constant pressure of 250 kgf/cm2, with the temperature range of 200-400oC, reaction time of 30 minutes, and catalyst mol ratio in glycerol of 1:10 and 1:8. The products of the non-catalytic glycerol degradation were acetaldehyde, methanol, and ethanol. The use of sulphate salt as catalyst has high selectivity to acetaldehyde and still allows the formation alcohol product in small quantities. The mechanism of ionic reaction and free radical reaction can occur at lower temperature in hydrothermal area or subcritical water. Conversion of glycerol on catalytic reaction showed a higher yield when compared with the reaction performed without catalyst

  8. Catalytic activity and effect of modifiers on Ni-based catalysts for the dry reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Barroso-Quiroga, Maria Martha; Castro-Luna, Adolfo Eduardo [Facultad de Ingenieria y Ciencias Economico-Sociales INTEQUI-CONICET-UNSL, Av. 25 de Mayo 384 (5730) Villa Mercedes (S.L.) (Argentina)

    2010-06-15

    Ni catalysts supported on different ceramic oxides (Al{sub 2}O{sub 3}, CeO{sub 2}, La{sub 2}O{sub 3}, ZrO{sub 2}) were prepared by wet impregnation. The catalytic behavior toward hydrogen production through the dry reforming of methane using a fixed-bed reactor was evaluated under certain experimental conditions, and the catalyst supported on ZrO{sub 2} showed the highest stable activity during the period of time studied. The catalyst supported on CeO{sub 2} has a relatively good activity, but shows signs of deactivation after a certain time during the reaction. This catalyst was chosen to be studied after the addition of 0.5 wt% Li and K as activity modifiers. The introduction of the alkaline metals produces a reduction of the catalytic activity but a better stability over the reactant conversion time. The reverse water-gas shift reaction influences the global system of reactions, and as the results indicate, should be considered near equilibrium. (author)

  9. Contributions to the theory of catalytic titrations-III Neutralization catalytic titrations.

    Science.gov (United States)

    Gaál, F F; Abramović, B F

    1985-07-01

    Neutralization catalytic titrations of weak monoprotic adds and bases with both volumetric and coulometric addition of the titrant (strong base/acid) have been simulated by taking into account the equilibrium concentration of the catalyst during the titration. The influence of several factors on the shape of the simulated catalytic titration curve has been investigated and is discussed.

  10. Physico-chemical characterisations and catalytic performance of Ni-based catalyst systems for dry reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Vlach, K.; Hoang, D.L.; Schneider, M.; Pohl, M.M.; Armbruster, U.; Martin, A. [Rostock Univ. (Germany). Leibniz-Institut fuer Katalyse e.V.

    2012-07-01

    In this study, ternary perovskite type oxides LaNi{sub x}Cu{sub 1-x}O{sub 3} (x = 0, 0.2, 0.5, 0.8, 1) were synthesized using NaOH and diethylenetriaminepentaacetic acid (H{sub 5}DTPA). The catalysts resulting from perovskite precursors exhibit catalytic activities for CO{sub 2} reforming of CH{sub 4} at 700 C that increase with a higher Ni content. Characterization methods showed that the activation led to formation of small metallic Ni/Cu particles. Methane and carbon dioxide conversions varied from 20 to 65% for CH{sub 4} and 3 to 58% for CO{sub 2}. Selectivities from 46 to 93% for CO and from 4 to 64% for H{sub 2} were obtained. (orig.)

  11. Progress in palladium-based catalytic systems for the sustainable synthesis of annulated heterocycles: a focus on indole backbones.

    Science.gov (United States)

    Platon, Mélanie; Amardeil, Régine; Djakovitch, Laurent; Hierso, Jean-Cyrille

    2012-05-21

    A survey highlighting the most recent palladium catalytic systems produced and their performances for progress in direct synthesis of indole backbones by heterocarbocyclization of reactive substrates is provided. The discussion is developed in relation with the principles of sustainable chemistry concerning atom and mass economy. In this respect, the general convergent character of the syntheses is of particular interest (one-pot, domino, cascade or tandem reactions), and the substrates accessibility and reactivity, together with the final waste production, are also important. This critical review clearly indicates that the development of ligand chemistry, mainly phosphines and carbenes, in the last few decades gave a significant impetus to powerful functionalization of indoles at virtually all positions of this ubiquitous backbone (118 references).

  12. The influence of calcination temperature on catalytic activities in a Co based catalyst for CO2 dry reforming

    International Nuclear Information System (INIS)

    Song, Sang-Hoon; Son, Ju-Hee; Budiman, Anatta Wahyu; Choi, Myoung-Jae; Chang, Tae-Sun; Shin, Chae-Ho

    2014-01-01

    The carbon dioxide dry reforming of methane (CDR) reaction could be thermodynamically favored in the range of 800 to 1,000 .deg. C. However, the catalyst in this reaction should be avoided at the calcination temperature over 800 .deg. C since strong metal support interaction (SMSI) in this temperature range can decrease activity due to loss of active sites. Therefore, we focused on optimizing the temperature of pretreatment and a comparison of surface characterization results for CDR. Results related to metal sintering over support, re-dispersion by changing of particle size of metal-support, and strong metal support interaction were observed and confirmed in this work. In our conclusion, optimum calcination temperature for a preparation of catalyst was proposed that 400 .deg. C showed a higher and more stable catalytic activity without changing of support characteristics

  13. Catalytic Oligopeptide Synthesis.

    Science.gov (United States)

    Liu, Zijian; Noda, Hidetoshi; Shibasaki, Masakatsu; Kumagai, Naoya

    2018-02-02

    Waste-free catalytic assembly of α-amino acids is fueled by a multiboron catalyst that features a characteristic B 3 NO 2 heterocycle, providing a versatile catalytic protocol wherein functionalized natural α-amino acid units are accommodated and commonly used protecting groups are tolerated. The facile dehydrative conditions eliminate the use of engineered peptide coupling reagents, exemplifying a greener catalytic alternative for peptide coupling. The catalysis is sufficiently robust to enable pentapeptide synthesis, constructing all four amide bond linkages in a catalytic fashion.

  14. Ferrous ion as a reducing agent in the generation of antibiofilm nitric oxide from a copper-based catalytic system.

    Science.gov (United States)

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

    2018-01-31

    The work found that the electron-donating properties of ferrous ions (Fe 2+ ) can be used for the conversion of nitrite (NO 2 - ) into the biofilm-dispersing signal nitric oxide (NO) by a copper(II) complex (CuDTTCT) catalyst, a potentially applicable biofilm control technology for the water industries. The availability of Fe 2+ varied depending on the characteristics of the aqueous systems (phosphate- and carbonate-containing nitrifying bacteria growth medium, NBGM and phosphate buffered saline, PBS at pH 6 to 8, to simulate conditions typically present in the water industries) and was found to affect the production of NO from nitrite by CuDTTCT (casted into PVC). Greater amounts of NO were generated from the CuDTTCT-nitrite-Fe 2+ systems in PBS compared to those in NBGM, which was associated with the reduced extent of Fe 2+ -to-Fe 3+ autoxidation by the iron-precipitating moieties phosphates and carbonate in the former system. Further, acidic conditions at pH 6.0 were found to favor NO production from the catalytic system in both PBS and NBGM compared to neutral or basic pH (pH 7.0 or 8.0). Lower pH was shown to stabilize Fe 2+ and reduce its autoxidation to Fe 3+ . These findings will be beneficial for the potential implementation of the NO-generating catalytic technology and indeed, a 'non-killing' biofilm dispersal activity of CuDTTCT-nitrite-Fe 2+ was observed on nitrifying bacteria biofilms in PBS at pH 6. Copyright © 2018 Elsevier Inc. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    K. Maduna Valkaj

    2015-01-01

    Full Text Available The necessity to remove organic pollutants from the industrial wastewater streams has forced the development of new technologies that can produce better results in terms of pollutant removal and process efficiency in combination with low investment and operating costs. One of the new emerging processes with a potential to fulfil these demands is catalytic wet peroxide oxidation, commonly known as the CWPO process. The oxidative effect of the hydrogen peroxide is intensified by the addition of a heterogeneous catalyst that can reduce the operating conditions to atmospheric pressure and temperatures below 383 K. Zeolites, among others, are especially appealing as catalysts for selective oxidation processes due to their unique characteristics such as shape selectivity, thermal and chemical stability, and benign effect on nature and the living world. In this work, catalytic activity, selectivity and stability of Cu/Y-5 zeolite in phenol oxidation with hydrogen peroxide was examined. Catalyst samples were prepared by ion exchange method of the protonic form of commercial zeolite. The catalysts were characterized with powder X-ray diffraction (XRD, scanning electron microscopy (SEM, and AAS elemental analysis, while the adsorption techniques were used for the measurement of the specific surface area. The catalytic tests were carried out in a stainless steel Parr reactor in batch operation mode at the atmospheric pressure and in the temperature range from 323 to 353 K. The catalyst was prepared in powdered form and the mass fraction of the active metal component on the zeolite was 3.46 %. The initial concentration of phenol solution was equal to 0.01 mol dm−3 and the concentration of hydrogen peroxide ranged from 0.01 to 0.10 mol dm−3. The obtained experimental data was tested to a proposed kinetic model for phenol oxidation r = k1 cF cVP and hydrogen peroxide decomposition rHP = k2 cHP. The kinetic parameters were estimated using the Nelder

  16. EQCM Immunoassay for Phosphorylated Acetylcholinesterase as a Biomarker for Organophosphate Exposures Based on Selective Zirconia Adsorption and Enzyme-Catalytic Precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hua; Wang, Jun; Choi, Daiwon; Tang, Zhiwen; Wu, Hong; Lin, Yuehe

    2009-03-01

    A zirconia (ZrO2) adsorption-based immunoassay by electrochemical quartz crystal microbalance (EQCM) has been initially developed, aiming at the detection of phosphorylated acetylcholinesterase (AChE) as a potential biomarker for bio-monitoring exposures to organophosphate (OP) pesticides and chemical warfare agents. Hydroxyl-derivatized monolayer was preferably chosen to modify the crystal serving as the template for directing the electro-deposition of ZrO2 film with uniform nanostructures. The resulting ZrO2 film was utilized to selectively capture phosphorylated AChE from the sample media. Horseradish peroxidase (HRP)-labeled anti-AChE antibodies were further employed to recognize the captured phosphorylated protein. Enzyme-catalytic oxidation of the benzidine substrate resulted in the accumulation of insoluble product on the functionalized crystal. Ultrasensitive EQCM quantification by mass-amplified frequency responses as well as rapid qualification by visual color changes of product could be thus achieved. Moreover, 4-chloro-1-naphthol (CN) was comparably studied as an ideal chromogenic substrate for the enzyme-catalytic precipitation. Experimental results show that the developed EQCM technique can allow for the detection of phosphorylated AChE in human plasma. Such an EQCM immunosensing format opens a new door towards the development of simple, sensitive, and field-applicable biosensor for biologically monitoring low-level OP exposures.

  17. Iminopyridine-Based Cobalt(II and Nickel(II Complexes: Synthesis, Characterization, and Their Catalytic Behaviors for 1,3-Butadiene Polymerization

    Directory of Open Access Journals (Sweden)

    Quanquan Dai

    2016-01-01

    Full Text Available A series of iminopyridine ligated Co(II (1a–7a and Ni(II (1b–7b complexes were synthesized. The structures of complexes 3a, 4a, 5a, 7a, 5b, and 6b were determined by X-ray crystallographic analyses. Complex 3a formed a chloro-bridged dimer, whereas 4a, 5a, and 7a, having a substituent (4a, 5a: CH3; 7a: Br at the 6-position of pyridine, producing the solid structures with a single ligand coordinated to the central metal. The nickel atom in complex 5b features distorted trigonal-bipyramidal geometry with one THF molecule ligating to the metal center. All the complexes activated by ethylaluminum sesquichloride (EASC were evaluated in 1,3-butadiene polymerization. The catalytic activity and selectivity were significantly influenced by the ligand structure and central metal. Comparing with the nickel complexes, the cobalt complexes exhibited higher catalytic activity and cis-1,4-selectivity. For both the cobalt and nickel complexes, the aldimine-based complexes showed higher catalyst activity than their ketimine counterparts.

  18. Proximity hybridization-regulated catalytic DNA hairpin assembly for electrochemical immunoassay based on in situ DNA template-synthesized Pd nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Fuyi [School of Chemistry and Chemical Engineering, Jiangsu Normal University, Xuzhou 221116 (China); Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, Department of Pharmaceutical Analysis, School of Pharmacy, Xuzhou Medical College, 221004, Xuzhou (China); Yao, Yao; Luo, Jianjun; Zhang, Xing; Zhang, Yu; Yin, Dengyang [Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, Department of Pharmaceutical Analysis, School of Pharmacy, Xuzhou Medical College, 221004, Xuzhou (China); Gao, Fenglei, E-mail: jsxzgfl@sina.com [Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, Department of Pharmaceutical Analysis, School of Pharmacy, Xuzhou Medical College, 221004, Xuzhou (China); Wang, Po, E-mail: wangpo@jsnu.edu.cn [School of Chemistry and Chemical Engineering, Jiangsu Normal University, Xuzhou 221116 (China)

    2017-05-29

    Novel hybridization proximity-regulated catalytic DNA hairpin assembly strategy has been proposed for electrochemical immunoassay based on in situ DNA template-synthesized Pd nanoparticles as signal label. The DNA template-synthesized Pd nanoparticles were characterized with atomic force microscopic and X-ray photoelectron spectroscopy. The highly efficient electrocatalysis by DNA template synthesized Pd nanoparticles for NaBH{sub 4} oxidation produced an intense detection signal. The label-free electrochemical method achieved the detection of carcinoembryonic antigen (CEA) with a linear range from 10{sup −15} to 10{sup −11} g mL{sup −1} and a detection limit of 0.43 × 10{sup −15} g mL{sup −1}. Through introducing a supersandwich reaction to increase the DNA length, the electrochemical signal was further amplified, leading to a detection limit of 0.52 × 10{sup −16} g mL{sup −1}. And it rendered satisfactory analytical performance for the determination of CEA in serum samples. Furthermore, it exhibited good reproducibility and stability; meanwhile, it also showed excellent specificity due to the specific recognition of antigen by antibody. Therefore, the DNA template synthesized Pd nanoparticles based signal amplification approach has great potential in clinical applications and is also suitable for quantification of biomarkers at ultralow level. - Graphical abstract: A novel label-free and enzyme-free electrochemical immunoassay based on proximity hybridization-regulated catalytic DNA hairpin assemblies for recycling of the CEA. - Highlights: • A novel enzyme-free electrochemical immunosensor was developed for detection of CEA. • The signal amplification was based on catalytic DNA hairpin assembly and DNA-template-synthesized Pd nanoparticles. • The biosensor could detect CEA down to 0.52 × 10{sup −16} g mL{sup −1} level with a dynamic range spanning 5 orders of magnitude.

  19. A catalytic and dual recycling amplification ATP sensor based on target-driven allosteric structure switching of aptamer beacons.

    Science.gov (United States)

    Peng, Ying; Li, Daxiu; Yuan, Ruo; Xiang, Yun

    2018-05-15

    Abnormal concentrations of ATP are associated with many diseases and cancers, and quantitative detection of ATP is thus of great importance for disease diagnosis and prognosis. In the present work, we report a new dual recycling amplification sensor integrated with catalytic hairpin assembly (CHA) to achieve high sensitivity for fluorescent detection of ATP. The association of the target ATP with the aptamer beacons causes the allosteric structure switching of the aptamer beacons to expose the toehold regions, which hybridize with and unfold the fluorescently quenched hairpin signal probes (HP1) to recycle the target ATP and to trigger CHA between HP1 and the secondary hairpin probes (HP2) to form HP1/HP2 duplexes. Due to the recycling amplification, the presence of ATP leads to the formation of many HP1/HP2 duplexes, generating dramatically amplified fluorescent signals for sensitive detection of ATP. Under optimal experimental conditions, our sensor linearly responds to ATP in the range from 25 to 600nM with a calculated detection limit of 8.2nM. Furthermore, the sensor shows a high selectivity and can also be used to detect ATP in human serums to realize its application for real samples. With the distinct advantage of significant signal amplification without the involvement of any nanomaterial and enzyme, the developed sensor thus holds great potential for simple and sensitive detection of different small molecules and proteins. Copyright © 2018 Elsevier B.V. All rights reserved.

  20. Enzyme catalytic amplification of miRNA-155 detection with graphene quantum dot-based electrochemical biosensor.

    Science.gov (United States)

    Hu, Tianxing; Zhang, Le; Wen, Wei; Zhang, Xiuhua; Wang, Shengfu

    2016-03-15

    A specific and sensitive method was developed for quantitative detection of miRNA by integrating horseradish peroxidase (HRP)-assisted catalytic reaction with a simple electrochemical RNA biosensor. The electrochemical biosensor was constructed by a double-stranded DNA structure. The structure was formed by the hybridization of thiol-tethered oligodeoxynucleotide probes (capture DNA), assembled on the gold electrode surface, with target DNA and aminated indicator probe (NH2-DNA). After the construction of the double-stranded DNA structure, the activated carboxyl groups of graphene quantum dots (GQDs) assembled on NH2-DNA. GQDs were used as a new platform for HRP immobilization through noncovalent assembly. HRP modified biosensor can effectively catalyze the hydrogen peroxide (H2O2)-mediated oxidation of 3,3',5,5'-tetramethylbenzidine (TMB), accompanied by a change from colorless to blue in solution color and an increased electrochemical current signal. Due to GQDs and enzyme catalysis, the proposed biosensor could sensitively detect miRNA-155 from 1 fM to 100 pM with a detection limit of 0.14 fM. High performance of the biosensor is attributed to the large surface-to-volume ratio, excellent compatibility of GQDs. For these advantages, the proposed method holds great potential for analysis of other interesting tumor makers. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Comparison and analysis of zinc and cobalt-based systems as catalytic entities for the hydration of carbon dioxide.

    Directory of Open Access Journals (Sweden)

    Edmond Y Lau

    Full Text Available In nature, the zinc metalloenzyme carbonic anhydrase II (CAII efficiently catalyzes the conversion of carbon dioxide (CO2 to bicarbonate under physiological conditions. Many research efforts have been directed towards the development of small molecule mimetics that can facilitate this process and thus have a beneficial environmental impact, but these efforts have met very limited success. Herein, we undertook quantum mechanical calculations of four mimetics, 1,5,9-triazacyclododedacane, 1,4,7,10-tetraazacyclododedacane, tris(4,5-dimethyl-2-imidazolylphosphine, and tris(2-benzimidazolylmethylamine, in their complexed form either with the Zn(2+ or the Co(2+ ion and studied their reaction coordinate for CO2 hydration. These calculations demonstrated that the ability of the complex to maintain a tetrahedral geometry and bind bicarbonate in a unidentate manner were vital for the hydration reaction to proceed favorably. Furthermore, these calculations show that the catalytic activity of the examined zinc complexes was insensitive to coordination states for zinc, while coordination states above four were found to have an unfavorable effect on product release for the cobalt counterparts.

  2. Comparison and analysis of zinc and cobalt-based systems as catalytic entities for the hydration of carbon dioxide.

    Science.gov (United States)

    Lau, Edmond Y; Wong, Sergio E; Baker, Sarah E; Bearinger, Jane P; Koziol, Lucas; Valdez, Carlos A; Satcher, Joseph H; Aines, Roger D; Lightstone, Felice C

    2013-01-01

    In nature, the zinc metalloenzyme carbonic anhydrase II (CAII) efficiently catalyzes the conversion of carbon dioxide (CO2) to bicarbonate under physiological conditions. Many research efforts have been directed towards the development of small molecule mimetics that can facilitate this process and thus have a beneficial environmental impact, but these efforts have met very limited success. Herein, we undertook quantum mechanical calculations of four mimetics, 1,5,9-triazacyclododedacane, 1,4,7,10-tetraazacyclododedacane, tris(4,5-dimethyl-2-imidazolyl)phosphine, and tris(2-benzimidazolylmethyl)amine, in their complexed form either with the Zn(2+) or the Co(2+) ion and studied their reaction coordinate for CO2 hydration. These calculations demonstrated that the ability of the complex to maintain a tetrahedral geometry and bind bicarbonate in a unidentate manner were vital for the hydration reaction to proceed favorably. Furthermore, these calculations show that the catalytic activity of the examined zinc complexes was insensitive to coordination states for zinc, while coordination states above four were found to have an unfavorable effect on product release for the cobalt counterparts.

  3. A broad spectrum catalytic system for removal of toxic organics from water by deep oxidation. 1998 annual progress report

    International Nuclear Information System (INIS)

    Sen, A.

    1998-01-01

    'Toxic organics and polymers pose a serious threat to the environment, especially when they are present in aquatic systems. The objective of the research is the design of practical procedures for the removal and/or recycling of such pollutants by oxidation. This report summarizes the work performed in the first one and half years of a three year project. The authors had earlier described a catalytic system for the deep oxidation of toxic organics, such as benzene, phenol and substituted phenols, aliphatic and aromatic halogenated compounds, organophosphorus, and organosulfur compounds [1]. In this system, metallic palladium was found to catalyze the oxidation of the substrate by dioxygen in aqueous medium at 80--100 C in the presence of carbon monoxide. For all the substrates examined, deep oxidation to carbon monoxide, carbon dioxide, and water occurred in high yields, resulting in up to several hundred turnovers over a 24 h period. Because of a pressing need for new procedures for the destruction of chemical warfare agents, the authors have examined in detail the deep oxidation of appropriate model compounds containing phosphorus-carbon and sulfur-carbon bonds using the same catalytic system. The result is the first observation of the efficient catalytic oxidative cleavage of phosphorus-carbon and sulfur-carbon bonds under mild conditions, using dioxygen as the oxidant [2]. In addition to the achievements described above, they have unpublished results in several other areas. For example, they have investigated the possibility of using dihydrogen rather than carbon monoxide as a coreductant in the catalytic deep oxidation of substrates. Even more attractive from a practical standpoint is the possibility of using a mixture of carbon monoxide and dihydrogen (synthesis gas). Indeed, experiments indicated that it is possible to substitute carbon monoxide by dihydrogen or synthesis gas. Significantly, in the case of nitro compounds, the deep oxidation in fact proceeded

  4. Catalytic wet air oxidation of bisphenol A solution in a batch-recycle trickle-bed reactor over titanate nanotube-based catalysts.

    Science.gov (United States)

    Kaplan, Renata; Erjavec, Boštjan; Senila, Marin; Pintar, Albin

    2014-10-01

    Catalytic wet air oxidation (CWAO) is classified as an advanced oxidation process, which proved to be highly efficient for the removal of emerging organic pollutant bisphenol A (BPA) from water. In this study, BPA was successfully removed in a batch-recycle trickle-bed reactor over bare titanate nanotube-based catalysts at very short space time of 0.6 min gCAT g(-1). The as-prepared titanate nanotubes, which underwent heat treatment at 600 °C, showed high activity for the removal of aqueous BPA. Liquid-phase recycling (5- or 10-fold recycle) enabled complete BPA conversion already at 200 °C, together with high conversion of total organic carbon (TOC), i.e., 73 and 98 %, respectively. The catalyst was chemically stable in the given range of operating conditions for 189 h on stream.

  5. 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.

  6. Catalytic Wittig and aza-Wittig reactions.

    Science.gov (United States)

    Lao, Zhiqi; Toy, Patrick H

    2016-01-01

    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.

  7. Cu-containing Keggin-type polyoxometalates-based organic-inorganic hybrids with double electro-catalytic behaviors

    Science.gov (United States)

    Zhou, Wanli; Zheng, Yanping; Peng, Jun

    2018-02-01

    Four new organic-inorganic hybrids consisting of Keggin-type polyoxometalates: [Cu5(bimpy)5(α-BW12O40)]·4H2O (1), [Cu4(bimpy)4(α-SiW12O40)]·2H2O (2), [Cu4(bimpy)4(α-HPMo12O40)2]·2H2O (3), [Cu2(bimpy)4(H2O)2(α-HPW12O40)2]·8H2O (4) (bimpy = 2,5-bis(1H-imidazol-1-yl)pyridine), have been hydrothermally synthesized. Compounds 1-4 are constructed from Cu/bimpy segments modified different types of Keggin POMs. The 1D double chains of compound 1 are featured by {-Cu/bimpy-POM-Cu/bimpy-}n chains and {-Cu-bimpy-Cu-}n metal-organic chains; compound 2 with 1D "ladder-like" structure stemmed from {-Cu-bimpy-Cu-}n wave-like chains and α-SiW12 clusters; In compound 3, [Cu4(bimpy)4]4+ motifs are linked by α-PMo12 clusters to give rise to a (3,4)-connected two-dimensional architecture with the (83)(86) topology, while compound 4 has a (3,4,5)-connected 3D framework with the (42,6)(42,6,83)(42,65,83) topology. Cyclic voltammetries of compounds 1-4 show discrepant double electro-catalytic properties for reduction of nitrite and oxidation of ascorbic acid owing to variant Keggin-type POMs and Cu/bimpy complexes.

  8. Cobalt-manganese-based spinels as multifunctional materials that unify catalytic water oxidation and oxygen reduction reactions.

    Science.gov (United States)

    Menezes, Prashanth W; Indra, Arindam; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Strasser, Peter; Driess, Matthias

    2015-01-01

    Recently, there has been much interest in the design and development of affordable and highly efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts that can resolve the pivotal issues that concern solar fuels, fuel cells, and rechargeable metal-air batteries. Here we present the synthesis and application of porous CoMn2 O4 and MnCo2 O4 spinel microspheres as highly efficient multifunctional catalysts that unify the electrochemical OER with oxidant-driven and photocatalytic water oxidation as well as the ORR. The porous materials were prepared by the thermal degradation of the respective carbonate precursors at 400 °C. The as-prepared spinels display excellent performances in electrochemical OER for the cubic MnCo2 O4 phase in comparison to the tetragonal CoMn2 O4 material in an alkaline medium. Moreover, the oxidant-driven and photocatalytic water oxidations were performed and they exhibited a similar trend in activity to that of the electrochemical OER. Remarkably, the situation is reversed in ORR catalysis, that is, the oxygen reduction activity and stability of the tetragonal CoMn2 O4 catalyst outperformed that of cubic MnCo2 O4 and rivals that of benchmark Pt catalysts. The superior catalytic performance and the remarkable stability of the unifying materials are attributed to their unique porous and robust microspherical morphology and the intrinsic structural features of the spinels. Moreover, the facile access to these high-performance materials enables a reliable and cost-effective production on a large scale for industrial applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. On the Structural Context and Identification of Enzyme Catalytic Residues

    Science.gov (United States)

    Chien, Yu-Tung; Huang, Shao-Wei

    2013-01-01

    Enzymes play important roles in most of the biological processes. Although only a small fraction of residues are directly involved in catalytic reactions, these catalytic residues are the most crucial parts in enzymes. The study of the fundamental and unique features of catalytic residues benefits the understanding of enzyme functions and catalytic mechanisms. In this work, we analyze the structural context of catalytic residues based on theoretical and experimental structure flexibility. The results show that catalytic residues have distinct structural features and context. Their neighboring residues, whether sequence or structure neighbors within specific range, are usually structurally more rigid than those of noncatalytic residues. The structural context feature is combined with support vector machine to identify catalytic residues from enzyme structure. The prediction results are better or comparable to those of recent structure-based prediction methods. PMID:23484160

  10. Numerical simulation of urea based selective non-catalytic reduction deNOx process for industrial applications

    International Nuclear Information System (INIS)

    Baleta, Jakov; Mikulčić, Hrvoje; Vujanović, Milan; Petranović, Zvonimir; Duić, Neven

    2016-01-01

    Highlights: • SNCR is a simple method for the NOx reduction from large industrial facilities. • Capabilities of the developed mathematical framework for SNCR simulation were shown. • Model was used on the geometry of experimental reactor and municipal incinerator. • Results indicate suitability of the developed model for real industrial cases. - Abstract: Industrial processes emit large amounts of diverse pollutants into the atmosphere, among which NOx takes a significant portion. Selective non-catalytic reduction (SNCR) is a relatively simple method for the NOx reduction in large industrial facilities such as power plants, cement plants and waste incinerator plants. It consists of injecting the urea-water solution in the hot flue gas stream and its reaction with the NOx. During this process flue gas enthalpy is used for the urea-water droplet heating and for the evaporation of water content. After water evaporates, thermolysis of urea occurs, during which ammonia, a known NO x reductant, and isocyanic acid are generated. In order to cope with the ever stringent environmental norms, equipment manufacturers need to develop energy efficient products that are at the same time benign to environment. This is becoming increasingly complicated and costly, and one way to reduce production costs together with the maintaining the same competitiveness level is to employ computational fluid dynamics (CFD) as a tool, in a process today commonly known under the term “virtual prototyping”. The aim of this paper is to show capabilities of the developed mathematical framework implemented in the commercial CFD code AVL FIRE®, to simulate physical processes of all relevant phenomena occurring during the SNCR process. First, mathematical models for description of SNCR process are presented and afterwards, models are used on the 3D geometry of an industrial reactor and a real industrial case to predict SNCR efficiency, temperature and velocity field. Influence of the main

  11. 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.

  12. 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

  13. Synthesis and characterization of two novel organic-inorganic compounds based on tetrahexyl and tetraheptyl ammonium ions and the Preyssler anion and their catalytic activities in the synthesis of 4-aminopyrazolo[3,4-d]- pyrimidines.

    Science.gov (United States)

    Bamoharram, Fatemeh Farrash

    2010-04-08

    Two novel organic-inorganic compounds based on tetrahexylammonium (THA) and tetraheptylammonium (THPA) ions and the Preyssler anion, [NaP5W30O110]14-, were synthesized and formulated as (THA)7.7H6.3 [NaP5W30O110] (A) and (THPA)7.5 H6.5[NaP5W30O110] (B). The synthesized compounds were characterized by IR, UV, and TGA and used for the catalytic synthesis of 4-aminopyrazolo[3,4,-d]pyrimidine derivatives 2a-2d. Our findings showed efficient catalytic activities for A and B.

  14. 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

  15. 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.

  16. Vapor Phase Catalytic Ammonia Reduction

    Science.gov (United States)

    Flynn, Michael T.; Harper, Lynn D. (Technical Monitor)

    1994-01-01

    This paper discusses the development of a Vapor Phase Catalytic Ammonia Reduction (VPCAR) teststand and the results of an experimental program designed to evaluate the potential of the technology as a water purification process. In the experimental program the technology is evaluated based upon product water purity, water recovery rate, and power consumption. The experimental work demonstrates that the technology produces high purity product water and attains high water recovery rates at a relatively high specific power consumption. The experimental program was conducted in 3 phases. In phase I an Igepon(TM) soap and water mixture was used to evaluate the performance of an innovative Wiped-Film Rotating-Disk evaporator and associated demister. In phase II a phenol-water solution was used to evaluate the performance of the high temperature catalytic oxidation reactor. In phase III a urine analog was used to evaluate the performance of the combined distillation/oxidation functions of the processor.

  17. Experimental investigation of the catalytic decomposition and combustion characteristics of a non-toxic ammonium dinitramide (ADN)-based monopropellant thruster

    Science.gov (United States)

    Chen, Jun; Li, Guoxiu; Zhang, Tao; Wang, Meng; Yu, Yusong

    2016-12-01

    Low toxicity ammonium dinitramide (ADN)-based aerospace propulsion systems currently show promise with regard to applications such as controlling satellite attitude. In the present work, the decomposition and combustion processes of an ADN-based monopropellant thruster were systematically studied, using a thermally stable catalyst to promote the decomposition reaction. The performance of the ADN propulsion system was investigated using a ground test system under vacuum, and the physical properties of the ADN-based propellant were also examined. Using this system, the effects of the preheating temperature and feed pressure on the combustion characteristics and thruster performance during steady state operation were observed. The results indicate that the propellant and catalyst employed during this work, as well as the design and manufacture of the thruster, met performance requirements. Moreover, the 1 N ADN thruster generated a specific impulse of 223 s, demonstrating the efficacy of the new catalyst. The thruster operational parameters (specifically, the preheating temperature and feed pressure) were found to have a significant effect on the decomposition and combustion processes within the thruster, and the performance of the thruster was demonstrated to improve at higher feed pressures and elevated preheating temperatures. A lower temperature of 140 °C was determined to activate the catalytic decomposition and combustion processes more effectively compared with the results obtained using other conditions. The data obtained in this study should be beneficial to future systematic and in-depth investigations of the combustion mechanism and characteristics within an ADN thruster.

  18. The influence of calcination temperatures on the acid-based properties and catalytic activity for the 1,3-butadiene synthesis from ethanol/acetaldehyde mixture

    Science.gov (United States)

    Gao, Meixiang; Jiang, Haoxi; Zhang, Minhua

    2018-05-01

    The influences of the calcination temperature on the catalysts' acid-based properties and catalytic activity for the 1,3-butadiene synthesis from ethanol are investigated. The results show that the 2 wt% ZrO2/Nano-SiO2 calcined at 773 K shows the best performance with the selectivity of 93.18% and conversion of 58.52% when reacted at 593 K, a WHSV of 1.8 h-1 and 3.5:1 volume ratio ethanol-to-acetaldehyde in an atmospheric fixed-bed reactor. Prepared catalysts were characterized by N2 adsorption-desorption, XRD, temperature-programmed desorption of NH3 and CO2, FTIR spectroscopy of adsorbed pyridine and CO2. Based on the relationship between the catalyst activity and its properties, the fact can be presumed that the formation and strength of Zrsbnd Osbnd Si bond determines the acid-based properties of the catalyst. In addition, moderate-intensity weak acid-basic sites are more suitable for ethanol conversion to BD with the amount of acid and basic sites as close as possible.

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

    Science.gov (United States)

    Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei

    2005-06-01

    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.

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

    OpenAIRE

    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 uni...

  1. Base Catalytic Approach: A Promising Technique for the Activation of Biochar for Equilibrium Sorption Studies of Copper, Cu(II Ions in Single Solute System

    Directory of Open Access Journals (Sweden)

    Sharifah Bee Abdul Hamid

    2014-04-01

    Full Text Available This study examines the feasibility of catalytically pretreated biochar derived from the dried exocarp or fruit peel of mangostene with Group I alkali metal hydroxide (KOH. The pretreated char was activated in the presence of carbon dioxide gas flow at high temperature to upgrade its physiochemical properties for the removal of copper, Cu(II cations in single solute system. The effect of three independent variables, including temperature, agitation time and concentration, on sorption performance were carried out. Reaction kinetics parameters were determined by using linear regression analysis of the pseudo first, pseudo second, Elovich and intra-particle diffusion models. The regression co-efficient, R2 values were best for the pseudo second order kinetic model for all the concentration ranges under investigation. This implied that Cu(II cations were adsorbed mainly by chemical interactions with the surface active sites of the activated biochar. Langmuir, Freundlich and Temkin isotherm models were used to interpret the equilibrium data at different temperature. Thermodynamic studies revealed that the sorption process was spontaneous and endothermic. The surface area of the activated sample was 367.10 m2/g, whereas before base activation, it was only 1.22 m2/g. The results elucidated that the base pretreatment was efficient enough to yield porous carbon with an enlarged surface area, which can successfully eliminate Cu(II cations from waste water.

  2. A catalytically and genetically optimized β-lactamase-matrix based assay for sensitive, specific, and higher throughput analysis of native henipavirus entry characteristics

    Directory of Open Access Journals (Sweden)

    Holbrook Michael R

    2009-07-01

    Full Text Available Abstract Nipah virus (NiV and Hendra virus (HeV are the only paramyxoviruses requiring Biosafety Level 4 (BSL-4 containment. Thus, study of henipavirus entry at less than BSL-4 conditions necessitates the use of cell-cell fusion or pseudotyped reporter virus assays. Yet, these surrogate assays may not fully emulate the biological properties unique to the virus being studied. Thus, we developed a henipaviral entry assay based on a β-lactamase-Nipah Matrix (βla-M fusion protein. We first codon-optimized the bacterial βla and the NiV-M genes to ensure efficient expression in mammalian cells. The βla-M construct was able to bud and form virus-like particles (VLPs that morphologically resembled paramyxoviruses. βla-M efficiently incorporated both NiV and HeV fusion and attachment glycoproteins. Entry of these VLPs was detected by cytosolic delivery of βla-M, resulting in enzymatic and fluorescent conversion of the pre-loaded CCF2-AM substrate. Soluble henipavirus receptors (ephrinB2 or antibodies against the F and/or G proteins blocked VLP entry. Additionally, a Y105W mutation engineered into the catalytic site of βla increased the sensitivity of our βla-M based infection assays by 2-fold. In toto, these methods will provide a more biologically relevant assay for studying henipavirus entry at less than BSL-4 conditions.

  3. Platinum from automotive catalytic converters: environmental health evaluation based on recent data on exposure and effects; Platin aus Automobilabgaskatalysatoren: Umweltmedizinische Bewertung auf Basis neuer Expositions- und Wirkungsdaten

    Energy Technology Data Exchange (ETDEWEB)

    Rosner, G. [Consulting-Buero Toxikologie - Umwelt, Merzhausen/Freiburg (Germany); Artelt, S. [Bayern Innovativ Gesellschaft fuer Innovation und Wissenstransfer mbH, Nuernberg (Germany); Mangelsdorf, I. [Fraunhofer-Institut fuer Toxikologie und Aerosolforschung (ITA), Hannover (Germany); Merget, R. [Berufsgenossenschaftliches Forschungsinstitut fuer Arbeitsmedizin (BGFA), Bochum (Germany)

    1998-12-01

    We estimated ambient air concentrations of platinum by applying dispersion models as well as recent emission factors that have been derived from engine test bench experiments with three-way, monolith-type catalytic converters. Predicted concentrations in various exposure scenarios range from 4 pg/m{sup 3} (street canyon, typical conditions) up to 112 pg/m{sup 3} (express-motorway, severe conditions). These values agree well with the few measurements of platinum ambient air concentrations. Platinum is emitted from catalytic converters in very small amounts (ng/km range) and is mainly in the oxidation state 0 (elemental platinum). The nanocrystalline platinum particles are attached to {mu}m-sized aluminum oxide particles. Whether free ultrafine platinum particles may be emitted and result in biological effects has not been studied sufficiently. Hence, risk assessment can only be based on the respiratory sensitizing effects of halogenated platinum salts, although this can be considered a very sensitive endpoint. The presence of such compounds in the soluble fraction ({<=}1%) of the total platinum emissions as well as their secondary formation from platinum particles cannot principally be excluded. Our risk assessment is based on recent occupational studies in a catalytic converter production plant, from which a conservative, no effect level (NOEL) of 1.5 ng/cm{sup 3} can be derived for soluble platinum. In a (reasonable) worst case approach we assume that halogenated platinum salts comprise 1% (0.1%) of the total platinum emissions. Applying an unsafety factor of 10 to account for inter-individual variability, a guidance value of 150 (15) ng/m{sup 3} is derived for catalyst-borne platinum. The exposure to platinum in ambient air as measured or predicted is at least two orders of magnitude below this `critical` range. (orig.) [Deutsch] In einer differenzierten Aktualisierung frueherer Expositionsabschaetzungen werden anhand von Ausbreitungsmodellen und aktuellen

  4. Catalytic production of Jatropha biodiesel and hydrogen with magnetic carbonaceous acid and base synthesized from Jatropha hulls

    International Nuclear Information System (INIS)

    Zhang, Fan; Tian, Xiao-Fei; Fang, Zhen; Shah, Mazloom; Wang, Yi-Tong; Jiang, Wen; Yao, Min

    2017-01-01

    Graphical abstract: Jatropha seeds were extracted oil for biodiesel production and the hulls were carbonized to load active sites as magnetic carbonaceous solid acid and base catalysts. Crude Jatropha oil was esterified to decrease its acid value to 1.3 from 17.2 mg KOH/g by the solid acid, and subsequently transesterified to biodiesel (96.7% yield) catalyzed by the solid base. After 3 cycles and magnetically separated, the deactivated base was catalyzed the hydrothermal gasification of biodiesel by-product (crude glycerol) with gasification rate of 81% and 82% H 2 purity. - Highlights: • High acid value (AV) crude oil was extracted from Jatropha seeds with waste hulls produced. • Carbonizing the hulls and loading active sites produced magnetic carbonaceous acid and base. • The acid reduced AV of crude oil to 1.3 from 17.2 mg KOH/g and separated for 3 cycles. • The base achieved 97.5% biodiesel yield and magnetically separated for recycles. • After 3 cycles, the deactivated base catalyzed the hydrothermal gasification of glycerol. - Abstract: Magnetic carbonaceous solid acid (C-SO 3 H@Fe/JHC) and base (Na 2 SiO 3 @Ni/JRC) catalysts were synthesized by loading active groups on the carbonaceous supporters derived from Jatropha-hull hydrolysate and hydrolysis residue. Characterization of their morphology, magnetic saturation, functional groups and total acid/base contents were performed by various techniques. Additional acidic functional groups that formed with Jatropha-hull hydrolysate contributed to the high acidity of C-SO 3 H@Fe/JHC catalyst for the pretreatment (esterification) of crude Jatropha oil with high acid values (AV). The AV of esterified Jatropha oil dropped down from 17.2 to 1.3 mg KOH/g, achieving a high biodiesel yield of 96.7% after subsequent transesterification reaction with Na 2 SiO 3 @Ni/JRC base that was cycled at least 3 times with little loss of catalysis activity. Both solid acid and base catalysts were easily recovered by magnetic

  5. Catalytic Conversion of Biomass Pyrolysis Vapours over Sodium-Based Catalyst; A Study on teh State of Sodium on the Catalyst

    NARCIS (Netherlands)

    Nguyen, T.S.; Lefferts, Leonardus; Gupta, K.B. Sai Sankar; Seshan, Kulathuiyer

    2015-01-01

    In situ upgrading of biomass pyrolysis vapours over Na2CO3/γ-Al2O3 catalysts was studied in a laboratory-scale fixed-bed reactor at 500 °C. Catalytic oil exhibits a significant improvement over its non-catalytic counterpart, such as lower oxygen content (12.3 wt % compared to 42.1 wt %), higher

  6. Characterization of the Trans Watson-Crick GU Base Pair Located in the Catalytic Core of the Antigenomic HDV Ribozyme

    Science.gov (United States)

    Lévesque, Dominique; Reymond, Cédric; Perreault, Jean-Pierre

    2012-01-01

    The HDV ribozyme’s folding pathway is, by far, the most complex folding pathway elucidated to date for a small ribozyme. It includes 6 different steps that have been shown to occur before the chemical cleavage. It is likely that other steps remain to be discovered. One of the most critical of these unknown steps is the formation of the trans Watson-Crick GU base pair within loop III. The U23 and G28 nucleotides that form this base pair are perfectly conserved in all natural variants of the HDV ribozyme, and therefore are considered as being part of the signature of HDV-like ribozymes. Both the formation and the transformation of this base pair have been studied mainly by crystal structure and by molecular dynamic simulations. In order to obtain physical support for the formation of this base pair in solution, a set of experiments, including direct mutagenesis, the site-specific substitution of chemical groups, kinetic studies, chemical probing and magnesium-induced cleavage, were performed with the specific goal of characterizing this trans Watson-Crick GU base pair in an antigenomic HDV ribozyme. Both U23 and G28 can be substituted for nucleotides that likely preserve some of the H-bond interactions present before and after the cleavage step. The formation of the more stable trans Watson-Crick base pair is shown to be a post-cleavage event, while a possibly weaker trans Watson-Crick/Hoogsteen interaction seems to form before the cleavage step. The formation of this unusually stable post-cleavage base pair may act as a driving force on the chemical cleavage by favouring the formation of a more stable ground state of the product-ribozyme complex. To our knowledge, this represents the first demonstration of a potential stabilising role of a post-cleavage conformational switch event in a ribozyme-catalyzed reaction. PMID:22768274

  7. Characterization of the trans Watson-Crick GU base pair located in the catalytic core of the antigenomic HDV ribozyme.

    Directory of Open Access Journals (Sweden)

    Dominique Lévesque

    Full Text Available The HDV ribozyme's folding pathway is, by far, the most complex folding pathway elucidated to date for a small ribozyme. It includes 6 different steps that have been shown to occur before the chemical cleavage. It is likely that other steps remain to be discovered. One of the most critical of these unknown steps is the formation of the trans Watson-Crick GU base pair within loop III. The U(23 and G(28 nucleotides that form this base pair are perfectly conserved in all natural variants of the HDV ribozyme, and therefore are considered as being part of the signature of HDV-like ribozymes. Both the formation and the transformation of this base pair have been studied mainly by crystal structure and by molecular dynamic simulations. In order to obtain physical support for the formation of this base pair in solution, a set of experiments, including direct mutagenesis, the site-specific substitution of chemical groups, kinetic studies, chemical probing and magnesium-induced cleavage, were performed with the specific goal of characterizing this trans Watson-Crick GU base pair in an antigenomic HDV ribozyme. Both U(23 and G(28 can be substituted for nucleotides that likely preserve some of the H-bond interactions present before and after the cleavage step. The formation of the more stable trans Watson-Crick base pair is shown to be a post-cleavage event, while a possibly weaker trans Watson-Crick/Hoogsteen interaction seems to form before the cleavage step. The formation of this unusually stable post-cleavage base pair may act as a driving force on the chemical cleavage by favouring the formation of a more stable ground state of the product-ribozyme complex. To our knowledge, this represents the first demonstration of a potential stabilising role of a post-cleavage conformational switch event in a ribozyme-catalyzed reaction.

  8. Steam reformer with catalytic combustor

    Science.gov (United States)

    Voecks, Gerald E. (Inventor)

    1990-01-01

    A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

  9. Cerium-based metal organic frameworks with UiO-66 architecture: synthesis, properties and redox catalytic activity.

    Science.gov (United States)

    Lammert, Martin; Wharmby, Michael T; Smolders, Simon; Bueken, Bart; Lieb, Alexandra; Lomachenko, Kirill A; Vos, Dirk De; Stock, Norbert

    2015-08-14

    A series of nine Ce(iv)-based metal organic frameworks with the UiO-66 structure containing linker molecules of different sizes and functionalities were obtained under mild synthesis conditions and short reaction times. Thermal and chemical stabilities were determined and a Ce-UiO-66-BDC/TEMPO system was successfully employed for the aerobic oxidation of benzyl alcohol.

  10. A Ligand Structure-Activity Study of DNA-Based Catalytic Asymmetric Hydration and Diels-Alder Reactions

    NARCIS (Netherlands)

    Rosati, F.; Roelfes, J.G.

    A structure-activity relationship study of the first generation ligands for the DNA-based asymmetric hydration of enones and Diels-Alder reaction in water is reported. The design of the ligand was optimized resulting in a maximum ee of 83% in the hydration reaction and 75% in the Diels-Alder

  11. Synthesis, characterization, crystal structure determination, thermal study and catalytic activity of a new oxidovanadium Schiff base complex

    Czech Academy of Sciences Publication Activity Database

    Grivani, G.; Ghavami, A.; Kučeráková, Monika; Dušek, Michal; Khalaji, A.D.

    2014-01-01

    Roč. 1076, Nov (2014), s. 326-332 ISSN 0022-2860 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : oxidovanadium(IV) * Schiff base * crystal structure * V 2 O 5 nano-particle * oxidation Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.602, year: 2014

  12. Radiolytic Synthesis of Pt-Ru Catalysts Based on Functional Polymer-Grafted MWNT and Their Catalytic Efficiency for CO and MeOH

    Directory of Open Access Journals (Sweden)

    Dae-Soo Yang

    2011-01-01

    Full Text Available Pt-Ru catalysts based on functional polymer-grafted MWNT (Pt-Ru@FP-MWNT were prepared by radiolytic deposition of Pt-Ru nanoparticles on functional polymer-grafted multiwalled carbon nanotube (FP-MWNT. Three different types of functional polymers, poly(acrylic acid (PAAc, poly(methacrylic acid (PMAc, and poly(vinylphenyl boronic acid (PVPBAc, were grafted on the MWNT surface by radiation-induced graft polymerization (RIGP. Then, Pt-Ru nanoparticles were deposited onto the FP-MWNT supports by the reduction of metal ions using γ-irradiation to obtain Pt-Ru@FP-MWNT catalysts. The Pt-Ru@FP-MWNT catalysts were then characterized by XRD, XPS, TEM ,and elemental analysis. The catalytic efficiency of Pt-Ru@FP-MWNT catalyst was examined for CO stripping and MeOH oxidation for use in a direct methanol fuel cell (DMFC. The Pt-Ru@PVPBAc-MWNT catalyst shows enhanced activity for electro-oxidation of CO and MeOH oxidation over that of the commercial E-TEK catalyst.

  13. Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification.

    Science.gov (United States)

    Castro-Dominguez, Bernardo; Mardilovich, Ivan P; Ma, Liang-Chih; Ma, Rui; Dixon, Anthony G; Kazantzis, Nikolaos K; Ma, Yi Hua

    2016-09-19

    Palladium-based catalytic membrane reactors (CMRs) effectively remove H₂ to induce higher conversions in methane steam reforming (MSR) and water-gas-shift reactions (WGS). Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H₂, CO and CO₂. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H₂O, CO₂ and H₂. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H₂ and induce higher methane and CO conversions while yielding ultrapure H₂ and compressed CO₂ ready for dehydration. Experimental results involving (i) a conventional packed bed reactor packed (PBR) for MSR, (ii) a PBR with five layers of two catalysts in series and (iii) a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD) model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H₂ permeance and purity, high CH₄ conversion levels and reduced CO yields.

  14. A DFT-Based Computational-Experimental Methodology for Synthetic Chemistry: Example of Application to the Catalytic Opening of Epoxides by Titanocene.

    Science.gov (United States)

    Jaraíz, Martín; Enríquez, Lourdes; Pinacho, Ruth; Rubio, José E; Lesarri, Alberto; López-Pérez, José L

    2017-04-07

    A novel DFT-based Reaction Kinetics (DFT-RK) simulation approach, employed in combination with real-time data from reaction monitoring instrumentation (like UV-vis, FTIR, Raman, and 2D NMR benchtop spectrometers), is shown to provide a detailed methodology for the analysis and design of complex synthetic chemistry schemes. As an example, it is applied to the opening of epoxides by titanocene in THF, a catalytic system with abundant experimental data available. Through a DFT-RK analysis of real-time IR data, we have developed a comprehensive mechanistic model that opens new perspectives to understand previous experiments. Although derived specifically from the opening of epoxides, the prediction capabilities of the model, built on elementary reactions, together with its practical side (reaction kinetics simulations of real experimental conditions) make it a useful simulation tool for the design of new experiments, as well as for the conception and development of improved versions of the reagents. From the perspective of the methodology employed, because both the computational (DFT-RK) and the experimental (spectroscopic data) components can follow the time evolution of several species simultaneously, it is expected to provide a helpful tool for the study of complex systems in synthetic chemistry.

  15. High efficiency chemical energy conversion system based on a methane catalytic decomposition reaction and two fuel cells: Part I. Process modeling and validation

    Science.gov (United States)

    Liu, Qinghua; Tian, Ye; Li, Hongjiao; Jia, Lijun; Xia, Chun; Thompson, Levi T.; Li, Yongdan

    A highly efficient integrated energy conversion system is built based on a methane catalytic decomposition reactor (MCDR) together with a direct carbon fuel cell (DCFC) and an internal reforming solid oxide fuel cell (IRSOFC). In the MCDR, methane is decomposed to pure carbon and hydrogen. Carbon is used as the fuel of DCFC to generate power and produce pure carbon dioxide. The hydrogen and unconverted methane are used as the fuel in the IRSOFC. A gas turbine cycle is also used to produce more power output from the thermal energy generated in the IRSOFC. The output performance and efficiency of both the DCFC and IRSOFC are investigated and compared by development of exact models of them. It is found that this system has a unique loading flexibility due to the good high-loading property of DCFC and the good low loading property of IRSOFC. The effects of temperature, pressure, current densities, and methane conversion on the performance of the fuel cells and the system are discussed. The CO 2 emission reduction is effective, up to 80%, can be reduced with the proposed system.

  16. Structural and catalytic effects of an invariant purine substitution in the hammerhead ribozyme: implications for the mechanism of acid-base catalysis.

    Science.gov (United States)

    Schultz, Eric P; Vasquez, Ernesto E; Scott, William G

    2014-09-01

    The hammerhead ribozyme catalyzes RNA cleavage via acid-base catalysis. Whether it does so by general acid-base catalysis, in which the RNA itself donates and abstracts protons in the transition state, as is typically assumed, or by specific acid-base catalysis, in which the RNA plays a structural role and proton transfer is mediated by active-site water molecules, is unknown. Previous biochemical and crystallographic experiments implicate an invariant purine in the active site, G12, as the general base. However, G12 may play a structural role consistent with specific base catalysis. To better understand the role of G12 in the mechanism of hammerhead catalysis, a 2.2 Å resolution crystal structure of a hammerhead ribozyme from Schistosoma mansoni with a purine substituted for G12 in the active site of the ribozyme was obtained. Comparison of this structure (PDB entry 3zd4), in which A12 is substituted for G, with three previously determined structures that now serve as important experimental controls, allows the identification of structural perturbations that are owing to the purine substitution itself. Kinetic measurements for G12 purine-substituted schistosomal hammerheads confirm a previously observed dependence of rate on the pK(a) of the substituted purine; in both cases inosine, which is similar to G in pK(a) and hydrogen-bonding properties, is unexpectedly inactive. Structural comparisons indicate that this may primarily be owing to the lack of the exocyclic 2-amino group in the G12A and G12I substitutions and its structural effect upon both the nucleotide base and phosphate of A9. The latter involves the perturbation of a previously identified and well characterized metal ion-binding site known to be catalytically important in both minimal and full-length hammerhead ribozyme sequences. The results permit it to be suggested that G12 plays an important role in stabilizing the active-site structure. This result, although not inconsistent with the potential

  17. Structural and catalytic effects of an invariant purine substitution in the hammerhead ribozyme: implications for the mechanism of acid–base catalysis

    Science.gov (United States)

    Schultz, Eric P.; Vasquez, Ernesto E.; Scott, William G.

    2014-01-01

    The hammerhead ribozyme catalyzes RNA cleavage via acid–base catalysis. Whether it does so by general acid–base catalysis, in which the RNA itself donates and abstracts protons in the transition state, as is typically assumed, or by specific acid–base catalysis, in which the RNA plays a structural role and proton transfer is mediated by active-site water molecules, is unknown. Previous biochemical and crystallographic experiments implicate an invariant purine in the active site, G12, as the general base. However, G12 may play a structural role consistent with specific base catalysis. To better understand the role of G12 in the mechanism of hammerhead catalysis, a 2.2 Å resolution crystal structure of a hammerhead ribozyme from Schistosoma mansoni with a purine substituted for G12 in the active site of the ribozyme was obtained. Comparison of this structure (PDB entry 3zd4), in which A12 is substituted for G, with three previously determined structures that now serve as important experimental controls, allows the identification of structural perturbations that are owing to the purine substitution itself. Kinetic measurements for G12 purine-substituted schistosomal hammerheads confirm a previously observed dependence of rate on the pK a of the substituted purine; in both cases inosine, which is similar to G in pK a and hydrogen-bonding properties, is unexpectedly inactive. Structural comparisons indicate that this may primarily be owing to the lack of the exocyclic 2-amino group in the G12A and G12I substitutions and its structural effect upon both the nucleotide base and phosphate of A9. The latter involves the perturbation of a previously identified and well characterized metal ion-binding site known to be catalytically important in both minimal and full-length hammerhead ribozyme sequences. The results permit it to be suggested that G12 plays an important role in stabilizing the active-site structure. This result, although not inconsistent with the

  18. Sugar-based micro/mesoporous hypercross-linked polymers with in situ embedded silver nanoparticles for catalytic reduction

    OpenAIRE

    Qing Yin; Qi Chen; Li-Can Lu; Bao-Hang Han

    2017-01-01

    Porous hypercross-linked polymers based on perbenzylated monosugars (SugPOP-1–3) have been synthesized by Friedel–Crafts reaction using formaldehyde dimethyl acetal as an external cross-linker. Three perbenzylated monosugars with similar chemical structure were used as monomers in order to tune the porosity. These obtained polymers exhibit microporous and mesoporous features. The highest Brunauer–Emmett–Teller specific surface area for the resulting polymers was found to be 1220 m2 g−1, and t...

  19. Synthesis, characterization, and tyrosinase biomimetic catalytic activity of copper(II) complexes with schiff base ligands derived from α-diketones with 2-methyl-3-amino-(3 H)-quinazolin-4-one

    Science.gov (United States)

    Ramadan, Abd El-Motaleb M.; Ibrahim, Mohamed M.; Shaban, Shaban Y.

    2011-12-01

    A template condensation of α-diketones (biacetyl, benzile and 2,3-pentanedione) with 2-methyl-3-amino-(3 H)-quinazolin-4-one (AMQ) in the presence of CuX 2 (X = Cl -, Br -, NO3- or ClO4-) resulted in the formation of tetradentate Schiff base copper(II) complexes of the type [CuLX]X and [CuL]X 2. Structural characterization of the complex species was achieved by several physicochemical methods, namely elemental analysis, electronic spectra, IR, ESR, molar conductivity, thermal analysis (TAG & DTG), and magnetic moment measurements. The stereochemistry, the nature of the metal chelates, and the catalytic reactivity are markedly dependent upon the type of counter anions and the ligand substituent within the carbonyl moiety. A square planar monomeric structure is proposed for the perchlorate, nitrate, and bromide complexes, in which the counter anions are loosely bonded to copper(II) ion. For the chloride complexes, the molar conductivities and the spectral data indicated that they have square-pyramidal environments around copper(II) center. The reported copper(II) complexes exhibit promising tyrosinase catalytic activity towards the hydroxylation of phenol followed by the aerobic oxidation of the resulting catechol. A linear correlation almost exists between the catalytic reactivity and the Lewis-acidity of the central copper(II) ion created by the donating properties of the parent ligand. The steric considerations could be accounted to clarify the difference in the catalytic activity of these functional models.

  20. Catalytic activity of acid and base with different concentration on sol-gel kinetics of silica by ultrasonic method.

    Science.gov (United States)

    Das, R K; Das, M

    2015-09-01

    The effects of both acid (acetic acid) and base (ammonia) catalysts in varying on the sol-gel synthesis of SiO2 nanoparticles using tetra ethyl ortho silicate (TEOS) as a precursor was determined by ultrasonic method. The ultrasonic velocity was received by pulsar receiver. The ultrasonic velocity in the sol and the parameter ΔT (time difference between the original pulse and first back wall echo of the sol) was varied with time of gelation. The graphs of ln[ln1/ΔT] vs ln(t), indicate two region - nonlinear region and a linear region. The time corresponds to the point at which the non-linear region change to linear region is considered as gel time for the respective solutions. Gelation time is found to be dependent on the concentration and types of catalyst and is found from the graphs based on Avrami equation. The rate of condensation is found to be faster for base catalyst. The gelation process was also characterized by viscosity measurement. Normal sol-gel process was also carried out along with the ultrasonic one to compare the effectiveness of ultrasonic. The silica gel was calcined and the powdered sample was characterized with scanning electron microscopy, energy dispersive spectra, X-ray diffractogram, and FTIR spectroscopy. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. An automated flow for directed evolution based on detection of promiscuous scaffolds using spatial and electrostatic properties of catalytic residues.

    Directory of Open Access Journals (Sweden)

    Sandeep Chakraborty

    Full Text Available The aspiration to mimic and accelerate natural evolution has fueled interest in directed evolution experiments, which endow or enhance functionality in enzymes. Barring a few de novo approaches, most methods take a template protein having the desired activity, known active site residues and structure, and proceed to select a target protein which has a pre-existing scaffold congruent to the template motif. Previously, we have established a computational method (CLASP based on spatial and electrostatic properties to detect active sites, and a method to quantify promiscuity in proteins. We exploit the prospect of promiscuous active sites to serve as the starting point for directed evolution and present a method to select a target protein which possesses a significant partial match with the template scaffold (DECAAF. A library of partial motifs, constructed from the active site residues of the template protein, is used to rank a set of target proteins based on maximal significant matches with the partial motifs, and cull out the best candidate from the reduced set as the target protein. Considering the scenario where this 'incubator' protein lacks activity, we identify mutations in the target protein that will mirror the template motif by superimposing the target and template protein based on the partial match. Using this superimposition technique, we analyzed the less than expected gain of activity achieved by an attempt to induce β-lactamase activity in a penicillin binding protein (PBP (PBP-A from T. elongatus, and attributed this to steric hindrance from neighboring residues. We also propose mutations in PBP-5 from E. coli, which does not have similar steric constraints. The flow details have been worked out in an example which aims to select a substitute protein for human neutrophil elastase, preferably related to grapevines, in a chimeric anti-microbial enzyme which bolsters the innate immune defense system of grapevines.

  2. A chiral mixed metal-organic framework based on a Ni(saldpen) metalloligand: synthesis, characterization and catalytic performances.

    Science.gov (United States)

    Ren, Yanwei; Cheng, Xiaofei; Yang, Shaorong; Qi, Chaorong; Jiang, Huanfeng; Mao, Qiuping

    2013-07-21

    A three-dimensional (3D) chiral mixed metal-organic framework [Cd4Cl(Ni-L)3(Ni-HL)(H2O)6(DMF)]·4DMF (CMOF 1) based on a new enantiopure dicarboxyl-functionalized Ni(saldpen) metalloligand Ni-H2L and a novel tetranuclear cadmium cluster [Cd4Cl(CO2)7(CO2H)] has been synthesized and characterized by elemental analyses, IR and UV-vis spectra, thermogravimetric analysis, nitrogen and carbon dioxide adsorption, powder and single-crystal X-ray diffractions. Each tetranuclear-cadmium cluster in 1 is linked by eight Ni-L ligands, and each Ni-L ligand is linked by two tetranuclear-cadmium clusters to generate a 3D framework with 1D open channels (∼1.1 × 0.9 nm(2)) along the b-axis. Based on its good stability, permanent porosity, Lewis acid sites and moderate uptake for CO2, 1 can be used as a self-supported heterogeneous catalyst for the synthesis of optically active propylene carbonate by asymmetric cycloaddition of CO2 with racemic propylene oxide under relatively mild conditions.

  3. Highly catalytic carbon nanotube counter electrode on plastic for dye solar cells utilizing cobalt-based redox mediator

    International Nuclear Information System (INIS)

    Aitola, Kerttu; Halme, Janne; Feldt, Sandra; Lohse, Peter; Borghei, Maryam; Kaskela, Antti; Nasibulin, Albert G.; Kauppinen, Esko I.; Lund, Peter D.; Boschloo, Gerrit; Hagfeldt, Anders

    2013-01-01

    A flexible, slightly transparent and metal-free random network of single-walled carbon nanotubes (SWCNTs) on plain polyethylene terephthalate (PET) plastic substrate outperformed platinum on conductive glass and on plastic as the counter electrode (CE) of a dye solar cell employing a Co(II/III)tris(2,2′-bipyridyl) complex redox mediator in 3-methoxypropionitrile solvent. The CE charge-transfer resistance of the SWCNT film was 0.60 Ω cm 2 , 4.0 Ω cm 2 for sputtered platinum on indium tin oxide-PET substrate and 1.7 Ω cm 2 for thermally deposited Pt on fluorine-doped tin oxide glass, respectively. The solar cell efficiencies were in the same range, thus proving that an entirely carbon-based SWCNT film on plastic is as good CE candidate for the Co electrolyte

  4. Catalytic enantioselective olefin metathesis in natural product synthesis. Chiral metal-based complexes that deliver high enantioselectivity and more.

    Science.gov (United States)

    Hoveyda, Amir H; Malcolmson, Steven J; Meek, Simon J; Zhugralin, Adil R

    2010-01-01

    Chiral olefin metathesis catalysts enable chemists to access enantiomerically enriched small molecules with high efficiency; synthesis schemes involving such complexes can be substantially more concise than those that would involve enantiomerically pure substrates and achiral Mo alkylidenes or Ru-based carbenes. The scope of research towards design and development of chiral catalysts is not limited to discovery of complexes that are merely the chiral versions of the related achiral variants. A chiral olefin metathesis catalyst, in addition to furnishing products of high enantiomeric purity, can offer levels of efficiency, product selectivity and/or olefin stereoselectivity that are unavailable through the achiral variants. Such positive attributes of chiral catalysts (whether utilized in racemic or enantiomerically enriched form) should be considered as general, applicable to other classes of transformations.

  5. Catalytic Enantioselective Olefin Metathesis in Natural Product Synthesis. Chiral Metal-Based Complexes that Deliver High Enantioselectivity and More

    Science.gov (United States)

    Malcolmson, Steven J.; Meek, Simon J.; Zhugralin, Adil R.

    2012-01-01

    Chiral olefin metathesis catalysts enable chemists to access enantiomerically enriched small molecules with high efficiency; synthesis schemes involving such complexes can be substantially more concise than those that would involve enantiomerically pure substrates and achiral Mo alkylidenes or Ru-based carbenes. The scope of research towards design and development of chiral catalysts is not limited to discovery of complexes that are merely the chiral versions of the related achiral variants. A chiral olefin metathesis catalyst, in addition to furnishing products of high enantiomeric purity, can offer levels of efficiency, product selectivity and/or olefin stereoselectivity that are unavailable through the achiral variants. Such positive attributes of chiral catalysts (whether utilized in racemic or enantiomerically enriched form) should be considered as general, applicable to other classes of transformations. PMID:19967680

  6. Catalytic Upgrading of 5-Hydroxymethylfurfural to Drop-in Biofuels by Solid Base and Bifunctional Metal-Acid Catalysts.

    Science.gov (United States)

    Bohre, Ashish; Saha, Basudeb; Abu-Omar, Mahdi M

    2015-12-07

    Design and synthesis of effective heterogeneous catalysts for the conversion of biomass intermediates into long chain hydrocarbon precursors and their subsequent deoxygenation to hydrocarbons is a viable strategy for upgrading lignocellulose into distillate range drop-in biofuels. Herein, we report a two-step process for upgrading 5-hydroxymethylfurfural (HMF) to C9 and C11 fuels with high yield and selectivity. The first step involves aldol condensation of HMF and acetone with a water tolerant solid base catalyst, zirconium carbonate (Zr(CO3 )x ), which gave 92 % C9 -aldol product with high selectivity at nearly 100 % HMF conversion. The as-synthesised Zr(CO3 )x was analysed by several analytical methods for elucidating its structural properties. Recyclability studies of Zr(CO3 )x revealed a negligible loss of its activity after five consecutive cycles over 120 h of operation. Isolated aldol product from the first step was hydrodeoxygenated with a bifunctional Pd/Zeolite-β catalyst in ethanol, which showed quantitative conversion of the aldol product to n-nonane and 1-ethoxynonane with 40 and 56 % selectivity, respectively. 1-Ethoxynonane, a low oxygenate diesel range fuel, which we report for the first time in this paper, is believed to form through etherification of the hydroxymethyl group of the aldol product with ethanol followed by opening of the furan ring and hydrodeoxygenation of the ether intermediate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Syntheses, structures, molecular and cationic recognitions and catalytic properties of two lanthanide coordination polymers based on a flexible tricarboxylate

    International Nuclear Information System (INIS)

    Zhu, Yu; Wang, Yan-Mei; Xu, Ji; Liu, Pan; Weththasinha, H.A.B.M.D.; Wu, Yun-Long; Lu, Xiao-Qing; Xie, Ji-Min

    2014-01-01

    Two lanthanide coordination polymers, namely, ([La(TTTA)(H 2 O) 2 ]·2H 2 O) n (La-TTTA) and [Nd(TTTA)(H 2 O) 2 ]·2H 2 O) n (Nd-TTTA) have been hydrothermally synthesized through the reaction of lanthanide ions (La 3+ and Nd 3+ ) with the flexible tripodal ligand 2,2′,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid (H 3 TTTA). La-TTTA and Nd-TTTA are isostructural and both show three dimensional structures. La-TTTA and Nd-TTTA show good recognition of amine molecules via quenching the luminescent intensities in amines emulsions. They can also recognize Fe 3+ , Cu 2+ , Mg 2+ , Cr 3+ and Co 2+ ions with the quenching the peak around 361 nm when the compounds immersed in ionic solutions. The two compounds act as efficient Lewis acid catalysts for the cyanosilylation of benzaldehyde and derivatives in high yields shortly due to the strong Lewis acidity and the possible open sites of the lanthanide ions. - Graphical abstract: We have synthesized two isostructural 3D compounds based on H 3 TTTA. They are chemical sensor of amine solvents and cations. They have higher yields and TOFs to catalyze cyanosilylation reactions. - Highlights: • The compounds show recognition of amine molecules via quenching luminescent intensities. • The compounds recognize Fe 3+ , Cu 2+ , Mg 2+ , Cr 3+ and Co 2+ ions via quenching the peak around 361 nm. • They act as efficient Lewis acid catalysts for the cyanosilylation reactions in high yields

  8. Model-based analysis of CO2 revalorization for di-methyl ether synthesis driven by solar catalytic reforming

    International Nuclear Information System (INIS)

    Luu, Minh Tri; Milani, Dia; Sharma, Manish; Zeaiter, Joseph; Abbas, Ali

    2016-01-01

    Highlights: • Solar energy applied for synthesis of di-methyl ether via dry methane reforming. • Concentrated solar energy at receiver reaction zone for syngas generation. • H 2 /CO molar ratio of ‘1’ is maintained via two alternative processing routes. • Assessed three days of operation under different insolation levels. • Improvements of 18.7%, 32.2% and 20% for methane, energy and CO 2 emission intensities. - Abstract: The application of solar energy is investigated for the synthesis of di-methyl ether (DME) in a solar irradiated dry methane reformer (DMR). Solar radiations are concentrated onto a receiver and distributed to the reaction zone to provide necessary energy for syngas (CO and H 2 ) generation. In order to maintain a H 2 /CO molar ratio of ‘1’, as required in DME synthesis, the produced syngas is processed via two alternative routes: solar reformer coupled in parallel with a non-solar reformer (SoR-NSoR) and solar reformer integrated with a water-gas shift reactor (SoR-WGS). It is found that steam methane reforming (SMR) is the most suitable methodology when coupled with a solar reformer due to high H 2 content in the SMR syngas. Further performance analysis is conducted by simulating three days of operation under different insolation levels (high, medium and low irradiations). The simulation results showed that the SoR-WGS configuration produces the highest improvements of 18.7%, 32.2% and 20% in terms of methane, energy and CO 2 emission intensity respectively. This enhanced process performance originates from the exothermic nature of the WGS process which helps in controlling the overall syngas composition, whereas the SoR-NSoR requires fossil based thermal energy to drive the NSoR process to similar control targets. This promising improvement of all metrics in SoR-WGS may stimulate in-depth techno-economic feasibility of this unique solar integration for DME and other synthetic fuels production.

  9. Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification

    Directory of Open Access Journals (Sweden)

    Bernardo Castro-Dominguez

    2016-09-01

    Full Text Available Palladium-based catalytic membrane reactors (CMRs effectively remove H2 to induce higher conversions in methane steam reforming (MSR and water-gas-shift reactions (WGS. Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H2, CO and CO2. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H2O, CO2 and H2. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H2 and induce higher methane and CO conversions while yielding ultrapure H2 and compressed CO2 ready for dehydration. Experimental results involving (i a conventional packed bed reactor packed (PBR for MSR, (ii a PBR with five layers of two catalysts in series and (iii a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H2 permeance and purity, high CH4 conversion levels and reduced CO yields.

  10. Removal of ethylene from air stream by adsorption and plasma-catalytic oxidation using silver-based bimetallic catalysts supported on zeolite.

    Science.gov (United States)

    Trinh, Quang Hung; Lee, Sang Baek; Mok, Young Sun

    2015-03-21

    Dynamic adsorption of ethylene on 13X zeolite-supported Ag and Ag-M(x)O(y) (M: Co, Cu, Mn, and Fe), and plasma-catalytic oxidation of the adsorbed ethylene were investigated. The experimental results showed that the incorporation of Ag into zeolite afforded a marked enhancement in the adsorptivity for ethylene. The addition of transition metal oxides was found to have a positive influence on the ethylene adsorption, except Fe(x)O(y). The presence of the additional metal oxides, however, appeared to somewhat interrupt the diffusion of ozone into the zeolite micro-pores, leading to a decrease in the plasma-catalytic oxidation efficiency of the ethylene adsorbed there. Among the second additional metal oxides, Fe(x)O(y) was able to reduce the emission of ozone during the plasma-catalytic oxidation stage while keeping a high effectiveness for the oxidative removal of the adsorbed ethylene. The periodical treatment consisting of adsorption followed by plasma-catalytic oxidation may be a promising energy-efficient ethylene abatement method. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Molybdenum-based additives to mixed-metal oxides for use in hot gas cleanup sorbents for the catalytic decomposition of ammonia in coal gases

    Science.gov (United States)

    Ayala, Raul E.

    1993-01-01

    This invention relates to additives to mixed-metal oxides that act simultaneously as sorbents and catalysts in cleanup systems for hot coal gases. Such additives of this type, generally, act as a sorbent to remove sulfur from the coal gases while substantially simultaneously, catalytically decomposing appreciable amounts of ammonia from the coal gases.

  12. Nickel-based xerogel catalysts: Synthesis via fast sol-gel method and application in catalytic hydrogenation of p-nitrophenol to p-aminophenol

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Jin; Wang, Qiang; Fan, Dongliang; Ma, Lirong; Jiang, Deli; Xie, Jimin, E-mail: xiejm391@sohu.com; Zhu, Jianjun, E-mail: zhjj029@sina.com

    2016-09-30

    out to investigate the reducibility of nickel species and the interaction between nickel species and alumina. The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over the prepared nickel-based xerogel catalysts. The conversion of p-nitrophenol was monitored by UV spectrophotometry and high performance liquid chromatography (HPLC). The results show that the catalysts are highly selective for the conversion of p-nitrophenol to p-aminophenol and the order of catalytic activities of the catalysts is Ni < Ni-Al{sub 2}O{sub 3} < Ni-Ca-Al{sub 2}O{sub 3}. The catalysts were recycled and were used to evaluate the reutilization.

  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. Synthesis, spectroscopic characterization and catalytic oxidation ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 3. Synthesis, spectroscopic characterization and catalytic oxidation properties of ONO/ONS donor Schiff base ruthenium(III) complexes containing PPh3/AsPh3. Priyarega M Muthu Tamizh R Karvembu R Prabhakaran K Natarajan. Volume 123 Issue 3 May ...

  15. Catalytic Converters Maintain Air Quality in Mines

    Science.gov (United States)

    2014-01-01

    At Langley Research Center, engineers developed a tin-oxide based washcoat to prevent oxygen buildup in carbon dioxide lasers used to detect wind shears. Airflow Catalyst Systems Inc. of Rochester, New York, licensed the technology and then adapted the washcoat for use as a catalytic converter to treat the exhaust from diesel mining equipment.

  16. Nonsolvent application of ionic liquids: organo-catalysis by 1-alkyl-3-methylimidazolium cation based room-temperature ionic liquids for chemoselective N-tert-butyloxycarbonylation of amines and the influence of the C-2 hydrogen on catalytic efficiency.

    Science.gov (United States)

    Sarkar, Anirban; Roy, Sudipta Raha; Parikh, Naisargee; Chakraborti, Asit K

    2011-09-02

    1-Alkyl-3-methylimidazolium cation based ionic liquids efficiently catalyze N-tert-butyloxycarbonylation of amines with excellent chemoselectivity. The catalytic role of the ionic liquid is envisaged as "electrophilic activation" of di-tert-butyl dicarbonate (Boc(2)O) through bifurcated hydrogen bond formation with the C-2 hydrogen of the 1-alkyl-3-methylimidazolium cation and has been supported by a downfield shift of the imidazolium C-2 hydrogen of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][NTf(2)]) from δ 8.39 to 8.66 in the presence of Boc(2)O in the (1)H NMR and a drastic reduction of the catalytic efficiency with 1-butyl-2,3-dimethylimidazolium ionic liquids that are devoid of the C-2 hydrogen. The differential time required for reaction with aromatic and aliphatic amines has offered means for selective N-t-Boc formation during inter and intramolecular competitions. Preferential N-t-Boc formation with secondary aliphatic amine has been achieved in the presence of primary aliphatic amine. Comparison of the catalytic efficiency for N-t-Boc formation with a common substrate revealed that [bmim][NTf(2)] is superior to the reported Lewis acid catalysts.

  17. Hybrid membrane with TiO2 based bio-catalytic nanoparticle suspension system for the degradation of bisphenol-A.

    Science.gov (United States)

    Hou, Jingwei; Dong, Guangxi; Luu, Belinda; Sengpiel, Robert G; Ye, Yun; Wessling, Matthias; Chen, Vicki

    2014-10-01

    The removal of micropollutant in wastewater treatment has become a key environmental challenge for many industrialized countries. One approach is to use enzymes such as laccase for the degradation of micropollutants such as bisphenol-A. In this work, laccase was covalently immobilized on APTES modified TiO2 nanoparticles, and the effects of particle modification on the bio-catalytic performance were examined and optimized. These bio-catalytic particles were then suspended in a hybrid membrane reactor for BPA removal with good BPA degradation efficiency observed. Substantial improvement in laccase stability was achieved in the hybrid system compared with free laccase under simulated harsh industrial wastewater treatment conditions (such as a wide range of pH and presence of inhibitors). Kinetic study provided insight of the effect of immobilization on the bio-degradation reaction. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Catalytic activity of some oxime-based Pd(II-complexes in Suzuki coupling of aryl and heteroaryl bromides in water

    Directory of Open Access Journals (Sweden)

    Kamal M. Dawood

    2017-05-01

    Full Text Available The catalytic activity of four Pd(II-complexes of benzoazole-oximes was extensively studied in Suzuki–Miyaura C–C cross coupling reactions in water, as an eco-friendly green solvent, under both thermal heating as well as microwave irradiation conditions. The cross-coupling reactions included different activated and deactivated aryl- or heteroaryl-bromides with several arylboronic acids. The protected oxime-complexes were found to be more efficient than the free ones.

  19. The performance of manganese-based catalysts with Ce0.65Zr0.35O2 as support for catalytic oxidation of toluene

    Science.gov (United States)

    Hou, Zhongyan; Feng, Jie; Lin, Tao; Zhang, Hailong; Zhou, Xiaoying; Chen, Yaoqiang

    2018-03-01

    Mesoporous Ce0.65Zr0.35O2 composites are synthesized by co-precipitation method and a series of novel MnOx/Ce0.65Zr0.35O2 monolithic catalysts with different content of manganese oxides are prepared for toluene catalytic oxidation. The results show that the catalytic activity of Ce0.65Zr0.35O2 is promoted by introduction of manganese and influenced remarkably by the amount of MnOx. In particular, the catalyst with 15 wt.% MnOx loading performs best activity in view of the lowest complete conversion temperature of 250 °C at a GHSV of 12000 h-1. According to the characterizations of N2 adsorption-desorption, XRD, SEM-EDX, H2-TPR, O2-TPD and XPS analyses, the superior catalytic activity could be attributed to the well-dispersed MnOx species, good low-temperature redox property, more Mn4+ species and more available surface and lattice oxygen species. Additionally, the optimized catalyst shows high stability during the thermal aging experiment and long-term testing experiment, and it also shows a good activity under the condition of high gas hourly space velocity, which presents a well application prospect.

  20. 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.

  1. Catalytic Antibodies: Concept and Promise

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 12; Issue 11. Catalytic Antibodies: Concept and Promise. Desirazu N Rao Bharath Wootla. General Article Volume 12 Issue ... Keywords. Catalytic antibodies; abzymes; hybridome technology; Diels– Alder reaction; Michaelis– Menten kinetics; Factor VIII.

  2. A new oxidovanadium(IV) Schiff base complex containing asymmetric tetradentate ONN′O′ Schiff base ligand: synthesis, characterization, crystal structure determination, thermal study and catalytic activity

    Czech Academy of Sciences Publication Activity Database

    Grivani, G.; Ghavami, A.; Eigner, Václav; Dušek, Michal; Khalaji, A.D.

    2015-01-01

    Roč. 26, č. 6 (2015), s. 779-784 ISSN 1001-8417 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : oxidovanadium(IV) * Schiff base * crystal structure * nanoparticle * epoxidation Subject RIV: CC - Organic Chemistry Impact factor: 1.947, year: 2015

  3. Synthesis, characterization, crystal structure, catalytic activity in oxidative bromination, and thermal study of a new oxidovanadium Schiff base complex containing O, N-bidentate Schiff base ligand

    Czech Academy of Sciences Publication Activity Database

    Grivani, G.; Tahmasebi, V.; Khalaji, A.D.; Eigner, Václav; Dušek, Michal

    2014-01-01

    Roč. 67, č. 22 (2014), s. 3664-3677 ISSN 0095-8972 Institutional support: RVO:68378271 Keywords : oxidovanadium(IV) * Schiff base * single crystal * oxidative bromination Subject RIV: CA - Inorganic Chemistry Impact factor: 2.012, year: 2014

  4. Catalytic interface erosion

    International Nuclear Information System (INIS)

    Meng, H.; Cohen, E.G.D.

    1995-01-01

    We study interface erosion processes: catalytic erosions. We present two cases. (1) The erosion of a completely occupied lattice by one single moving particle starting from somewhere inside the lattice, considering deterministic as well as probabilistic erosion rules. In the latter case, the eroded regions appear to have interfaces with continuously tunable fractal dimensions. (2) The kinetic roughening of an initially flat surface, where ballistic or diffusion-limited particles, which remain intact themselves, erode the surface coming from the outside, using the same erosion rules as in (1). Many features resembling realistic interfaces, for example, islands and inlets, are generated. The dependence of the surface width on the system size is due to both the erosion mechanism and the way particles move before reaching the surface

  5. Catalytic detritiation of water

    International Nuclear Information System (INIS)

    Rogers, M.L.; Lamberger, P.H.; Ellis, R.E.; Mills, T.K.

    1977-01-01

    A pilot-scale system has been used at Mound Laboratory to investigate the catalytic detritiation of water. A hydrophobic, precious metal catalyst is used to promote the exchange of tritium between liquid water and gaseous hydrogen at 60 0 C. Two columns are used, each 7.5 m long by 2.5 cm ID and packed with catalyst. Water flow is 5-10 cm 3 /min and countercurrent hydrogen flow is 9,000-12,000 cm 3 /min. The equipment, except for the columns, is housed in an inert atmosphere glovebox and is computer controlled. The hydrogen is obtained by electrolysis of a portion of the water stream. Enriched gaseous tritium is withdrawn for further enrichment. A description of the system is included along with an outline of its operation. Recent experimental data are discussed

  6. Hydrodehalogenation of alkyl iodides with base-mediated hydrogenation and catalytic transfer hydrogenation: application to the asymmetric synthesis of N-protected α-methylamines.

    Science.gov (United States)

    Mandal, Pijus K; Birtwistle, J Sanderson; McMurray, John S

    2014-09-05

    We report a very mild synthesis of N-protected α-methylamines from the corresponding amino acids. Carboxyl groups of amino acids are reduced to iodomethyl groups via hydroxymethyl intermediates. Reductive deiodination to methyl groups is achieved by hydrogenation or catalytic transfer hydrogenation under alkaline conditions. Basic hydrodehalogenation is selective for the iodomethyl group over hydrogenolysis-labile protecting groups, such as benzyloxycarbonyl, benzyl ester, benzyl ether, and 9-fluorenyloxymethyl, thus allowing the conversion of virtually any protected amino acid into the corresponding N-protected α-methylamine.

  7. 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.

  8. Pd(II and Zn(II Based Complexes with Schiff Base Ligands: Synthesis, Characterization, Luminescence, and Antibacterial and Catalytic Activities

    Directory of Open Access Journals (Sweden)

    Zhi-Qiang Feng

    2013-01-01

    Full Text Available Two new metal complexes involving Schiff base ligands, namely, [Pd(L12] (1 and [Zn(L22] (2, [HL1: 2,4-dibromo-6-((E-(mesityliminomethylphenol and HL2: 2-((E-(2,6-diisopropylphenyliminomethyl-4,6-dibromophenol], have been solvothermally synthesized and characterized by elemental analysis, IR-spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. Both 1 and 2 are mononuclear cyclometalated complexes with square planar and tetrahedral coordination geometry, respectively. 1 and 2 display photoluminescence in the solid state at 298 K (fluorescence lifetimes τ = 5.521 μs at 508 nm for 1; τ = 3.697 μs at 506 nm for 2. These Schiff base ligands and their metal complexes have been screened for antibacterial activity against several bacteria strains, and the results are compared with the activity of penicillin. Moreover, the Suzuki reaction of 4-bromoanisole with phenylboronic acid by 1 has also been studied.

  9. Processing and structural characterization of porous reforming catalytic films

    International Nuclear Information System (INIS)

    Hou Xianghui; Williams, Jey; Choy, Kwang-Leong

    2006-01-01

    Nickel-based catalysts are often used to reform methanol into hydrogen. The preparation and installation of these catalysts are costly and laborious. As an alternative, directly applying catalytic films onto the separator components can improve the manufacturing efficiency. This paper reports the successful deposition of adherent porous NiO-Al 2 O 3 -based catalytic films with well-controlled stoichiometry, using a single-step Aerosol Assisted Chemical Vapour Deposition (AACVD) method. The microstructure, composition and crystalline phase of the as-deposited catalytic films are characterized using a combination of X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared (FTIR) Spectrometer. The results have demonstrated the capability of AACVD to produce porous NiO-Al 2 O 3 -based catalytic films

  10. Catalytic cracking with deasphalted oil

    Energy Technology Data Exchange (ETDEWEB)

    Beaton, W.I.; Taylor, J.L.; Peck, L.B.; Mosby, J.F.

    1990-07-10

    This patent describes a catalytic cracking process. It comprises: hydrotreating resid; thereafter deasphalting the hydrotreated resid to produce substantially deasphalted oil; catalytically cracking the hydrotreated oil in a catalytic cracking unit in the presence of a cracking catalyst to produce upgraded oil leaving coked catalyst; and regenerating the coked catalyst in the presence of a combustion-supporting gas comprising excess molecular oxygen in an amount greater than the stoichiometric amount required for substantially completely combusting the coke on the catalyst to carbon dioxide.

  11. Method to produce catalytically active nanocomposite coatings

    Energy Technology Data Exchange (ETDEWEB)

    Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat

    2017-12-19

    A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

  12. Method to produce catalytically active nanocomposite coatings

    Science.gov (United States)

    Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat

    2016-02-09

    A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

  13. 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.

  14. 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.)

  15. Nd(III) and Dy(III) coordination compounds based on 1H-tetrazolate-5-acetic acid ligands: Synthesis, crystal structures and catalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Li Qiaoyun; Chen Dianyu; He Minghua [Jiangsu Laboratory of Advanced Functional Materials, Department of Chemistry and Materials Engineering, Changshu Institute of Technology, Changshu 215500, Jiangsu (China); Yang Gaowen, E-mail: ygwsx@126.com [Jiangsu Laboratory of Advanced Functional Materials, Department of Chemistry and Materials Engineering, Changshu Institute of Technology, Changshu 215500, Jiangsu (China); Shen Lei; Zhai Chun; Shen Wei; Gu Kun; Zhao Jingjing [Jiangsu Laboratory of Advanced Functional Materials, Department of Chemistry and Materials Engineering, Changshu Institute of Technology, Changshu 215500, Jiangsu (China)

    2012-06-15

    Reactions of 1H-tetrazolate-5-acetic acid(H{sub 2}tza) with Nd(NO{sub 3}){sub 3}{center_dot}6H{sub 2}O or Dy(NO{sub 3}){sub 3}{center_dot}6H{sub 2}O with the presence of KOH under solvothermal conditions, produced two new coordination compounds, [M{sub 2}(tza){sub 3}(H{sub 2}O){sub 6}]{center_dot}2H{sub 2}O [M=Nd(1), Dy(2)]. Both compounds were structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Compounds 1 and 2 reveal 1D structures via bridging tza as linker. Furthermore, the compounds 1 and 2 showed a specific and good catalytic behavior for the polymerization of styrene, and the polymerization showed controlled characteristics. - Graphical Abstract: Two new coordination compounds, [M{sub 2}(tza){sub 3}(H{sub 2}O){sub 6}]{center_dot}2H{sub 2}O [M=Nd(1), Dy(2)] have been synthesis. 1 and 2 reveal 1D structures via bridging tza as linker, and showed a specific and good catalytic behavior for the polymerization of styrene. Highlights: Black-Right-Pointing-Pointer we have reported two novel compounds formed by H{sub 2}tza and Nd(III) or Dy(III). Black-Right-Pointing-Pointer Compounds 1 and 2 were found to have catalysis property for the photo-polymerization of styrene. Black-Right-Pointing-Pointer The high molecular weight polymers with narrow molecular weight distributions were obtained.

  16. Catalytic pyrolysis of lignocellulosic biomass

    NARCIS (Netherlands)

    Seshan, Kulathuiyer; Sa, Jacinto

    2014-01-01

    This chapter reports on the latest developments of biomass catalytic pyrolysis for the production of fuels. The primary focus is on the role of catalysts in the process, namely, their influence in the liquefaction of lignocellulosic biomass.

  17. 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.

  18. Kinetic Parameters of Non-Isothermal Thermogravimetric Non-Catalytic and Catalytic Pyrolysis of Empty Fruit Bunch with Alumina by Kissinger and Ozawa Methods

    Science.gov (United States)

    Rahayu Mohamed, Alina; Li, Nurfahani; Sohaimi, Khairunissa Syairah Ahmad; Izzati Iberahim, Nur; Munirah Rohaizad, Nor; Hamzah, Rosniza

    2018-03-01

    The non-isothermal thermogravimetric non-catalytic and catalytic empty fruit bunch (EFB) pyrolysis with alumina were performed at different heating rates of 10, 15, 20, 25, 30 and 40 K/min under nitrogen atmosphere at a flow rate of 100 ml/min under dynamic conditions from 301 K to 1273 K. The activation energy were calculated based on Kissinger and Ozawa methods. Both reactions followed first order reactions. By Kissinger method, the activation energy and Ln A values for non-catalytic and catalytic EFB pyrolysis with alumina were 188.69 kJ mol-1 and 201.67 kJ/mol respectively. By Ozawa method, the activation energy values for non-catalytic and catalytic EFB pyrolysis with alumina were 189.13 kJ/mol and 201.44 kJ/mol respectively. The presence of catalyst increased the activation energy values for EFB pyrolysis as calculated by Kissinger and Ozawa methods.

  19. Perovskite-type catalytic materials for environmental applications.

    Science.gov (United States)

    Labhasetwar, Nitin; Saravanan, Govindachetty; Kumar Megarajan, Suresh; Manwar, Nilesh; Khobragade, Rohini; Doggali, Pradeep; Grasset, Fabien

    2015-06-01

    Perovskites are mixed-metal oxides that are attracting much scientific and application interest owing to their low price, adaptability, and thermal stability, which often depend on bulk and surface characteristics. These materials have been extensively explored for their catalytic, electrical, magnetic, and optical properties. They are promising candidates for the photocatalytic splitting of water and have also been extensively studied for environmental catalysis applications. Oxygen and cation non-stoichiometry can be tailored in a large number of perovskite compositions to achieve the desired catalytic activity, including multifunctional catalytic properties. Despite the extensive uses, the commercial success for this class of perovskite-based catalytic materials has not been achieved for vehicle exhaust emission control or for many other environmental applications. With recent advances in synthesis techniques, including the preparation of supported perovskites, and increasing understanding of promoted substitute perovskite-type materials, there is a growing interest in applied studies of perovskite-type catalytic materials. We have studied a number of perovskites based on Co, Mn, Ru, and Fe and their substituted compositions for their catalytic activity in terms of diesel soot oxidation, three-way catalysis, N 2 O decomposition, low-temperature CO oxidation, oxidation of volatile organic compounds, etc. The enhanced catalytic activity of these materials is attributed mainly to their altered redox properties, the promotional effect of co-ions, and the increased exposure of catalytically active transition metals in certain preparations. The recent lowering of sulfur content in fuel and concerns over the cost and availability of precious metals are responsible for renewed interest in perovskite-type catalysts for environmental applications.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-07-15

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

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

    International Nuclear Information System (INIS)

    Lee, Minjae; Kim, Bohyun; Lee, Yuna; Kim, Beomtae; Park, Joon B.

    2014-01-01

    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 2 and O 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

  2. Shape and catalytic mechanism of RuO{sub 2} particles at CO oxidation reaction conditions. First-principles based multi-scale modeling

    Energy Technology Data Exchange (ETDEWEB)

    Reuter, Karsten [TU Muenchen (Germany). Lehrstuhl fuer Theoretische Chemie

    2016-11-01

    For model catalyst studies on low-index single-crystal surfaces close agreement between detailed measurements and quantitative microkinetic modeling can increasingly be achieved. However, for 'real' catalyst particles, such structure-morphology-activity relationships are only scarcely established. This is prototypically reflected by the situation for RuO{sub 2}, as a most active catalyst for CO oxidation. Here, existing first-principles kinetic modeling is restricted to just one facet, namely the RuO{sub 2}(110) surface, which is not able to fully account for activity data obtained from polycrystalline RuO{sub 2} powder catalysts. The overarching objective of this project was correspondingly to close this gap and demonstrate that similarly close agreement as for individual single-crystal model catalysts can also be achieved for catalyst particles. Specifically, we addressed experiments where an intact RuO{sub 2} bulk structure is conserved, and establish the atomic-scale structure and reactivity of other RuO{sub 2} low-index facets under the gas-phase conditions characteristic for catalytic CO oxidation.

  3. Catalytic hydrogen recombination for nuclear containments

    International Nuclear Information System (INIS)

    Koroll, G.W.; Lau, D.W.P.; Dewit, W.A.; Graham, W.R.C.

    1994-01-01

    Catalytic recombiners appear to be a credible option for hydrogen mitigation in nuclear containments. The passive operation, versatility and ease of back fitting are appealing for existing stations and new designs. Recently, a generation of wet-proofed catalyst materials have been developed at AECL which are highly specific to H 2 -O 2 , are active at ambient temperatures and are being evaluated for containment applications. Two types of catalytic recombiners were evaluated for hydrogen removal in containments based on the AECL catalyst. The first is a catalytic combustor for application in existing air streams such as provided by fans or ventilation systems. The second is an autocatalytic recombiner which uses the enthalpy of reaction to produce natural convective flow over the catalyst elements. Intermediate-scale results obtained in 6 m 3 and 10 m 3 spherical and cylindrical vessels are given to demonstrate self-starting limits, operating limits, removal capacity, scaling parameters, flow resistance, mixing behaviour in the vicinity of an operating recombiner and sensitivity to poisoning, fouling and radiation. (author). 13 refs., 10 figs

  4. Catalytic bioreactors and methods of using same

    Science.gov (United States)

    Worden, Robert Mark; Liu, Yangmu Chloe

    2017-07-25

    Various embodiments provide a bioreactor for producing a bioproduct comprising one or more catalytically active zones located in a housing and adapted to keep two incompatible gaseous reactants separated when in a gas phase, wherein each of the one or more catalytically active zones may comprise a catalytic component retainer and a catalytic component retained within and/or thereon. Each of the catalytically active zones may additionally or alternatively comprise a liquid medium located on either side of the catalytic component retainer. Catalytic component may include a microbial cell culture located within and/or on the catalytic component retainer, a suspended catalytic component suspended in the liquid medium, or a combination thereof. Methods of using various embodiments of the bioreactor to produce a bioproduct, such as isobutanol, are also provided.

  5. Iridium complexes containing mesoionic C donors: selective C(sp3)-H versus C(sp2)-H bond activation, reactivity towards acids and bases, and catalytic oxidation of silanes and water.

    Science.gov (United States)

    Petronilho, Ana; Woods, James A; Mueller-Bunz, Helge; Bernhard, Stefan; Albrecht, Martin

    2014-11-24

    Metalation of a C2-methylated pyridylimidazolium salt with [IrCp*Cl2]2 affords either an ylidic complex, resulting from C(sp(3))-H bond activation of the C2-bound CH3 group if the metalation is performed in the presence of a base, such as AgO2 or Na2CO3, or a mesoionic complex via cyclometalation and thermally induced heterocyclic C(sp(2))-H bond activation, if the reaction is performed in the absence of a base. Similar cyclometalation and complex formation via C(sp(2))-H bond activation is observed when the heterocyclic ligand precursor consists of the analogous pyridyltriazolium salt, that is, when the metal bonding at the C2 position is blocked by a nitrogen rather than a methyl substituent. Despite the strongly mesoionic character of both the imidazolylidene and the triazolylidene, the former reacts rapidly with D(+) and undergoes isotope exchange at the heterocyclic C5 position, whereas the triazolylidene ligand is stable and only undergoes H/D exchange under basic conditions, where the imidazolylidene is essentially unreactive. The high stability of the Ir-C bond in aqueous solution over a broad pH range was exploited in catalytic water oxidation and silane oxidation. The catalytic hydrosilylation of ketones proceeds with turnover frequencies as high as 6,000 h(-1) with both the imidazolylidene and the triazolylidene system, whereas water oxidation is enhanced by the stronger donor properties of the imidazol-4-ylidene ligands and is more than three times faster than with the triazolylidene analogue. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Immobilization of glucose oxidase onto a novel platform based on modified TiO2 and graphene oxide, direct electrochemistry, catalytic and photocatalytic activity

    International Nuclear Information System (INIS)

    Haghighi, Nasibeh; Hallaj, Rahman; Salimi, Abdollah

    2017-01-01

    In this work a new organic–inorganic nanocomposite has been introduced for enzyme immobilization. The composite consisting of graphene oxide (GO) and titanium oxide nanoparticles (TiO 2 ) modified with 2, 2′-dithioxo-3, 3′-bis (3-(triethoxysilyl) propyl)-2H, 2′H-[5, 5′-bithiazolylidene]-4, 4′(3H, 3′H)-dione as Organic-Inorganic Supporting Ligand (OISL). The OISL was covalently attached to TiO 2 nanoparticles and employed for obtaining a suitable solid surface to enzyme attachment. The glucose oxidase (GOD) was irreversibly loaded on the GC/GO/TiO 2 -OISL using consecutive cyclic voltammetry. The enzyme immobilization and the enzymatic activity were determined by electrochemical methods. The cyclic voltammogram displayed a pair of well-defined and nearly symmetric redox peaks with a formal potential of − 0.465 V and an apparent electron transfer rate constant of 1.74 s −1 . The GO/TiO 2 -OISL can catalyze the electroreduction and electrooxidation of hydrogen peroxide. The GC/GO/TiO 2 -OISL/GOD electrode was used in the hydrogen peroxide determination. The fabricated nanobiocomposite shows dramatic photoelectrocatalytic activity which evaluated by studying the electrocatalytic activity of the fabricated electrode toward hydrogen peroxide in darkness and in the presences of light. - Highlights: • In this work a novel platform used to successful immobilization of glucose oxidase. Due to its large functional group this modified nanoparticles load enzyme (GOD) and remain enzyme whit out denaturation for a long time. • The loaded enzyme shows direct electron transfer and excellent charge transfer kinetic. Also the fabricated nano-bio-composite has good catalytic activity toward hydrogen peroxide during electrooxidation and electro reduction process. • The nano-bio-composite shows excellent photocatalytic activity.

  7. 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...

  8. 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...

  9. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    ... 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 ...

  10. Catalytic properties of niobium compounds

    International Nuclear Information System (INIS)

    Tanabe, K.; Iizuka, T.

    1983-04-01

    The catalytic activity and selectivity of niobium compounds including oxides, salts, organometallic compounds and others are outlined. The application of these compounds as catalysts to diversified reactions is reported. The nature and action of niobium catalysts are characteristic and sometimes anomalous, suggesting the necessity of basic research and the potential use as catalysts for important processes in the chemical industry. (Author) [pt

  11. Catalytic carboxyester hydrolysis by diaminodiphenols

    Indian Academy of Sciences (India)

    Administrator

    Two diaminodiphenols, 1 and 2, have been examined as catalysts for the hydrolysis of 4- nitrophenyl acetate (NA) and 4-nitrophenylphosphate (NP) in aqueous-acetonitrile (25% acetonitrile v/v) media at 35ºC, I = 1·0 mol dm–3. The compound 1 enhances the hydrolysis rate of NA more than 105 times. Its catalytic efficiency ...

  12. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    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 ...

  13. Plasma-catalytic reforming of liquid hydrocarbons

    International Nuclear Information System (INIS)

    Nedybaliuk, O.A.; Chernyak, V.Ya; Kolgan, V.V.; Iukhymenko, V.V.; Solomenko, O.V.; Fedirchyk, I.I.; Martysh, E.V.; Demchina, V.P.; Klochok, N.V.; Dragnev, S.V.

    2015-01-01

    The series of experiments studying the plasma-catalytic reforming of liquid hydrocarbons was carried out. The dynamic plasma-liquid system based on a low-power rotating gliding arc with solid electrodes was used for the investigation of liquid hydrocarbons reforming process. Conversion was done via partial oxidation. A part of oxidant flow was activated by the discharge. Synthesis-gas composition was analysed by means of mass-spectrometry and gas-chromatography. A standard boiler, which operates on natural gas and LPG, was used for the burning of synthesis-gas

  14. Atomic Distribution in Catalytic Amorphous Metals

    Directory of Open Access Journals (Sweden)

    Sanghita Mridha

    2015-01-01

    Full Text Available The atomic distribution in catalytically active metallic glass alloys, Pd43Cu27Ni10P20 and Pt57.5Cu14.7Ni5.3P22.5, was investigated using three-dimensional atom probe microscopy. Atom probe analysis showed uniform distribution of constituent elements for both the starting amorphous alloys, with no phase separation. Both the crystallized alloys showed eutectic microstructure with a very sharp interface (~0.5 nm as determined from atom probe. The atomic distribution in the devitrified state is explained based on the “fragile liquid” behavior for these noble-metal glassy alloys.

  15. Catalytic Stereoinversion of L-Alanine to Deuterated D-Alanine.

    Science.gov (United States)

    Moozeh, Kimia; So, Soon Mog; Chin, Jik

    2015-08-03

    A combination of an achiral pyridoxal analogue and a chiral base has been developed for catalytic deuteration of L-alanine with inversion of stereochemistry to give deuterated D-alanine under mild conditions (neutral pD and 25 °C) without the use of any protecting groups. This system can also be used for catalytic deuteration of D-alanine with retention of stereochemistry to give deuterated D-alanine. Thus a racemic mixture of alanine can be catalytically deuterated to give an enantiomeric excess of deuterated D-alanine. While catalytic deracemization of alanine is forbidden by the second law of thermodynamics, this system can be used for catalytic deracemization of alanine with deuteration. Such green and biomimetic approach to catalytic stereocontrol provides insights into efficient amino acid transformations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Catalytically enhanced combustion process

    International Nuclear Information System (INIS)

    Rodriguez, C.

    1992-01-01

    This patent describes a fuel having improved combustion efficiency. It comprises a petroleum based liquid hydrocarbon; and a combustion catalyst comprising from about 18 to about 21 weight percent naphthalene, from about 75 to about 80 weight percent toluene, and from about 2.8 to about 3.2 weight percent benzyl alcohol

  17. 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.

  18. Catalytic Conversion of Carbohydrates

    DEFF Research Database (Denmark)

    Osmundsen, Christian Mårup

    with the production of commodity chemicals from the most abundantly available renewable source of carbon, carbohydrates. The production of alkyl lactates by the Lewis acid catalyzed conversion of hexoses is an interesting alternative to current fermentation based processes. A range of stannosilicates were....... The synthesis of these by the cycloaddition of ethylene to furanic compounds, followed by dehydrative aromatization, was demonstrated in good yields, using a strong Brønsted acidic catalyst, WOx/ZrO2. As both ethylene and furanics can be derived from carbohydrates by known processes, this constitutes...

  19. Mass spectrometry–based relative quantification of proteins in precatalytic and catalytically active spliceosomes by metabolic labeling (SILAC), chemical labeling (iTRAQ), and label-free spectral count

    Science.gov (United States)

    Schmidt, Carla; Grønborg, Mads; Deckert, Jochen; Bessonov, Sergey; Conrad, Thomas; Lührmann, Reinhard; Urlaub, Henning

    2014-01-01

    The spliceosome undergoes major changes in protein and RNA composition during pre-mRNA splicing. Knowing the proteins—and their respective quantities—at each spliceosomal assembly stage is critical for understanding the molecular mechanisms and regulation of splicing. Here, we applied three independent mass spectrometry (MS)–based approaches for quantification of these proteins: (1) metabolic labeling by SILAC, (2) chemical labeling by iTRAQ, and (3) label-free spectral count for quantification of the protein composition of the human spliceosomal precatalytic B and catalytic C complexes. In total we were able to quantify 157 proteins by at least two of the three approaches. Our quantification shows that only a very small subset of spliceosomal proteins (the U5 and U2 Sm proteins, a subset of U5 snRNP-specific proteins, and the U2 snRNP-specific proteins U2A′ and U2B′′) remains unaltered upon transition from the B to the C complex. The MS-based quantification approaches classify the majority of proteins as dynamically associated specifically with the B or the C complex. In terms of experimental procedure and the methodical aspect of this work, we show that metabolically labeled spliceosomes are functionally active in terms of their assembly and splicing kinetics and can be utilized for quantitative studies. Moreover, we obtain consistent quantification results from all three methods, including the relatively straightforward and inexpensive label-free spectral count technique. PMID:24448447

  20. Inorganic membranes and catalytic reactors

    OpenAIRE

    Rangel, Maria do Carmo

    1997-01-01

    Membrane reactors are reviewed with emphasis in their applications in catalysis field. The basic principles of these systems are presented as well as a historical development. The several kinds of catalytic membranes and their preparations are discussed including the problems, needs and challenges to be solved in order to use these reactors in commercial processes. Some applications of inorganic membrane reactors are also shown. It was concluded that these systems have a great potential for i...

  1. Catalytic Conversion of Biofuels

    DEFF Research Database (Denmark)

    Jørgensen, Betina

    catalysts, and two different experimental methods, namely, a batch system and a continuous flow system. In the batch reaction the process was carried out in the liquid phase using a gold catalyst and atmospheric air as the oxidant. Experiments were conducted at moderate pressures and temperatures (90-200 °C......, 30-45 bar) with an aqueous solution of ethanol. It was possible to produce acetic acid in yields above 90 %. Two different support materials were investigated (MgAl2O4 and TiO2) and there did not seem to be any significant effect in changing the support. The kinetics of the reaction was also...... the major product. In the continuous flow system, the oxidation reaction was carried out as a gas phase reaction using a vanadium based catalyst. For this series of experiments, a 50 wt% aqueous ethanol was oxidized with a diluted gas stream of O2 in helium, the reaction temperature and pressure were kept...

  2. Evolution of prokaryotic subtilases: genome-wide analysis reveals novel subfamilies with different catalytic residues

    NARCIS (Netherlands)

    Siezen, R.J.; Renckens, B.A.M.; Boekhorst, J.

    2007-01-01

    Subtilisin-like serine proteases (subtilases) are a very diverse family of serine proteases with low sequence homology, often limited to regions surrounding the three catalytic residues. Starting with different Hidden Markov Models (HMM), based on sequence alignments around the catalytic residues of

  3. High-Capacity Sodium Peroxide Based NaO2 Batteries with Low Charge Overpotential via a Nanostructured Catalytic Cathode

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Lu; Zhang, Dongzhou [Partnership; Lei, Yu [Department; Yuan, Yifei; Wu, Tianpin; Lu, Jun; Amine, Khalil

    2018-01-05

    The superoxide based Na-O-2 battery has circumvented the issue of large charge overpotential in Li-O-2 batteries; however, the one-electron process leads to limited capacity. Herein, a sodium peroxide based low-overpotential (similar to 0.5 V) Na-O-2 battery with a capacity as high as 7.5 mAh/cm(2) is developed with Pd nanoparticles as catalysts on the cathode.

  4. Carbonates-based noble metal-free lean NOx trap catalysts MOx-K2CO3/K2Ti8O17 (M = Ce, Fe, Cu, Co) with superior catalytic performance

    Science.gov (United States)

    Zhang, Yuxia; You, Rui; Liu, Dongsheng; Liu, Cheng; Li, Xingang; Tian, Ye; Jiang, Zheng; Zhang, Shuo; Huang, Yuying; Zha, Yuqing; Meng, Ming

    2015-12-01

    A series of base metal-based lean NOx trap (LNT) catalysts MOx-K2CO3/K2Ti8O17 (M = Ce, Fe, Cu, Co) were synthesized by successive impregnations and employed for the storage and reduction of NOx in the emissions of lean-burn engines at 350 °C. The XRD and XANES/EXAFS results reveal that the active phases in the corresponding catalysts exist as CeO2, Fe2O3, CuO and Co3O4, respectively. Among all the catalysts, CoOx-K2CO3/K2Ti8O17 exhibits the best performance, which cannot only trap the NOx quickly and completely at lean condition, giving the highest storage capacity (3.32 mmol/g) reported so far, but also reduce the NOx at rich condition, showing a NOx reduction percentage as high as 99.0%. Meanwhile, this catalyst displays an ultralow NOx to N2O selectivity (0.3%) during NOx reduction. The excellent performance of CoOx-K2CO3/K2Ti8O17 results from its largest amount of surface active oxygen species as revealed by XPS, O2-TPD and NO-TPD. HRTEM, FT-IR and CO2-TPD results illustrate that several kinds of K species such as sbnd OK groups, K2O, surface carbonates and bulk or bulk-like carbonates coexist in the catalysts. Based upon the in situ DRIFTS results, the participation of K2CO3 in NOx storage is confirmed, and the predominant NOx storage species is revealed as bidentate nitrites formed via multiple kinetic pathways. The low cost and high catalytic performance of the CoOx-based LNT catalyst make it most promising for the substitution of noble metal-based LNT catalysts.

  5. Hydrophilic Pt nanoflowers: synthesis, crystallographic analysis and catalytic performance.

    Science.gov (United States)

    Mourdikoudis, Stefanos; Altantzis, Thomas; Liz-Marzán, Luis M; Bals, Sara; Pastoriza-Santos, Isabel; Pérez-Juste, Jorge

    2016-05-21

    Water-soluble Pt nanoflowers (NFs) were prepared by diethylene glycol-mediated reduction of Pt acetylacetonate (Pt(acac) 2 ) in the presence of polyethylenimine. Advanced electron microscopy analysis showed that the NFs consist of multiple branches with a truncated cubic morphology and different crystallographic orientations. We demonstrate that the nature of the solvent strongly influences the resulting morphology. The catalytic performance of the Pt NFs in 4-nitrophenol reduction was found to be superior to that of other nanoparticle-based catalysts. Additionally, the Pt NFs display good catalytic reusability with no loss of activity after five consecutive cycles.

  6. 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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Imaging Catalytic Surfaces by Multiplexed Capillary Electrophoresis With Absorption Detection

    Energy Technology Data Exchange (ETDEWEB)

    Christodoulou, Michael [Iowa State Univ., Ames, IA (United States)

    2002-01-01

    A new technique for in situ imaging and screening heterogeneous catalysts by using multiplexed capillary electrophoresis with absorption detection was developed. By bundling the inlets of a large number of capillaries, an imaging probe can be created that can be used to sample products formed directly from a catalytic surface with high spatial resolution. In this work, they used surfaces made of platinum, iron or gold wires as model catalytic surfaces for imaging. Various shapes were recorded including squares and triangles. Model catalytic surfaces consisting of both iron and platinum wires in the shape of a cross were also imaged successfully. Each of the two wires produced a different electrochemical product that was separated by capillary electrophoresis. Based on the collected data they were able to distinguish the products from each wire in the reconstructed image.

  8. 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.

  9. Flow in axisymmetric expansion in a catalytic converter

    DEFF Research Database (Denmark)

    Gotfredsen, Erik; Meyer, Knud Erik

    The flow in an axisymmetric expansion (circular diffusor) is used in many different engineering applications, such as heat exchangers, catalytic converters and filters. These applications require a relatively uniform flow at the inlet. To minimise the pressure loss, an ideal solution would...... for a specific local flow rate and a non-uniform inflow to the catalyst will severely reduce the efficiency of the process. Since each ship will have a unique design the flow system, it is desirable to be able to design the system using Computational Fluid Dynamics (CFD). However, CFD fails to predict flow......-scaled model of the catalytic converter is constructed, see figure 1. The experiments are performed at laboratory conditions, with lower pressure, temperature and velocity than the full-scale catalytic converter. The Reynolds number based on the velocity in the inlet pipe and the diameter of the converter...

  10. 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

  11. Spectrophotometric determination of nitrite by its catalytic effect on ...

    African Journals Online (AJOL)

    A novel simple, sensitive and rapid kinetic-spectrophotometric method for the determination of trace amounts of nitrite is proposed. The method is based on its catalytic effect on the oxidation of congo red (CR) by potassium bromate in acidic solution. The oxidation reaction is monitored spectrophotometrically by measuring ...

  12. Automatic prediction of catalytic residues by modeling residue structural neighborhood

    Directory of Open Access Journals (Sweden)

    Passerini Andrea

    2010-03-01

    Full Text Available Abstract Background Prediction of catalytic residues is a major step in characterizing the function of enzymes. In its simpler formulation, the problem can be cast into a binary classification task at the residue level, by predicting whether the residue is directly involved in the catalytic process. The task is quite hard also when structural information is available, due to the rather wide range of roles a functional residue can play and to the large imbalance between the number of catalytic and non-catalytic residues. Results We developed an effective representation of structural information by modeling spherical regions around candidate residues, and extracting statistics on the properties of their content such as physico-chemical properties, atomic density, flexibility, presence of water molecules. We trained an SVM classifier combining our features with sequence-based information and previously developed 3D features, and compared its performance with the most recent state-of-the-art approaches on different benchmark datasets. We further analyzed the discriminant power of the information provided by the presence of heterogens in the residue neighborhood. Conclusions Our structure-based method achieves consistent improvements on all tested datasets over both sequence-based and structure-based state-of-the-art approaches. Structural neighborhood information is shown to be responsible for such results, and predicting the presence of nearby heterogens seems to be a promising direction for further improvements.

  13. 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...

  14. Catalytic synthesis of alcoholic fuels for transportation from syngas

    DEFF Research Database (Denmark)

    Wu, Qiongxiao

    This work has investigated the catalytic conversion of syngas into methanol and higher alcohols. Based on input from computational catalyst screening, an experimental investigation of promising catalyst candidates for methanol synthesis from syngas has been carried out. Cu-Ni alloys of different ...

  15. RUTHENIUM(III) DETERMINATION BY KINETIC-CATALYTIC ...

    African Journals Online (AJOL)

    +, H+, ClO2- and catalyst. The pertinent mechanism, consistent with the experimental results is proposed. Based on the high sensitivity and selectivity of the reaction to the presence of Ru(III), using its catalytic efficiency on the oxidation of Nile ...

  16. Carbogenic molecular sieves for reaction and separation by design: A novel approach to shape selective super base, super acid and catalytic membranes. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Foley, Henry C.

    2002-03-18

    This report details the findings of three years of research plus one year of a no-cost extension. Primary results are the work with supported nanoporous carbon membranes for separation and reaction as well as with cesium-nanoporous carbon catalysts. The work resulted in 17 plus 2 papers (2 are in progress) and partial or full support for five Ph.D. students. Two patents were filed based on this research.

  17. Carbon nanofibers: a versatile catalytic support

    Directory of Open Access Journals (Sweden)

    Nelize Maria de Almeida Coelho

    2008-09-01

    Full Text Available The aim of this article is present an overview of the promising results obtained while using carbon nanofibers based composites as catalyst support for different practical applications: hydrazine decomposition, styrene synthesis, direct oxidation of H2S into elementary sulfur and as fuel-cell electrodes. We have also discussed some prospects of the use of these new materials in total combustion of methane and in ammonia decomposition. The macroscopic carbon nanofibers based composites were prepared by the CVD method (Carbon Vapor Deposition employing a gaseous mixture of hydrogen and ethane. The results showed a high catalytic activity and selectivity in comparison to the traditional catalysts employed in these reactions. The fact was attributed, mainly, to the morphology and the high external surface of the catalyst support.

  18. The Influence of Base Metal (M Oxidation State in Au-M-O/TiO2 Systems on Their Catalytic Activity in Carbon Monoxide Oxidation

    Directory of Open Access Journals (Sweden)

    Katarzyna Samson

    2011-12-01

    Full Text Available Base metal promoted gold/titania catalysts were synthesized, characterized and tested in CO oxidation reaction. Catalysts containing dopant metals in higher oxidation states exhibited higher activity than catalysts containing dopants in reduced states. The activity of fresh catalysts promoted by Cu, Fe and Ni was similar to the unpromoted one, but treatment in reducing and oxidizing atmospheres revealed the supremacy of the copper promoted catalyst. The sequential deposition method proved to be better than the co-deposition—precipitation method. An attempt to explain these differences using XPS, FTIR and H2 TPR was performed.

  19. Amperometric glucose sensor based on enhanced catalytic reduction of oxygen using glucose oxidase adsorbed onto core-shell Fe3O4-silica-Au magnetic nanoparticles

    International Nuclear Information System (INIS)

    Wang Aijun; Li Yongfang; Li Zhonghua; Feng Jiuju; Sun Yanli; Chen Jianrong

    2012-01-01

    Monodisperse Fe 3 O 4 magnetic nanoparticles (NPs) were prepared under facile solvothermal conditions and successively functionalized with silica and Au to form core/shell Fe 3 O 4 -silica-Au NPs. Furthermore, the samples were used as matrix to construct a glucose sensor based on glucose oxidase (GOD). The immobilized GOD retained its bioactivity with high protein load of 3.92 × 10 −9 mol·cm −2 , and exhibited a surface-controlled quasi-reversible redox reaction, with a fast heterogeneous electron transfer rate of 7.98 ± 0.6 s −1 . The glucose biosensor showed a broad linear range up to 3.97 mM with high sensitivity of 62.45 μA·mM −1 cm −2 and fast response (less than 5 s). - Graphical abstract: Core-shell structured Fe 3 O 4 -silica-Au nanoparticles were prepared and used as matrix to construct an amperometric glucose sensor based on glucose oxidase, which showed broad linear range, high sensitivity, and fast response. Highlights: ► Synthesis of monodispersed Fe 3 O 4 nanoparticles. ► Fabrication of core/shell Fe 3 O 4 -silica-Au nanoparticles. ► Construction of a novel glucose sensor with wide linear range, high sensitivity and fast response.

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

    Directory of Open Access Journals (Sweden)

    Ye Wang

    2015-09-01

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

  1. Kinetic studies of the impact of thiocyanate moiety on the catalytic properties of Cu(II) and Fe(III) complexes of a new Mannich base

    Science.gov (United States)

    Ayeni, Ayowole O.; Watkins, Gareth M.

    2018-04-01

    Four new metal complexes of a novel Mannich base 5-methyl-2-((4-(pyridin-2-yl)piperazin-1-yl)methyl)phenol (HL) have been prepared. The compounds were characterized by an array of analytical and spectroscopic methods including Nuclear Magnetic Resonance, Infra-red and UV-Visible spectroscopy. Compounds 1-4 behaved as effective catalysts towards the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to its corresponding quinone in the presence of molecular oxygen in DMF solution while compound 4 proved to be the best catalyst with a turnover rate of 17.93 ± 1.10 h-1 as other complexes showed lower rates of oxidation. Also with the exception of dinuclear iron complex (4); thiocyanate containing Cu(II) complex exhibited lower catecholase activity compared to the Cu(II) complex without it.

  2. Bipyridine- and phenanthroline-based metal-organic frameworks for highly efficient and tandem catalytic organic transformations via directed C-H activation

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Kuntal [Univ. of Chicago, Chicago, IL (United States); Zhang, Teng [Univ. of Chicago, Chicago, IL (United States); Greene, Francis X. [Univ. of Chicago, Chicago, IL (United States); Lin, Wenbin [Univ. of Chicago, Chicago, IL (United States)

    2015-02-16

    We report here the synthesis of a series of robust and porous bipyridyl- and phenanthryl-based metal–organic frameworks (MOFs) of UiO topology (BPV-MOF, mBPV-MOF, and mPT-MOF) and their postsynthetic metalation to afford highly active single-site solid catalysts. While BPV-MOF was constructed from only bipyridyl-functionalized dicarboxylate linker, both mBPV- and mPT-MOF were built with a mixture of bipyridyl- or phenanthryl-functionalized and unfunctionalized dicarboxylate linkers. The postsynthetic metalation of these MOFs with [Ir(COD)(OMe)]2 provided Ir-functionalized MOFs (BPV-MOF-Ir, mBPV-MOF-Ir, and mPT-MOF-Ir), which are highly active catalysts for tandem hydrosilylation of aryl ketones and aldehydes followed by dehydrogenative ortho-silylation of benzylicsilyl ethers as well as C–H borylation of arenes using B₂pin₂. Both mBPV-MOF-Ir and mPT-MOF-Ir catalysts displayed superior activities compared to BPV-MOF-Ir due to the presence of larger open channels in the mixed-linker MOFs. Impressively, mBPV-MOF-Ir exhibited high TONs of up to 17000 for C–H borylation reactions and was recycled more than 15 times. The mPT-MOF-Ir system is also active in catalyzing tandem dehydrosilylation/dehydrogenative cyclization of N-methylbenzyl amines to azasilolanes in the absence of a hydrogen acceptor. Importantly, MOF-Ir catalysts are significantly more active (up to 95 times) and stable than their homogeneous counterparts for all three reactions, strongly supporting the beneficial effects of active site isolation within MOFs. This work illustrates the ability to increase MOF open channel sizes by using the mixed linker approach and shows the enormous potential of developing highly active and robust single-site solid catalysts based on MOFs containing nitrogen-donor ligands for important organic transformations.

  3. Synthesis and reactivity of iron complexes with a new pyrazine-based pincer ligand, and application in catalytic low-pressure hydrogenation of carbon dioxide.

    Science.gov (United States)

    Rivada-Wheelaghan, Orestes; Dauth, Alexander; Leitus, Gregory; Diskin-Posner, Yael; Milstein, David

    2015-05-04

    A novel pincer ligand based on the pyrazine backbone (PNzP) has been synthesized, (2,6-bis(di(tert-butyl)phosphinomethyl)pyrazine), tBu-PNzP. It reacts with FeBr2 to yield [Fe(Br)2(tBu-PNzP)], 1. Treatment of 1 with NaBH4 in MeCN/MeOH gives the hydride complex [Fe(H)(MeCN)2(tBu-PNzP)][X] (X = Br, BH4), 2·X. Counterion exchange and exposure to CO atmosphere yields the complex cis-[Fe(H)(CO)(MeCN)(tBu-PNzP)][BPh4] 4·BPh4, which upon addition of Bu4NCl forms [Fe(H)(Cl)(CO)(tBu-PNzP)] 5. Complex 5, under basic conditions, catalyzes the hydrogenation of CO2 to formate salts at low H2 pressure. Treatment of complex 5 with a base leads to aggregates, presumably of dearomatized species B, stabilized by bridging to another metal center by coordination of the nitrogen at the backbone of the pyrazine pincer ligand. Upon dissolution of compound B in EtOH the crystallographically characterized complex 7 is formed, comprised of six iron units forming a 6-membered ring. The dearomatized species can activate CO2 and H2 by metal-ligand cooperation (MLC), leading to complex 8, trans-[Fe(PNzPtBu-COO)(H)(CO)], and complex 9, trans-[Fe(H)2(CO)(tBu-PNzP)], respectively. Our results point at a very likely mechanism for CO2 hydrogenation involving MLC.

  4. 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.

  5. Catalytic Organometallic Reactions of Ammonia

    Science.gov (United States)

    Klinkenberg, Jessica L.

    2012-01-01

    Until recently, ammonia had rarely succumbed to catalytic transformations with homogeneous catalysts, and the development of such reactions that are selective for the formation of single products under mild conditions has encountered numerous challenges. However, recently developed catalysts have allowed several classes of reactions to create products with nitrogen-containing functional groups from ammonia. These reactions include hydroaminomethylation, reductive amination, alkylation, allylic substitution, hydroamination, and cross-coupling. This Minireview describes examples of these processes and the factors that control catalyst activity and selectivity. PMID:20857466

  6. Studies of Catalytic Model Systems

    DEFF Research Database (Denmark)

    Holse, Christian

    of the Cu/ZnO nanoparticles is highly relevant to industrial methanol synthesis for which the direct interaction of Cu and ZnO nanocrystals synergistically boost the catalytic activity. The dynamical behavior of the nanoparticles under reducing and oxidizing environments were studied by means of ex situ X...... as the nanoparticles are reduced. The Cu/ZnO nanoparticles are tested on a  µ-reactor platform and prove to be active towards methanol synthesis, making it an excellent model system for further investigations into activity depended morphology changes....

  7. Catalytic Combustion of Ethyl Acetate

    OpenAIRE

    ÖZÇELİK, Tuğba GÜRMEN; ATALAY, Süheyda; ALPAY, Erden

    2014-01-01

    The catalytic combustion of ethyl acetate over prepared metal oxide catalysts was investigated. CeO, Co2O3, Mn2O3, Cr2O3, and CeO-Co2O3 catalysts were prepared on monolith supports and they were tested. Before conducting the catalyst experiments, we searched for the homogeneous gas phase combustion reaction of ethyl acetate. According to the homogeneous phase experimental results, 45% of ethyl acetate was converted at the maximum reactor temperature tested (350 °C). All the prepare...

  8. 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

  9. Structured materials for catalytic and sensing applications

    Science.gov (United States)

    Hokenek, Selma

    been synthesized and characterized to establish the effects of nanoparticle size on catalytic activity in methanol decomposition. The physicochemical properties of the synthesized palladium-nickel nanoparticles will be discussed, as a function of the synthesis parameters. The optical characteristics of the Ag and Pd nanoparticles will be determined, with a view toward tuning the response of the nanoparticles for incorporation in sensors. Analysis of the monometallic palladium particles revealed a dependence of syngas production on nanoparticle size. The peak and steady state TOFs increased roughly linearly with the average nanoparticle diameter. The amount of coke deposited on the particle surfaces was found to be independent on the size of the nanoparticles. Shape control of the nickel-palladium nanoparticles with a high selectivity for (100) and (110) facets (≤ 80%) has been demonstrated. The resulting alloy nanoparticles were found to have homogeneous composition throughout their volume and maintain FCC crystal structure. Substitution of Ni atoms in the Pd lattice at a 1:3 molar ratio was found to induce lattice strains of ~1%. The Ag nanocubes synthesized exhibited behavior very similar to literature values, when taken on their own, exhibiting a pair of distinct absorbance peaks at 350 nm and 455 nm. In physical mixtures with the Pd nanoparticles synthesized, their behavior showed that the peak position of the Ag nanocubes' absorbance in UV-Vis could be tuned based on the relative proportions of the Ag and Pd nanoparticles present in the suspension analysed. The Ag polyhedra synthesized for comparison showed a broad doublet peak throughout the majority of the visible range before testing as a component in a physical mixture with the Pd nanoparticles. The addition of Pd nanoparticles to form a physical mixture resulted in some damping of the doublet peak observed as well as a corresponding shift in the baseline absorbance proportional to the amount of Pd added to

  10. DNA-based electrochemical determination of mercury(II) by exploiting the catalytic formation of gold amalgam and of silver nanoparticles

    International Nuclear Information System (INIS)

    Tang, Juan; Huang, Yapei; Zhang, Cengceng; Liu, Huiqiong; Tang, Dianping

    2016-01-01

    The authors describe an electrochemical assay for mercury ion (Hg 2+ ) by using a glassy carbon electrode (GCE) to which a 25-base thymine oligomer was covalently immobilized. On addition of Hg(II) ion, it is captured via T-Hg(II)-T coordination. The T-Hg(II)-T complex catalyzes the reduction of auric acid by hydroxylamine and this leads to the formation of gold amalgam (AuHg). The electrode is then placed in an ammoniacal solution of silver nitrate. On applying a deposition potential of −0.12 V for 60 s, silver nanoparticles are deposited on the surface that serve as signal reporters to indicate the concentration of Hg(II) in the sample solution. The electrode, if operated at 50 mV (vs. Ag/AgCl) enables Hg(II) to be detected in the 0.005 to 80 nM concentration range, with a detection limit as low as 2 pM. The method was successfully applied to the determination of Hg(II) in spiked river water. (author)

  11. Modeling the selective catalytic reduction of NOx by ammonia over a Vanadia-based catalyst from heavy duty diesel exhaust gases

    International Nuclear Information System (INIS)

    Yun, Byoung Kyu; Kim, Man Young

    2013-01-01

    A numerical simulation for prediction of NO X conversion over a commercial V 2 O 5 catalyst with NH 3 as a reductant was performed for a heavy duty diesel engine applications. The chemical behaviors of the SCR reactor are described by using the global NO X kinetics including standard, fast, and NH 3 oxidation reactions with the Langmuir–Hinshelwood (LH) mechanism incorporated into the commercial Boost code. After introducing mathematical models for the SCR reaction with specific reaction parameters, the effects of various parameters such as space velocities, the O 2 , H 2 O, NO 2 , and NH 3 concentrations on the NOx conversion are thoroughly studied and validated by comparing with the experimental data available in the literature. It is found that NO X conversion increases with decreasing space velocity, H 2 O concentration, and NH 3 /NO X ratio, and increasing O 2 concentration and NO 2 /NO X ratio. The study shows that not only is the present approach adopted is flexible in treating performance of the commercial V 2 O 5 based SCR catalyst, it is also accurate and efficient for the prediction of NO X conversion in diesel exhaust environments. - Highlights: ► To find the reaction parameters for LH mechanism over a commercial V2O5 catalyst. ► To investigate the effects of various parameters on the SCR NO X conversion. ► To present benchmark solutions on SCR behavior with diesel exhaust environments.

  12. Catalytic enantioselective Reformatsky reaction with ketones

    NARCIS (Netherlands)

    Fernandez-Ibanez, M. Angeles; Macia, Beatriz; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    Chiral tertiary alcohols were obtained with good yields and enantioselectivities via a catalytic Reformatsky reaction with ketones, including the challenging diaryl ketones, using chiral BINOL derivatives.

  13. Bio-hydrogen production based on catalytic reforming of volatiles generated by cellulose pyrolysis: An integrated process for ZnO reduction and zinc nanostructures fabrication

    International Nuclear Information System (INIS)

    Maciel, Adriana Veloso; Job, Aldo Eloizo; Nova Mussel, Wagner da; Brito, Walter de; Duarte Pasa, Vanya Marcia

    2011-01-01

    The paper presents a process of cellulose thermal degradation with bio-hydrogen generation and zinc nanostructures synthesis. Production of zinc nanowires and zinc nanoflowers was performed by a novel processes based on cellulose pyrolysis, volatiles reforming and direct reduction of ZnO. The bio-hydrogen generated in situ promoted the ZnO reduction with Zn nanostructures formation by vapor-solid (VS) route. The cellulose and cellulose/ZnO samples were characterized by thermal analyses (TG/DTG/DTA) and the gases evolved were analyzed by FTIR spectroscopy (TG/FTIR). The hydrogen was detected by TPR (Temperature Programmed Reaction) tests. The results showed that in the presence of ZnO the cellulose thermal degradation produced larger amounts of H 2 when compared to pure cellulose. The process was also carried out in a tubular furnace with N 2 atmosphere, at temperatures up to 900 o C, and different heating rates. The nanostructures growth was catalyst-free, without pressure reduction, at temperatures lower than those required in the carbothermal reduction of ZnO with fossil carbon. The nanostructures were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The optical properties were investigated by photoluminescence (PL). One mechanism was presented in an attempt to explain the synthesis of zinc nanostructures that are crystalline, were obtained without significant re-oxidation and whose morphologies are dependent on the heating rates of the process. This route presents a potential use as an industrial process taking into account the simple operational conditions, the low costs of cellulose and the importance of bio-hydrogen and nanostructured zinc.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1999-07-01

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

  15. Photo-catalytic degradation of VOCs in gas phase on modified TiO{sub 2} systems; Degradation photocatalytique de COV en phase gaz sur des systemes a base de TiO{sub 2} modifie

    Energy Technology Data Exchange (ETDEWEB)

    Barraud, E.; Keller, N.; Keller, V.; Garin, F. [Laboratoire des Materiaux, Surfaces et Procedes pour la Catalyse (LMSPC), UMR 7515 du CNRS et ELCASS - European Laboratory for Catalysis and Surface Science, 67 - Strasbourg (France)

    2004-07-01

    The aim of this work is to develop new TiO{sub 2} photo-catalytic materials, obtained by addition of metals or oxides or by combination with others semi-conductors leading to composite coupled semi-conductors systems. The results obtained on TiO{sub 2} (P25-Degussa), Pt/TiO{sub 2}, WO{sub 3}/TiO{sub 2}, SiC-TiO{sub 2}, WO{sub 3}/SiC-TiO{sub 2}... systems are compared and discussed in terms of the composition of the composite systems for the photo-catalytic oxidation reactions of butyl acetate, methyl-ethyl-ketone and toluene. It has been particularly shown that the effect of the coupling is totally different following to the organic function to oxidize and to the coupled semi-conductor, leading in some cases to a considerable increase of the photo-catalytic efficiency. (O.M.)

  16. Catalytic converters in the fireplace

    International Nuclear Information System (INIS)

    Kouki, J.

    1995-01-01

    In addition to selecting the appropriate means of heating and using dry fuel, the amount of harmful emissions contained by flue gases produced by fireplaces can be reduced by technical means. One such option is to use an oxidising catalytic converter. Tests at TTS Institute's Heating Studies Experimental Station have focused on two such converters (dense and coarse) mounted in light-weight iron heating stoves. The ability of the dense catalytic converter to oxidise carbon monoxide gases proved to be good. The concentration of carbon monoxide in the flue gases was reduced by as much as 90 %. Measurements conducted by VTT (Technical Research Centre of Finland) showed that the conversion of other gases, e.g. of methane, was good. The exhaust resistance caused by the dense converter was so great as to necessitate the mounting of a fluegas evacuation fan in the chimney for the purpose of creating sufficient draught. When relying on natural draught, the dense converter requires a chimney of at least 7 metres and a by-pass connection while the fire is being lit. In addition, the converter will have to be constructed to be less dense and this will mean that it's capability to oxidise non-combusted gases will be reduced. The coarse converter did not impair the draught but it's oxidising property was insufficient. With the tests over, the converter was not observed to have become blocked up by impurities

  17. 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).

  18. Catalytic Conia-ene and related reactions.

    Science.gov (United States)

    Hack, Daniel; Blümel, Marcus; Chauhan, Pankaj; Philipps, Arne R; Enders, Dieter

    2015-10-07

    Since its initial inception, the Conia-ene reaction, known as the intramolecular addition of enols to alkynes or alkenes, has experienced a tremendous development and appealing catalytic protocols have emerged. This review fathoms the underlying mechanistic principles rationalizing how substrate design, substrate activation, and the nature of the catalyst work hand in hand for the efficient synthesis of carbocycles and heterocycles at mild reaction conditions. Nowadays, Conia-ene reactions can be found as part of tandem reactions, and the road for asymmetric versions has already been paved. Based on their broad applicability, Conia-ene reactions have turned into a highly appreciated synthetic tool with impressive examples in natural product synthesis reported in recent years.

  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. Flowthrough Reductive Catalytic Fractionation of Biomass

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Eric M.; Stone, Michael L.; Katahira, Rui; Reed, Michelle; Beckham, Gregg T.; Román-Leshkov, Yuriy

    2017-11-01

    Reductive catalytic fractionation (RCF) has emerged as a leading biomass fractionation and lignin valorization strategy. Here, flowthrough reactors were used to investigate RCF of poplar. Most RCF studies to date have been conducted in batch, but a flow-based process enables the acquisition of intrinsic kinetic and mechanistic data essential to accelerate the design, optimization, and scale-up of RCF processes. Time-resolved product distributions and yields obtained from experiments with different catalyst loadings were used to identify and deconvolute events during solvolysis and hydrogenolysis. Multi-bed RCF experiments provided unique insights into catalyst deactivation, showing that leaching, sintering, and surface poisoning are causes for decreased catalyst performance. The onset of catalyst deactivation resulted in higher concentrations of unsaturated lignin intermediates and increased occurrence of repolymerization reactions, producing high-molecular-weight species. Overall, this study demonstrates the concept of flowthrough RCF, which will be vital for realistic scale-up of this promising approach.

  1. Lignin Valorization using Heterogenous Catalytic Oxidation

    DEFF Research Database (Denmark)

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

    The research interests in biomass conversion to fuels and chemicals has increased significantly in the last decade in view of current problems such as global warming, high oil prices, food crisis and other geopolitical scenarios. Many different reactions and processes to convert biomass into high......-value products and fuels have been proposed in the literature, giving special attention to the conversion of lignocellulosic biomass, which does not compete with food resources and is widely available as a low cost feedstock 1. Lignocellulose biomass is a complex material composed of three main fractions...... be obtained 2. Heiko Lange et al., has reported that the catalytic oxidation products of lignin and lignin model compounds range from aromatic aldehyde and carboxylic acid and they must be originate form oxidation of side chain. The products we obtained in these reactions are based on the severity...

  2. Catalytic upgrading of butyric acid towards fine chemicals and biofuels.

    Science.gov (United States)

    Sjöblom, Magnus; Matsakas, Leonidas; Christakopoulos, Paul; Rova, Ulrika

    2016-04-01

    Fermentation-based production of butyric acid is robust and efficient. Modern catalytic technologies make it possible to convert butyric acid to important fine chemicals and biofuels. Here, current chemocatalytic and biocatalytic conversion methods are reviewed with a focus on upgrading butyric acid to 1-butanol or butyl-butyrate. Supported Ruthenium- and Platinum-based catalyst and lipase exhibit important activities which can pave the way for more sustainable process concepts for the production of green fuels and chemicals. © FEMS 2016.

  3. Catalytic upgrading of butyric acid towards fine chemicals and biofuels

    OpenAIRE

    Sj?blom, Magnus; Matsakas, Leonidas; Christakopoulos, Paul; Rova, Ulrika

    2016-01-01

    Fermentation-based production of butyric acid is robust and efficient. Modern catalytic technologies make it possible to convert butyric acid to important fine chemicals and biofuels. Here, current chemocatalytic and biocatalytic conversion methods are reviewed with a focus on upgrading butyric acid to 1-butanol or butyl-butyrate. Supported Ruthenium- and Platinum-based catalyst and lipase exhibit important activities which can pave the way for more sustainable process concepts for the produc...

  4. Heterogeneous catalytic degradation of polyacrylamide solution | Hu ...

    African Journals Online (AJOL)

    Modified with trace metal elements, the catalytic activity of Fe2O3/Al2O3 could be changed greatly. Among various trace metal elements, Fe2O3/Al2O3 catalysts modified with Co and Cu showed great increase on catalytic activity. International Journal of Engineering, Science and Technology, Vol. 2, No. 7, 2010, pp. 110- ...

  5. Catalytic gasification of dry and wet biomass

    NARCIS (Netherlands)

    van Rossum, G.; Potic, B.; Kersten, Sascha R.A.; van Swaaij, Willibrordus Petrus Maria

    2009-01-01

    Catalytic gasification of dry biomass and of wet biomass streams in hot compressed water are reviewed and discussed as potential technologies for the production of synthesis gas, hydrogen- and methane-rich gas. Next to literature data also new experimental results from our laboratory on catalytic

  6. Catalytic destruction of tar in biomass derived producer gas

    International Nuclear Information System (INIS)

    Zhang Ruiqin; Brown, Robert C.; Suby, Andrew; Cummer, Keith

    2004-01-01

    The purpose of this study is to investigate catalytic destruction of tar formed during gasification of biomass, with the goal of improving the quality of the producer gas. This work focuses on nickel based catalysts treated with alkali in an effort to promote steam gasification of the coke that deposits on catalyst surfaces. A tar conversion system consisting of a guard bed and catalytic reactor was designed to treat the producer gas from an air blown, fluidized bed biomass gasifier. The guard bed used dolomite to crack the heavy tars. The catalytic reactor was used to evaluate three commercial steam reforming catalysts. These were the ICI46-1 catalyst from Imperial Chemical Industry and Z409 and RZ409 catalysts from Qilu Petrochemical Corp. in China. A 0.5-3 l/min slipstream from a 5 tpd biomass gasifier was used to test the tar conversion system. Gas and tar were sampled before and after the tar conversion system to evaluate the effectiveness of the system. Changes in gas composition as functions of catalytic bed temperature, space velocity and steam/TOC (total organic carbon) ratio are presented. Structural changes in the catalysts during the tests are also described

  7. Catalytic Activity Control via Crossover between Two Different Microstructures

    KAUST Repository

    Zhou, Yuheng

    2017-09-08

    Metal nanocatalysts hold great promise for a wide range of heterogeneous catalytic reactions, while the optimization strategy of catalytic activity is largely restricted by particle size or shape control. Here, we demonstrate that a reversible microstructural control through the crossover between multiply-twinned nanoparticle (MTP) and single crystal (SC) can be readily achieved by solvent post-treatment on gold nanoparticles (AuNPs). Polar solvents (e.g. water, methanol) direct the transformation from MTP to SC accompanied by the disappearance of twinning and stacking faults. A reverse transformation from SC to MTP is achieved in non-polar solvent (e.g. toluene) mixed with thiol ligands. The transformation between two different microstructures is directly observed by in-situ TEM and leads to a drastic modulation of catalytic activity towards the gas-phase selective oxidation of alcohols. There is a quasi-linear relationship between TOFs and MTP concentrations. Based on the combined experimental and theoretical investigations of alcohol chemisorption on these nanocatalysts, we propose that the exposure of {211}-like microfacets associated with twin boundaries and stack faults accounts for the strong chemisorption of alcohol molecules on MTP AuNPs and thus the exceptionally high catalytic activity.

  8. Non-Catalytic Ignition System for High Performance Advanced Monopropellant Thrusters, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Systima Technologies, Inc. is developing a non-catalytic ignition technology for advanced green ionic salt monopropellants such as HAN-based monopropellant AF-M315E....

  9. Non-Catalytic Thruster for High Performance Advanced Monopropellant, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Systima Technologies, Inc. has demonstrated a low power non-catalytic ignition technology for advanced green monopropellant thrusters operating with HAN-based...

  10. Next Generation Hybrid Photo-Catalytic Oxidation (PCO) for Trace Contaminant Control

    Data.gov (United States)

    National Aeronautics and Space Administration — Photocatalytic oxidation (PCO) is a primary candidate as an alternative to thermal-catalytic or sorbent- based technologies for VOC trace contaminant control due to...

  11. Application of BiFeO3-based on nickel foam composites with a highly efficient catalytic activity and easily recyclable in Fenton-like process under microwave irradiation

    Science.gov (United States)

    Li, Shuo; Zhang, Guangshan; Zheng, Heshan; Zheng, Yongjie; Wang, Peng

    2018-05-01

    In this study, BiFeO3 (BFO) powders decorated on nickel foam (NF) with a high catalytic activity are prepared via a one-step microwave-assisted hydrothermal method. The factors that influence the degradation of bisphenol A (BPA) with BFO/NFs as catalysts are optimized to improve the catalytic activity in a microwave-enhanced Fenton-like process. BFO/NF exhibit a superior catalytic activity with a high BPA removal ratio (98.4%) and TOC removal ratio (69.5%) within 5 min. Results indicate that NF significantly affect the improvement of the catalytic activity of BFO because it served as a source of hydroxyl radicals (•OH) during degradation. The amount of •OH generated by BFO/NF is approximately 1.65-fold higher than that by pure BFO. After six reaction cycles, the stability and reusability of •OH remain high. These findings provide new insights into the synthesis of composites on heterogeneous catalysts with high efficiency and easy recyclability for water treatment applications.

  12. Non-catalytic recuperative reformer

    Science.gov (United States)

    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.

  13. 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.

  14. 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.)

  15. Diesel engine catalytic combustor system. [aircraft engines

    Science.gov (United States)

    Ream, L. W. (Inventor)

    1984-01-01

    A low compression turbocharged diesel engine is provided in which the turbocharger can be operated independently of the engine to power auxiliary equipment. Fuel and air are burned in a catalytic combustor to drive the turbine wheel of turbine section which is initially caused to rotate by starter motor. By opening a flapper value, compressed air from the blower section is directed to catalytic combustor when it is heated and expanded, serving to drive the turbine wheel and also to heat the catalytic element. To start, engine valve is closed, combustion is terminated in catalytic combustor, and the valve is then opened to utilize air from the blower for the air driven motor. When the engine starts, the constituents in its exhaust gas react in the catalytic element and the heat generated provides additional energy for the turbine section.

  16. The evolution of catalytic function

    Science.gov (United States)

    Maurel, Marie-Christine; Ricard, Jacques

    2006-03-01

    It is very likely that the main driving force of enzyme evolution is the requirement to improve catalytic and regulatory efficiency which results from the intrinsic performance as well as from the spatial and functional organization of enzymes in living cells. Kinetic co-operativity may occur in simple monomeric proteins if they display “slow” conformational transitions, at the cost of catalytic efficiency. Oligomeric enzymes on the other hand can be both efficient and co-operative. We speculate that the main reason for the emergence of co-operative oligomeric enzymes is the need for catalysts that are both cooperative and efficient. As it is not useful for an enzyme to respond to a change of substrate concentration in a complex kinetic way, the emergence of symmetry has its probable origin in a requirement for “functional simplicity”. In a living cell, enzyme are associated with other macromolecules and membranes. The fine tuning of their activity may also be reached through mutations of the microenvironment. Our hypothesis is that these mutations are related to the vectorial transport of molecules, to achieve the hysteresis loops of enzyme reactions generated by the coupling of reaction and diffusion, through the co-operativity brought about by electric interactions between a charged substrate and a membrane, and last but not least, through oscillations. As the physical origins of these effects are very simple and do not require complex molecular devices, it is very likely that the functional advantage generated by the spatial and functional organization of enzyme molecules within the cell have appeared in prebiotic catalysis or very early during the primeval stages of biological evolution. We shall began this paper by presenting the nature of the probable earliest catalysts in the RNA world.

  17. 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

  18. Catalytic reduction of N2O over Ag-Pd/Al2O3 bimetallic catalysts.

    Science.gov (United States)

    Tzitzios, V K; Georgakilas, V

    2005-05-01

    A study of the catalytic conversion of N2O to N2 over a bimetallic Ag-Pd catalyst is described in this article. Several Ag-Pd catalytic systems were prepared supported on Al2O3 with different ratios and their catalytic activity for the direct decomposition of N2O and their reduction with CO was measured. Based on the experimental results, it was observed that Ag-Pd bimetallic catalyst (5-0.5%) was the most active for both nitrous oxide reduction and direct decomposition. This high activity seems to be connected with a synergistic effect between Ag and Pd.

  19. Forced concentration oscillations for catalytic reactions with stop-effect

    OpenAIRE

    Thullie, Jan; Renken, Albert

    1991-01-01

    The effect of forced concn. oscillations on a catalytic reaction with stop-effect was studied based on 2 different adsorption-desorption models. Both models predict mean reaction rates which can be more than twice as high as the max. rate under optimum steady-state conditions. An anal. soln. is presented to describe the mean performance as a function of concn., length of period, and cycle split. [on SciFinder (R)

  20. New self-assembled material based on Ru nanoparticles and 4-sulfocalix[4]arene as an efficient and recyclable catalyst for reduction of brilliant yellow azo dye in water: a new model catalytic reaction

    Energy Technology Data Exchange (ETDEWEB)

    Rambabu, Darsi; Pradeep, Chullikkattil P.; Dhir, Abhimanew, E-mail: abhimanew@iitmandi.ac.in [Indian Institute of Technology (India)

    2016-12-15

    New self-assembled material (Ru@SC) with ruthenium nanoparticles (Ru NPs) and 4-sulfocalix[4]arene (SC) is synthesized in water at room temperature. Ru@SC is characterized by thermal gravimetric analysis, FT-IR, powder x-ray diffraction, TEM and SEM analysis. The size of Ru nanoparticles in the self-assembly is approximately 5 nm. The self-assembled material Ru@SC shows an efficient catalytic reduction of toxic ‘brilliant yellow’ (BY) azo dye. The reduced amine products were successfully separated and confirmed by single-crystal XRD, NMR and UV-Vis spectroscopy. Ru@SC showed a better catalytic activity in comparison with commercial catalysts Ru/C (ruthenium on charcoal 5 %) and Pd/C (palladium on charcoal 5 and 10 %). The catalyst also showed a promising recyclability and heterogeneous nature as a catalyst for reduction of ‘BY’ azo dye.

  1. 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.

  2. 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.

  3. 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.

  4. Catalytic determination of ultratrace amounts of ruthenium with oscillopolarography monitoring

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Zhi-Liang; Wang Li-Sheng (Guangxi Normal Univ., Guilin (China))

    1993-09-01

    The single sweep oscillopolarographic behaviour of Rhodamine B in sulphuric acid medium was investigated. A novel, sensitive and selective catalytic method with oscillopolarography monitoring for the determination of ultratrace amounts of ruthenium was described, based on the catalytic effect of Ru(III) on the slow redox reaction occurring between Rhodamine B and potassium periodate in sulphuric acid medium at 25[degrees]C. Single sweep oscillopolarography is used to monitor the changes in concentration of Rhodamine B by means of the second derivative wave [minus]0.55 V vs. SCE. The determination range from 8.2x10[sup [minus]10] to 2.5x10[sup [minus]8] M Ru was obtained by the initial rate procedure. Influence of 30 foreign ions was considered. Ru in ore samples was analysed by this method, with satisfactory results.

  5. Catalytic Science and Technology in Sustainable Energy II

    DEFF Research Database (Denmark)

    Wang, Yuxin; Xiao, Feng-Shou; Seshan, Kulathu K.

    2017-01-01

    as compared with the 29 contributions published twoyears ago in the previous special issue of Catalysis Today under the same title "Catalytic Science and Technology in Sustainable Energy". We gratefully acknowledge all the authors and reviewers of the manuscripts and the editorial team of Elsevier, without......This special issue of Catalysis Today results from four sessions, under the collective theme "Catalysis in Sustainable Energy", of the 2ndInternational Symposium on Catalytic Science and Technology in Sustainable Energy and Environment, held in Tianjin, China during October 12-14, 2016....... This biennial symposium offers an international forum for discussing and sharing the cutting-edge researches and the most recent breakthroughsin energy and environmental technologies based on catalysis principles. Included in this special issue are 36 invited contributions, which is a noticeable expansion...

  6. Catalytic determination of vanadium in water

    Science.gov (United States)

    Fishman, M. J.; Skougstad, M.W.

    1964-01-01

    A rapid, accurate, and sensitive spectrophotometric method for the quantitative determination of trace amounts of vanadium in water is based on the catalytic effect of vanadium on the rate of oxidation of gallic acid by persulfate in acid solution. Under given conditions of concentrations of reactants, temperature, and reaction time, the extent of oxidation of gallic acid is proportional to the concentration of vanadium present. Vanadium is determined by measuring the absorbance of the sample at 415 m?? and comparison with standard solutions treated in an identical manner. Concentrations in the range of from 0.1 to 8.0 ??g. per liter may be determined with a standard deviation of 0.2 or less. By reducing the reaction time, the method may be extended to cover the range from 1 to 100 ??g. with a standard deviation of 0.8 or less. Several substances interfere, including chloride above 100 p.p.m., and bromide and iodide in much lower concentrations. Interference from the halides is eliminated or minimized by the addition of mercuric nitrate solution. Most other substances do not interfere at the concentration levels at which they commonly occur in natural waters.

  7. Additive Manufacturing of Catalytically Active Living Materials.

    Science.gov (United States)

    Saha, Abhijit; Johnston, Trevor G; Shafranek, Ryan T; Goodman, Cassandra J; Zalatan, Jesse G; Storti, Duane W; Ganter, Mark A; Nelson, Alshakim

    2018-04-10

    Living materials, which are composites of living cells residing in a polymeric matrix, are designed to utilize the innate functionalities of the cells to address a broad range of applications such as fermentation and biosensing. Herein, we demonstrate the additive manufacturing of catalytically active living materials (AMCALM) for continuous fermentation. A multi-stimuli-responsive yeast-laden hydrogel ink, based on F127-dimethacrylate, was developed and printed using a direct-write 3D printer. The reversible stimuli-responsive behaviors of the polymer hydrogel inks to temperature and pressure are critical, as they enabled the facile incorporation of yeast cells and subsequent fabrication of 3D lattice constructs. Subsequent photo-cross-linking of the printed polymer hydrogel afforded a robust elastic material. These yeast-laden living materials were metabolically active in the fermentation of glucose into ethanol for 2 weeks in a continuous batch process without significant reduction in efficiency (∼90% yield of ethanol). This cell immobilization platform may potentially be applicable toward other genetically modified yeast strains to produce other high-value chemicals in a continuous biofermentation process.

  8. 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.

  9. A Self-Switchable Polymer Reactor for Controlled Catalytic Chemistry Processes with a Hyperbranched Structure

    Directory of Open Access Journals (Sweden)

    Rong Luo

    2018-02-01

    Full Text Available A self-switchable polymer reactor with a hyperbranched structure for controlled catalytic chemistry processes is reported. This polymer reactor was made of silver nanoparticles and a polymer carrier consisting of hyperbranched polyethylenimine and hydroxyethyl acrylate that behaved as thermally switchable domains. Below the transfer temperature, relatively strong catalytic reactivity was demonstrated due to the leading role of hydrophilic groups in the switchable domains, which opened access to the substrate for the packaged silver nanoparticles. In contrast, it showed weak catalysis at relatively high temperatures, reducing from the significantly increased hydrophobicity in the switchable domains. In this way, the polymer reactor displays controllable, tunable, catalytic activity based on this approach. This novel design opens up the opportunity to develop intelligent polymer reactors for controlled catalytic processes.

  10. Formalization of hydrocarbon conversion scheme of catalytic cracking for mathematical model development

    Science.gov (United States)

    Nazarova, G.; Ivashkina, E.; Ivanchina, E.; Kiseleva, S.; Stebeneva, V.

    2015-11-01

    The issue of improving the energy and resource efficiency of advanced petroleum processing can be solved by the development of adequate mathematical model based on physical and chemical regularities of process reactions with a high predictive potential in the advanced petroleum refining. In this work, the development of formalized hydrocarbon conversion scheme of catalytic cracking was performed using thermodynamic parameters of reaction defined by the Density Functional Theory. The list of reaction was compiled according to the results of feedstock structural-group composition definition, which was done by the n-d-m-method, the Hazelvuda method, qualitative composition of feedstock defined by gas chromatography-mass spectrometry and individual composition of catalytic cracking gasoline fraction. Formalized hydrocarbon conversion scheme of catalytic cracking will become the basis for the development of the catalytic cracking kinetic model.

  11. Structural basis for catalytically restrictive dynamics of a high-energy enzyme state

    Science.gov (United States)

    Kovermann, Michael; Ådén, Jörgen; Grundström, Christin; Elisabeth Sauer-Eriksson, A.; Sauer, Uwe H.; Wolf-Watz, Magnus

    2015-07-01

    An emerging paradigm in enzymology is that transient high-energy structural states play crucial roles in enzymatic reaction cycles. Generally, these high-energy or `invisible' states cannot be studied directly at atomic resolution using existing structural and spectroscopic techniques owing to their low populations or short residence times. Here we report the direct NMR-based detection of the molecular topology and conformational dynamics of a catalytically indispensable high-energy state of an adenylate kinase variant. On the basis of matching energy barriers for conformational dynamics and catalytic turnover, it was found that the enzyme's catalytic activity is governed by its dynamic interconversion between the high-energy state and a ground state structure that was determined by X-ray crystallography. Our results show that it is possible to rationally tune enzymes' conformational dynamics and hence their catalytic power--a key aspect in rational design of enzymes catalysing novel reactions.

  12. CSmetaPred: a consensus method for prediction of catalytic residues.

    Science.gov (United States)

    Choudhary, Preeti; Kumar, Shailesh; Bachhawat, Anand Kumar; Pandit, Shashi Bhushan

    2017-12-22

    Knowledge of catalytic residues can play an essential role in elucidating mechanistic details of an enzyme. However, experimental identification of catalytic residues is a tedious and time-consuming task, which can be expedited by computational predictions. Despite significant development in active-site prediction methods, one of the remaining issues is ranked positions of putative catalytic residues among all ranked residues. In order to improve ranking of catalytic residues and their prediction accuracy, we have developed a meta-approach based method CSmetaPred. In this approach, residues are ranked based on the mean of normalized residue scores derived from four well-known catalytic residue predictors. The mean residue score of CSmetaPred is combined with predicted pocket information to improve prediction performance in meta-predictor, CSmetaPred_poc. Both meta-predictors are evaluated on two comprehensive benchmark datasets and three legacy datasets using Receiver Operating Characteristic (ROC) and Precision Recall (PR) curves. The visual and quantitative analysis of ROC and PR curves shows that meta-predictors outperform their constituent methods and CSmetaPred_poc is the best of evaluated methods. For instance, on CSAMAC dataset CSmetaPred_poc (CSmetaPred) achieves highest Mean Average Specificity (MAS), a scalar measure for ROC curve, of 0.97 (0.96). Importantly, median predicted rank of catalytic residues is the lowest (best) for CSmetaPred_poc. Considering residues ranked ≤20 classified as true positive in binary classification, CSmetaPred_poc achieves prediction accuracy of 0.94 on CSAMAC dataset. Moreover, on the same dataset CSmetaPred_poc predicts all catalytic residues within top 20 ranks for ~73% of enzymes. Furthermore, benchmarking of prediction on comparative modelled structures showed that models result in better prediction than only sequence based predictions. These analyses suggest that CSmetaPred_poc is able to rank putative catalytic

  13. Recyclable Nanostructured Catalytic Systems in Modern Environmentally Friendly Organic Synthesis

    Directory of Open Access Journals (Sweden)

    Irina Beletskaya

    2010-07-01

    Full Text Available Modern chemical synthesis makes heavy use of different types of catalytic systems: homogeneous, heterogeneous and nano-sized. The latter – nano-sized catalysts – have given rise in the 21st century to a rapidly developing area of research encompassing several prospects and opportunities for new technologies. Catalytic reactions ensure high regio- and stereoselectivity of chemical transformations, as well as better yields and milder reaction conditions. In recent years several novel catalytic systems were developed for selective formation of carbon-heteroatom and carbon-carbon bonds. This review presents the achievements of our team in our studies on various types of catalysts containing metal nanoparticles: palladium-containing diblock copolymer micelles; soluble palladium-containing polymers; metallides on a support; polymeric metal salts and oxides; and, in addition, metal-free organic catalysts based on soluble polymers acting as nanoreactors. Representative examples are given and discussed in light of possible applications to solve important problems in modern organic synthesis.

  14. Measurements of H-atom density by a catalytic probe

    International Nuclear Information System (INIS)

    Vesel, A.; Drenik, A.; Mozetic, M.

    2006-01-01

    One of the important plasma parameters in tokamaks is the density of neutral hydrogen atoms which can be measured by catalytic probes. The method is based on the catalytic recombination of H atoms on the metal surface. In order to prevent a substantial drain of atoms by the probe, it should be made as small as possible. But still this effect can not be neglected. Therefore a study of the influence of a catalytic probe on the H-atom density was performed. The source of neutral H-atoms was inductively coupled RF hydrogen plasma. The gas from the discharge vessel was leaked to an experimental chamber through a narrow tube with the diameter of 5 mm and the length of 6 cm. Charged particles created in the discharge vessel were recombined on the walls of the narrow tube, so that the gas entering the experimental chamber was a mixture of hydrogen atoms and molecules only. The density of H-atoms in the experimental chamber was measured with two nickel catalytic probes. One probe was at fixed position and the other one was made movable. A change in the probe signal of the fixed probe was measured versus the position of the movable probe. The measurements were performed at the pressures between 10 Pa and 200 Pa and at two different RF powers 200 W and 300 W. It was found that the density of neutral hydrogen atoms was reduced for about 20% due to the presence of the probe. This result was independent from the pressure in the experimental chamber. (author)

  15. Catalytic strategy used by the myosin motor to hydrolyze ATP.

    Science.gov (United States)

    Kiani, Farooq Ahmad; Fischer, Stefan

    2014-07-22

    Myosin is a molecular motor responsible for biological motions such as muscle contraction and intracellular cargo transport, for which it hydrolyzes adenosine 5'-triphosphate (ATP). Early steps of the mechanism by which myosin catalyzes ATP hydrolysis have been investigated, but still missing are the structure of the final ADP·inorganic phosphate (Pi) product and the complete pathway leading to it. Here, a comprehensive description of the catalytic strategy of myosin is formulated, based on combined quantum-classical molecular mechanics calculations. A full exploration of catalytic pathways was performed and a final product structure was found that is consistent with all experiments. Molecular movies of the relevant pathways show the different reorganizations of the H-bond network that lead to the final product, whose γ-phosphate is not in the previously reported HPγO4(2-) state, but in the H2PγO4(-) state. The simulations reveal that the catalytic strategy of myosin employs a three-pronged tactic: (i) Stabilization of the γ-phosphate of ATP in a dissociated metaphosphate (PγO3(-)) state. (ii) Polarization of the attacking water molecule, to abstract a proton from that water. (iii) Formation of multiple proton wires in the active site, for efficient transfer of the abstracted proton to various product precursors. The specific role played in this strategy by each of the three loops enclosing ATP is identified unambiguously. It explains how the precise timing of the ATPase activation during the force generating cycle is achieved in myosin. The catalytic strategy described here for myosin is likely to be very similar in most nucleotide hydrolyzing enzymes.

  16. 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

  17. 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.

  18. 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.

  19. 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

  20. 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

  1. Highly Dense Isolated Metal Atom Catalytic Sites

    DEFF Research Database (Denmark)

    Chen, Yaxin; Kasama, Takeshi; Huang, Zhiwei

    2015-01-01

    -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......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...

  2. 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.

  3. PINGU: PredIction of eNzyme catalytic residues usinG seqUence information.

    Directory of Open Access Journals (Sweden)

    Priyadarshini P Pai

    Full Text Available Identification of catalytic residues can help unveil interesting attributes of enzyme function for various therapeutic and industrial applications. Based on their biochemical roles, the number of catalytic residues and sequence lengths of enzymes vary. This article describes a prediction approach (PINGU for such a scenario. It uses models trained using physicochemical properties and evolutionary information of 650 non-redundant enzymes (2136 catalytic residues in a support vector machines architecture. Independent testing on 200 non-redundant enzymes (683 catalytic residues in predefined prediction settings, i.e., with non-catalytic per catalytic residue ranging from 1 to 30, suggested that the prediction approach was highly sensitive and specific, i.e., 80% or above, over the incremental challenges. To learn more about the discriminatory power of PINGU in real scenarios, where the prediction challenge is variable and susceptible to high false positives, the best model from independent testing was used on 60 diverse enzymes. Results suggested that PINGU was able to identify most catalytic residues and non-catalytic residues properly with 80% or above accuracy, sensitivity and specificity. The effect of false positives on precision was addressed in this study by application of predicted ligand-binding residue information as a post-processing filter. An overall improvement of 20% in F-measure and 0.138 in Correlation Coefficient with 16% enhanced precision could be achieved. On account of its encouraging performance, PINGU is hoped to have eventual applications in boosting enzyme engineering and novel drug discovery.

  4. Toward a catalytic site in DNA

    DEFF Research Database (Denmark)

    Jakobsen, Ulla; Rohr, Katja; Vogel, Stefan

    2007-01-01

    A number of functionalized polyaza crown ether building blocks have been incorporated into DNA-conjugates as catalytic Cu(2+) binding sites. The effect of the DNA-conjugate catalyst on the stereochemical outcome of a Cu(2+)-catalyzed Diels-Alder reaction will be presented.......A number of functionalized polyaza crown ether building blocks have been incorporated into DNA-conjugates as catalytic Cu(2+) binding sites. The effect of the DNA-conjugate catalyst on the stereochemical outcome of a Cu(2+)-catalyzed Diels-Alder reaction will be presented....

  5. 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.

  6. Catalytic Wastewater Treatment Using Pillared Clays

    Science.gov (United States)

    Perathoner, Siglinda; Centi, Gabriele

    After introduction on the use of solid catalysts in wastewater treatment technologies, particularly advanced oxidation processes (AOPs), this review discussed the use of pillared clay (PILC) materials in three applications: (i) wet air catalytic oxidation (WACO), (ii) wet hydrogen peroxide catalytic oxidation (WHPCO) on Cu-PILC and Fe-PILC, and (iii) behavior of Ti-PILC and Fe-PILC in the photocatalytic or photo-Fenton conversion of pollutants. Literature data are critically analyzed to evidence the main direction to further investigate, in particularly with reference to the possible practical application of these technologies to treat industrial, municipal, or agro-food production wastewater.

  7. 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.)

  8. Towards the rationalization of catalytic activity values by means of local hyper-softness on the catalytic site: a criticism about the use of net electric charges.

    Science.gov (United States)

    Ignacio Martínez-Araya, Jorge; Grand, André; Glossman-Mitnik, Daniel

    2015-11-28

    By means of the Spin-Polarized Conceptual Density Functional Theory (SP-CDFT), three 2,6-bis(imino)pyridine catalysts based on iron(II), used for polymerization of ethylene, were studied. The catalysts differed by the substituent group, bearing either -H, -NO2 or -OCH3. To date, catalytic activity, a purely experimental parameter measuring the mass of polyethylene produced per millimole of iron per time and pressure unit at a fixed temperature, has not been explained in terms of local hyper-softness. The latter is a purely theoretical parameter designed for quantifying electronic effects; it is measured using the metal atom responsible for the coordination process with the monomer (ethylene). Because steric effects are not relevant in these kinds of catalysts and only electronic effects drive the catalytic process, an interesting link is found between catalytic activity and the local hyper-softness condensed on the iron atom by means of four functionals (B3LYP, BP86, B97D, and VSXC). This work demonstrates that the use of local hyper-softness, predicted by the SP-CDFT, is a suitable parameter for explaining order relationships among catalytic activity values, thus quantifying the electronic influence of the substituent group inducing this difference; the use of only net electric charges does not lead to clear conclusions. This finding can aid in estimating catalytic activities leading to a more rational design of new catalysts via computational chemistry.

  9. Discussion of risks of platinum resources based on a function orientated criticality assessment. Shown by cytostatic drugs and automotive catalytic converters; Diskussion der Risiken der Ressource Platin auf Basis eines um funktionale Faktoren erweiterten Kritikalitaetsassessments. Dargestellt am Beispiel platinhaltiger Zytostatika und Autoabgaskatalysatoren

    Energy Technology Data Exchange (ETDEWEB)

    Thorenz, Andrea; Reller, Armin [University of Augsburg, Chair of Resource Strategy, Environment Science Center, Augsburg (Germany)

    2011-12-15

    The purpose of the study is the enhancement of criticality assessments for resources in order to address function specific factors like dissipation, recycling, bio-activity and toxicity. The developed methodology is applied to platinum-containing cytostatic drugs and automotive catalytic converters. Methods: The study is methodically based on an analysis of resource specific factors like exploration rates, reserves-to-production ratio and regional distribution of exploration areas as well as on the investigation of product/functional depending factors like recycling rates, dissipation rates, bio-diversity and toxicity. Taking into account that economic and ecological risks may occur at any stage of the supply, consumption and dissipation processes, the whole life cycles of the two analyzed products (cytostatic drugs and automotive catalytic converters) are considered. As an approach to reduce potential economic and ecological risks the study is especially focused on recycling strategies. In order to get a better understanding of platinum as an essential resource for the development of our society the history and the cultural impact of the term ''resource'' are introduced. The availability of platinum is crucial for several products of our modern society. Areas of application are e.g. jewellery, automotive catalytic converters, investments (coins, bars), computers, mobile devices, fertilizers and cytostatic drugs. Economic risks are caused by limited sources and dynamic demand of new application areas like fuel cells and drugs. Platinum-containing drugs are used for the treatment of several kinds of cancer such as testicular, breast, colon and prostate. Currently the pharmaceutical industry requires 6,9 tons per year (3 percent of the total demand of platinum). Due to the improvement of medical standards and the ageing society, especially in developing countries, the demand of platinum-containing drugs will rise significantly. The dissipation of

  10. Heterogeneous Catalytic Oligomerization of Ethylene

    Science.gov (United States)

    Jan, Oliver Dennis

    increased with temperature, with 17 wt.% observed at 190ºC. Higher reaction temperatures led to the formation of odd-numbered oligomers primarily due to acid-catalyzed cracking reactions. In the range of space velocities tested, a moderate WHSV of 2.0 hr-1 resulted in a local maximum of 10.6 wt.% of liquid hydrocarbon yield. A moderate nickel loading of 3.4 wt.% also resulted in the highest liquid yield out of the three loadings tested (10.6 wt.%). The variation in nickel loading revealed the importance of having a synergistic balance of nickel and acid sites on the catalyst to maximize ethylene conversion and maintain high liquid hydrocarbon yield. Lastly, we used supercritical ethylene as both a solvent and as a reactant for ethylene oligomerization over two silica-alumina type catalysts: Ni-Hbeta and Ni-Al-SBA-15. Specifically, the effect of pressure and temperature on the overall conversion and product selectivity were evaluated in the range from 0 to 65 bar and 30 to 120ºC. At subcritical conditions, the ethylene conversion reached a plateau of around 50%. By increasing the pressure past the critical point of ethylene, the conversion drastically increased to 71%. The increased conversion can be attributed to the solubility of certain oligomers, namely butene, in supercritical ethylene that promotes desorption from catalytic active site before further oligomerization. We also tested a mesoporous catalyst, Ni-Al-SBA-15 and observed conversion trends analogous to that of Ni-Hbeta. At supercritical conditions, ethylene oligomerization over Ni-Al-SBA-15 was more selective towards the butene product, with nearly 74 wt.% butenes observed. The catalyst activity increased with temperature from 30ºC to 120ºC. The experiment conducted at 30ºC showed very little activity and ethylene conversion, however it effectively heavy molecular weight species from the catalyst. This condition, albeit being not effective for ethylene oligomerization, could be implemented as an in

  11. CATALYTIC SPECTROPHOTOMETRIC DETERMINATION OF Mn(II ...

    African Journals Online (AJOL)

    Preferred Customer

    The aim of the present study was to develop a new precise and accurate catalytic spectrophotometric ... manganese sulfate monohydrate (Merck, Darmstadt, Germany) in water and diluted to 250 mL. The working .... and potassium hydrogen phthalate-HCl buffer solutions, the slope of calibration graph was unsatisfactory.

  12. Catalytic enantioselective conjugate addition with Grignard reagents

    NARCIS (Netherlands)

    Lopez, Fernando; Minnaard, Adriaan J.; Feringa, Ben L.

    In this Account, recent advances in catalytic asymmetric conjugate addition of Grignard reagents are discussed. Synthetic methodology to perform highly enantioselective Cu-catalyzed conjugate addition of Grignard reagents to cyclic enones with ee's up to 96% was reported in 2004 from our

  13. Catalytic models developed through social work

    DEFF Research Database (Denmark)

    Jensen, Mogens

    2015-01-01

    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...

  14. Fluid catalytic cracking : Feedstocks and reaction mechanism

    NARCIS (Netherlands)

    Dupain, X.

    2006-01-01

    The Fluid Catalytic Cracking (FCC) process is one of the key units in a modern refinery. Traditionally, its design is primarily aimed for the production of gasoline from heavy oil fractions, but as co-products also diesel blends and valuable gasses (e.g. propene and butenes) are formed in

  15. Catalytic dehydrogenations of ethylbenzene to styrene

    NARCIS (Netherlands)

    Nederlof, C.

    2012-01-01

    This research work on the catalytic dehydrogenation of ethylbenzene (EB) to styrene (ST) had a primary goal of developing improved catalysts for dehydrogenation processes both in CO2 as well as with O2 that can compete with the conventional dehydrogenation process in steam. In order to achieve this

  16. DEALUMINATION OF MORDENITE ZEOLITE AND ITS CATALYTIC ...

    African Journals Online (AJOL)

    The xylene mixtures result from the catalytic reforming of petroleum NAFTA and the isomers of xylenes are usually obtained from this mixture by separation. After separation of o-isomers and p-isomers, the remainder richer in m-xylene, needs to be subjected to isomerization [2]. Xylene isomerization has received growing ...

  17. Novel Metal Nanomaterials and Their Catalytic Applications

    Directory of Open Access Journals (Sweden)

    Jiaqing Wang

    2015-09-01

    Full Text Available In the rapidly developing areas of nanotechnology, nano-scale materials as heterogeneous catalysts in the synthesis of organic molecules have gotten more and more attention. In this review, we will summarize the synthesis of several new types of noble metal nanostructures (FePt@Cu nanowires, Pt@Fe2O3 nanowires and bimetallic Pt@Ir nanocomplexes; Pt-Au heterostructures, Au-Pt bimetallic nanocomplexes and Pt/Pd bimetallic nanodendrites; Au nanowires, CuO@Ag nanowires and a series of Pd nanocatalysts and their new catalytic applications in our group, to establish heterogeneous catalytic system in “green” environments. Further study shows that these materials have a higher catalytic activity and selectivity than previously reported nanocrystal catalysts in organic reactions, or show a superior electro-catalytic activity for the oxidation of methanol. The whole process might have a great impact to resolve the energy crisis and the environmental crisis that were caused by traditional chemical engineering. Furthermore, we hope that this article will provide a reference point for the noble metal nanomaterials’ development that leads to new opportunities in nanocatalysis.

  18. 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...

  19. THEORETICAL STUDY OF CATALYTIC HYDROGENATION OF ...

    African Journals Online (AJOL)

    Preferred Customer

    Catalytic hydrotreating process is a technique of purification of the crude oil with the aim of the improvement of the quality and the stability of fuels and lubricants. This is performed by the destruction of heterocyclic compounds and by the saturation of unsaturated hydrocarbons under the effect of the hydrogen pressure in ...

  20. 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...

  1. Method for low temperature catalytic production of hydrogen

    Science.gov (United States)

    Mahajan, Devinder

    2003-07-22

    The invention provides a process for the catalytic production of a hydrogen feed by exposing a hydrogen feed to a catalyst which promotes a base-catalyzed water-gas-shift reaction in a liquid phase. The hydrogen feed can be provided by any process known in the art of making hydrogen gas. It is preferably provided by a process that can produce a hydrogen feed for use in proton exchange membrane fuel cells. The step of exposing the hydrogen feed takes place preferably from about 80.degree. C. to about 150.degree. C.

  2. Catalytic Isomerization of Biomass‐Derived Aldoses: A Review

    Science.gov (United States)

    Delidovich, Irina

    2016-01-01

    Abstract Selected aldohexoses (d‐glucose, d‐mannose, and d‐galactose) and aldopentoses (d‐xylose, l‐arabinose, and d‐ribose) are readily available components of biopolymers. Isomerization reactions of these substances are very attractive as carbon‐efficient processes to broaden the portfolio of abundant monosaccharides. This review focuses on the chemocatalytic isomerization of aldoses into the corresponding ketoses as well as epimerization of aldoses at C2. Recent advances in the fields of catalysis by bases and Lewis acids are considered. The emphasis is laid on newly uncovered catalytic systems and mechanisms of carbohydrate transformations. PMID:26948404

  3. Catalytic Conversion of Bio-oil to Fuel for Transportation

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard

    The incitement for decreasing the modern society's dependency on fossil based fuel and energy is both environmentally and politically driven. Development of biofuels could be part of the future solution. The combination of ash pyrolysis and catalytic upgrading of the produced bio-oil has been...... identied as a prospective route to bio-fuels. The upgrading is most favorably done by hydrodeoxygenation (HDO), producing bio-fuels at a quality equivalent to conventional fossil fuels. The topic of this Ph.D. thesis has been the development of active and stable catalysts for this reaction. In the search...

  4. Sintering of Catalytic Nanoparticles: Particle Migration or Ostwald Ripening?

    DEFF Research Database (Denmark)

    Hansen, Thomas Willum; DeLaRiva, Andrew T.; Challa, Sivakumar R.

    2013-01-01

    deactivation, is an important mechanism for the loss of catalyst activity. This is especially true for high temperature catalytic processes, such as steam reforming, automotive exhaust treatment, or catalytic combustion. With dwindling supplies of precious metals and increasing demand, fundamental...

  5. Reactivity and Catalytic Activity of Hydrogen Atom Chemisorbed Silver Clusters.

    Science.gov (United States)

    Manzoor, Dar; Pal, Sourav

    2015-06-18

    Metal clusters of silver have attracted recent interest of researchers as a result of their potential in different catalytic applications and low cost. However, due to the completely filled d orbital and very high first ionization potential of the silver atom, the silver-based catalysts interact very weakly with the reacting molecules. In the current work, density functional theory calculations were carried out to investigate the effect of hydrogen atom chemisorption on the reactivity and catalytic properties of inert silver clusters. Our results affirm that the hydrogen atom chemisorption leads to enhancement in the binding energy of the adsorbed O2 molecule on the inert silver clusters. The increase in the binding energy is also characterized by the decrease in the Ag-O and increase in the O-O bond lengths in the case of the AgnH silver clusters. Pertinent to the increase in the O-O bond length, a significant red shift in the O-O stretching frequency is also noted in the case of the AgnH silver clusters. Moreover, the hydrogen atom chemisorbed silver clusters show low reaction barriers and high heat of formation of the final products for the environmentally important CO oxidation reaction as compared to the parent catalytically inactive clusters. The obtained results were compared with those of the corresponding gold and hydrogen atom chemisorbed gold clusters obtained at the same level of theory. It is expected the current computational study will provide key insights for future advances in the design of efficient nanosilver-based catalysts through the adsorption of a small atom or a ligand.

  6. Active Component Migration and Catalytic Properties of Nitrogen Modified Composite Catalytic Materials

    Directory of Open Access Journals (Sweden)

    Miaomiao Li

    2018-03-01

    Full Text Available During the catalytic combustion reaction of methane, the migration of the active species on surface facilitates the catalytic reaction, and the element doping can improve the redox performance of the catalyst. Nitrogen-modified perovskite type composite catalysts were prepared by hydrothermal method and then characterized by X-ray diffractometer (XRD, scanning electron microscopy (SEM, Brunauer-Emmett-Teller (BET, temperature-programmed reductions (TPR, and X-ray photoelectron spectra (XPS. The results revealed that nitrogen sources (urea, biuret, melamine, carbohydrazide, and semicarbazide hydrochloride and nitrogen source addition changed the catalytic performance in physical and chemical properties, the migration of reactive species and the catalytic performance. When the addition amount of semicarbazide hydrochloride was three times that of LaCoO3, the composite catalysts had high Co3+/Co2+ (1.39 and Oads/Olat (15.18 and showed the best catalytic performance: the temperatures that are required for achieving methane conversion of 50% and 90% were 277 and 360 °C, which are more effective than noble metal oxides. Moreover, the in situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS were applied to elucidate the efficient for CH4 removal and also can further explain the surface reaction mechanism of the composite catalyst during the methane catalytic combustion.

  7. Structural determinants of APOBEC3B non-catalytic domain for molecular assembly and catalytic regulation

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Xiao; Yang, Hanjing; Arutiunian, Vagan; Fang, Yao; Besse, Guillaume; Morimoto, Cherie; Zirkle, Brett; Chen, Xiaojiang S. (USC)

    2017-05-30

    The catalytic activity of human cytidine deaminase APOBEC3B (A3B) has been correlated with kataegic mutational patterns within multiple cancer types. The molecular basis of how the N-terminal non-catalytic CD1 regulates the catalytic activity and consequently, biological function of A3B remains relatively unknown. Here, we report the crystal structure of a soluble human A3B-CD1 variant and delineate several structural elements of CD1 involved in molecular assembly, nucleic acid interactions and catalytic regulation of A3B. We show that (i) A3B expressed in human cells exists in hypoactive high-molecular-weight (HMW) complexes, which can be activated without apparent dissociation into low-molecular-weight (LMW) species after RNase A treatment. (ii) Multiple surface hydrophobic residues of CD1 mediate the HMW complex assembly and affect the catalytic activity, including one tryptophan residue W127 that likely acts through regulating nucleic acid binding. (iii) One of the highly positively charged surfaces on CD1 is involved in RNA-dependent attenuation of A3B catalysis. (iv) Surface hydrophobic residues of CD1 are involved in heterogeneous nuclear ribonucleoproteins (hnRNPs) binding to A3B. The structural and biochemical insights described here suggest that unique structural features on CD1 regulate the molecular assembly and catalytic activity of A3B through distinct mechanisms.

  8. Greatly Enhancing Catalytic Activity of Graphene by Doping the Underlying Metal Substrate.

    Science.gov (United States)

    Guo, Na; Xi, Yongjie; Liu, Shuanglong; Zhang, Chun

    2015-07-09

    Graphene-based solid-state catalysis represents a new direction in applications of graphene and has attracted a lot of interests recently. However, the difficulty in fine control and large-scale production of previously proposed graphene catalysts greatly limits their industrial applications. Here we present a novel way to enhance the catalytic activity of graphene, which is highly efficient yet easy to fabricate and control. By first-principles calculations, we show that when the underlying metal substrate is doped with impurities, the catalytic activity of the supported graphene can be drastically enhanced. Graphene supported on a Fe/Ni(111) surface is chosen as a model catalyst, and the chemical reaction of CO oxidation is used to probe the catalytic activity of graphene. When the underlying Fe/Ni(111) substrate is impurity free, the graphene is catalytically inactive. When a Zn atom is doped into the substrate, the catalytic activity of the supported graphene is greatly enhanced, and the reaction barrier of the catalyzed CO oxidation is reduced to less than 0.5 eV. Intriguing reaction mechanism of catalyzed CO oxidation is revealed. These studies suggest a new class of graphene-based catalysts and pave the way for future applications of graphene in solid-state catalysis.

  9. Improving the modelling of the kinetics of the catalytic tar elimination in biomass gasification

    Energy Technology Data Exchange (ETDEWEB)

    Corella, J.; Toledo, J.M. [Department of Chemical Engineering, University ' Complutense' of Madrid (Spain); Aznar, M.P. [Dept. of Chem. and Environm. Engineering, University of Saragossa (Spain)

    2002-10-01

    A single one-lump first order reaction for the catalytic elimination of tar present in the flue gas from biomass fluidised-bed gasifiers is not good enough for some applications. A new and more advanced reacting network and microkinetic model has been generated and is here presented. It is based on two lumps, the more and the less reactive tar species, and has four kinetic constants. Each lump reacts (disappears) by both catalytic and thermal reactions. The microkinetic model is applied to results obtained, at around 840 deg C and at small pilot plant level, with two very different solids: silica sand and a commercial (ICI 46-1) nickel-based steam-reforming catalyst. The values found for the four kinetic constants are self-consistent, fit well the results and mean a clear step forward in the modelling of the catalytic tar abatement. (orig.)

  10. Surface Modification of Catalytic Materials

    DEFF Research Database (Denmark)

    Nierhoff, Anders Ulrik Fregerslev

    aggregation techniques. With the use of two different filter mechanisms, the Quadrupole and the Lateral Time Of Flight, the nanoparticles were mass selected. This was done to correlate nanoparticle size with reactivity. Selected key findings can be summarized as: 1) CO induced surface changes of Pt based...... methanol synthesis. The importance of conducting well controlled UHV experiments and characterization in combination with experiments at higher pressures to span the pressure gap between UHV and operando conditions is definitely highlighted in this thesis....

  11. Catalytic applications of niobium compounds

    International Nuclear Information System (INIS)

    Wright, C.J.; England, W.A.

    1984-01-01

    This article examines the potential uses of niobium, and its compounds, as catalysts in chemical processing. The word potential is deliberately chosen because in 1978 none of the world's twenty-five major catalysts (1) contained niobium. On the other hand, catalysts containing molybdenum and vanadium, neighbors of niobium in the periodic table, realized over 80 x 10 6 of sales in that same year. At the same time many of the patents for niobium catalysts cover applications in which niobium improves the activity of, or substitutes for, molybdenum based compounds. With favorable cost differentials and improvements in understanding, niobium may be able to replace molybdenum in some its traditional uses

  12. Development of a new paper based nano-biosensor using the co-catalytic effect of tyrosinase from banana peel tissue (Musa Cavendish) and functionalized silica nanoparticles for voltammetric determination of l-tyrosine.

    Science.gov (United States)

    Rahimi-Mohseni, Mohadeseh; Raoof, Jahan Bakhsh; Ojani, Reza; Aghajanzadeh, Tahereh A; Bagheri Hashkavayi, Ayemeh

    2018-02-12

    In this paper, a new and facile method for the electrochemical determination of l-tyrosine was designed. First, 3-mercaptopropyl trimethoxysilane-functionalized silica nanoparticles were added to a paper disc. Then, the banana peel tissue and the mediator potassium hexacyanoferrate were dropped onto the paper, respectively. The modified paper disc was placed on the top of the graphite screen printed electrode and electrochemical characterization of this biosensor was studied by cyclic voltammetry and electrochemical impedance spectroscopy methods. The effective parameters like pH, banana peel tissue percentage, and the amount of mediator loading were optimized. l-tyrosine measurements were done by differential pulse voltammetry with a little sample (3 μL) for analysis. The biosensor showed a linear response for l-tyrosine in the wide concentration range of 0.05-600 μM and a low detection limit about 0.02 μM because of the co-catalytic effect of enzyme and nanoparticles. The stability of the biosensor and its selectivity were evaluated. This biosensor was applied for the voltammetric determination of l-tyrosine in the blood plasma sample. The results of the practical application study were comparable with the standard method (HPLC). In conclusion, a simple, inexpensive, rapid, sensitive and selective technique was successfully applied to the l-tyrosine analysis of the little samples. Copyright © 2018 Elsevier B.V. All rights reserved.

  13. Fluorogenic, catalytic, photochemical reaction for amplified detection of nucleic acids.

    Science.gov (United States)

    Dutta, Subrata; Fülöp, Annabelle; Mokhir, Andriy

    2013-09-18

    Photochemical, nucleic acid-induced reactions, which are controlled by nontoxic red light, are well-suited for detection of nucleic acids in live cells, since they do not require any additives and can be spatially and temporally regulated. We have recently described the first reaction of this type, in which a phenylselenyl derivative of thymidine (5'-PhSeT-ODNa) is cleaved in the presence of singlet oxygen (Fülöp, A., Peng, X., Greenberg, M. M., Mokhir, A. (2010) A nucleic acid directed, red light-induced chemical reaction. Chem. Commun. 46, 5659-5661). The latter reagent is produced upon exposure of a photosensitizer 3'-PS-ODNb (PS = Indium(III)-pyropheophorbide-a-chloride: InPPa) to >630 nm light. In 2012 we reported on a fluorogenic version of this reaction (Dutta, S., Flottmann, B., Heilemann, M., Mokhir, A. (2012) Hybridization and reaction-based, fluorogenic nucleic acid probes. Chem. Commun. 47, 9664-9666), which is potentially applicable for the detection of nucleic acids in cells. Unfortunately, its yield does not exceed 25% and no catalytic turnover could be observed in the presence of substrate excess. This problem occurs due to the efficient, competing oxidation of the substrate containing an electron rich carbon-carbon double bonds (SCH═CHS) in the presence of singlet oxygen with formation of a noncleavable product (SCH═CHSO). Herein we describe a related, but substantially improved photochemical, catalytic transformation of a fluorogenic, organic substrate, which consists of 9,10-dialkoxyanthracene linked to fluorescein, with formation of a bright fluorescent dye. In highly dilute solution this reaction occurs only in the presence of a nucleic acid template. We developed three types of such a reaction and demonstrated that they are high yielding and generate over 7.7 catalytic turnovers, are sensitive to single mismatches in nucleic acid targets, and can be applied for determination of both the amount of nucleic acids and potentially their

  14. Direct observation of enhanced plasmon-driven catalytic reaction activity of Au nanoparticles supported on reduced graphene oxides by SERS.

    Science.gov (United States)

    Liang, Xiu; You, Tingting; Liu, Dapeng; Lang, Xiufeng; Tan, Enzhong; Shi, Jihua; Yin, Penggang; Guo, Lin

    2015-04-21

    Graphene-based nanocomposites have recently attracted tremendous research interest in the field of catalysis due to their unique optical and electronic properties. However, direct observation of enhanced plasmon-driven catalytic activity of Au nanoparticles (NPs) supported on reduced graphene oxides (Au/rGO) has rarely been reported. Herein, based on the reduction from 4-nitrobenzenethiol (4-NBT) to p,p'-dimercaptoazobenzene (DMAB), the catalytic property of Au/rGO nanocomposites was investigated and compared with corresponding Au NP samples with similar size distribution. Our results show that Au/rGO nanocomposites could serve as a good catalytic and analytic platform for plasmon-driven chemical reactions. In addition, systematic comparisons were conducted during power- and time-dependent surface-enhanced Raman scattering (SERS) experiments, which exhibited a lower power threshold and higher catalytic efficiency for Au/rGO as compared to Au NPs toward the reaction.

  15. Effect of inlet cone pipe angle in catalytic converter

    Science.gov (United States)

    Amira Zainal, Nurul; Farhain Azmi, Ezzatul; Arifin Samad, Mohd

    2018-03-01

    The catalytic converter shows significant consequence to improve the performance of the vehicle start from it launched into production. Nowadays, the geometric design of the catalytic converter has become critical to avoid the behavior of backpressure in the exhaust system. The backpressure essentially reduced the performance of vehicles and increased the fuel consumption gradually. Consequently, this study aims to design various models of catalytic converter and optimize the volume of fluid flow inside the catalytic converter by changing the inlet cone pipe angles. Three different geometry angles of the inlet cone pipe of the catalytic converter were assessed. The model is simulated in Solidworks software to determine the optimum geometric design of the catalytic converter. The result showed that by decreasing the divergence angle of inlet cone pipe will upsurge the performance of the catalytic converter.

  16. Synthesis and catalytic properties of ferrocenophane phosphines

    OpenAIRE

    Škoch, Karel

    2014-01-01

    6 Title: Sythesis and catalytic properties of ferrocenophane phosphines Author: Karel Škoch Institution: Faculty of Science, Charles University in Prague, Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. Keywords: ferrocene, ferrocenophane, phosphine ligands, palladium, asymetric catalysis, aza- Morita-Baylis-Hillman reaction, asymetric allylic alkylation Abstract: This Thesis describes the preparation of five sterically and electronically different ferrocene ph...

  17. 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

  18. Enantioselective catalytic fluorinative aza-semipinacol rearrangement.

    Science.gov (United States)

    Romanov-Michailidis, Fedor; Pupier, Marion; Besnard, Céline; Bürgi, Thomas; Alexakis, Alexandre

    2014-10-03

    An efficient and highly stereoselective fluorinative aza-semipinacol rearrangement is described. The catalytic reaction requires use of Selectfluor in combination with the chiral, enantiopure phosphate anion derived from acid L3. Under optimized conditions, cyclopropylamines A were transformed into β-fluoro cyclobutylimines B in good yields and high levels of diastereo- and enantiocontrol. Furthermore, the optically active cyclobutylimines were reduced diastereoselectively with L-Selectride in the corresponding fluorinated amines C, compounds of significant interest in the pharmacological industry.

  19. Zeolitic catalytic conversion of alcohols to hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

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

    2018-04-10

    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.

  20. 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.

  1. Synthesis of ceramic catalytic system based on CuO/CeO{sub 2} for preferential oxidation reaction of CO; Sintese de sistemas cataliticos ceramicos de CuO/CeO{sub 2} destinados a reacao de oxidacao preferencial do CO

    Energy Technology Data Exchange (ETDEWEB)

    Neiva, L.S.; Ribeiro, M.A.; Bispo, A.; Gama, L., E-mail: lsoutoneiva@yahoo.com.b [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academica de Engenharia de Materiais

    2010-07-01

    The aim this is work is to develop catalysts based on CuO/CeO{sub 2} by means two different types of synthesis methods: combustion synthesis and Pechini. CuO/CeO{sub 2} catalysts were synthesized with 0.5 mol of CuO for both synthesis methods used. The catalysts were characterized by XRD with the Rietveld refinement, EDX and textural analysis by the BET method. The results show that both methods of synthesis led to the formation of catalysts with segregated phases formed on the structures of the obtained materials, such segregated phases were formed by the presence of catalytic active species CuO and these phases had different characteristics depending on the type of method synthesis used. Small differences were observed in the evaluation of textural characteristics of the catalysts developed in this work according to the synthesis method employed. (author)

  2. Hydrogen production from biomass tar by catalytic steam reforming

    International Nuclear Information System (INIS)

    Yoon, Sang Jun; Choi, Young-Chan; Lee, Jae-Goo

    2010-01-01

    The catalytic steam reforming of model biomass tar, toluene being a major component, was performed at various conditions of temperature, steam injection rate, catalyst size, and space time. Two kinds of nickel-based commercial catalyst, the Katalco 46-3Q and the Katalco 46-6Q, were evaluated and compared with dolomite catalyst. Production of hydrogen generally increased with reaction temperature, steam injection rate and space time and decreased with catalyst size. In particular, zirconia-promoted nickel-based catalyst, Katalco 46-6Q, showed a higher tar conversion efficiency and shows 100% conversion even relatively lower temperature conditions of 600 deg. C. Apparent activation energy was estimated to 94 and 57 kJ/mol for dolomite and nickel-based catalyst respectively.

  3. Solid State, Surface and Catalytic Studies of Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Kung, H. H.

    2004-11-23

    This project investigates the catalytic properties of oxides for the selective oxidative dehydrogenation of light alkanes and for hydrocarbon reduction of NO{sub x}. Various vanadium oxide based catalysts were investigated to elucidate the relationship between the chemical and structural properties of the catalysts and their selectivity for the formation of alkenes. It was found that vanadium oxide units that are less reducible give higher selectivities. For hydrocarbon reduction of NO{sub x}, it was found that alumina-based catalysts can be effective at higher temperatures than the corresponding zeolite-based catalysts. On some catalysts, such as SnO{sub 2}/Al{sub 2}O{sub 3}. Ag/Al{sub 2}O{sub 3}, the alumina participates directly in the reaction, making the catalyst bifunctional. These results are useful in research to improve the performance of this stress of catalysts.

  4. Transfer Hydrogenation: Employing a Simple, In Situ Prepared Catalytic System

    KAUST Repository

    Ang, Eleanor Pei Ling

    2017-04-01

    Transfer hydrogenation has been recognized to be an important synthetic method in both academic and industrial research to obtain valuable products including alcohols. Transition metal catalysts based on precious metals, such as Ru, Rh and Ir, are typically employed for this process. In recent years, iron-based catalysts have attracted considerable attention as a greener and more sustainable alternative since iron is earth abundant, inexpensive and non-toxic. In this work, a combination of iron disulfide with chelating bipyridine ligand was found to be effective for the transfer hydrogenation of a variety of ketones to the corresponding alcohols in the presence of a simple base. It provided a convenient and economical way to conduct transfer hydrogenation. A plausible role of sulfide next to the metal center in facilitating the catalytic reaction is demonstrated.

  5. 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.

  6. Antibody proteases: induction of catalytic response.

    Science.gov (United States)

    Gabibov, A G; Friboulet, A; Thomas, D; Demin, A V; Ponomarenko, N A; Vorobiev, I I; Pillet, D; Paon, M; Alexandrova, E S; Telegin, G B; Reshetnyak, A V; Grigorieva, O V; Gnuchev, N V; Malishkin, K A; Genkin, D D

    2002-10-01

    Most of the data accumulated throughout the years on investigation of catalytic antibodies indicate that their production increases on the background of autoimmune abnormalities. The different approaches to induction of catalytic response toward recombinant gp120 HIV-1 surface protein in mice with various autoimmune pathologies are described. The peptidylphosphonate conjugate containing structural part of gp120 molecule is used for reactive immunization of NZB/NZW F1, MRL, and SJL mice. The specific modification of heavy and light chains of mouse autoantibodies with Val-Ala-Glu-Glu-Glu-Val-PO(OPh)2 reactive peptide was demonstrated. Increased proteolytic activity of polyclonal antibodies in SJL mice encouraged us to investigate the production of antigen-specific catalytic antibodies on the background of induced experimental autoimmune encephalomyelitis (EAE). The immunization of autoimmune-prone mice with the engineered fusions containing the fragments of gp120 and encephalitogenic epitope of myelin basic protein (MBP(89-104)) was made. The proteolytic activity of polyclonal antibodies isolated from the sera of autoimmune mice immunized by the described antigen was shown. Specific immune response of SJL mice to these antigens was characterized. Polyclonal antibodies purified from sera of the immunized animals revealed proteolytic activity. The antiidiotypic approach to raise the specific proteolytic antibody as an "internal image" of protease is described. The "second order" monoclonal antibodies toward subtilisin Carlsberg revealed pronounced proteolytic activity.

  7. 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.

  8. Electrochemical catalytic treatment of phenol wastewater

    International Nuclear Information System (INIS)

    Ma Hongzhu; Zhang Xinhai; Ma Qingliang; Wang Bo

    2009-01-01

    The slurry bed catalytic treatment of contaminated water appears to be a promising alternative for the oxidation of aqueous organic pollutants. In this paper, the electrochemical oxidation of phenol in synthetic wastewater catalyzed by ferric sulfate and potassium permanganate adsorbed onto active bentonite in slurry bed electrolytic reactor with graphite electrode has been investigated. In order to determine the optimum operating condition, the orthogonal experiments were devised and the results revealed that the system of ferric sulfate, potassium permanganate and active bentonite showed a high catalytic efficiency on the process of electrochemical oxidation phenol in initial pH 5. When the initial concentration of phenol was 0.52 g/L (the initial COD 1214 mg/L), up to 99% chemical oxygen demand (COD) removal was obtained in 40 min. According to the experimental results, a possible mechanism of catalytic degradation of phenol was proposed. Environmental estimation was also done and the results showed that the treated wastewater have little impact on plant growth and could totally be applied to irrigation.

  9. Flow-injection determination of 9,10-phenanthrenequinone with catalytic photometric detection.

    Science.gov (United States)

    Kiba, N; Suzuki, H; Goto, E; Furusawa, M

    1993-03-01

    A catalytic photometric method with a flow-injection system is described for the determination of 9,10-phenanthrenequinone. It is based on the catalytic effect of 9,10-phenanthrenequinone on the redox reaction of 1,2-dinitrobenzene with formaldehyde under alkaline conditions. 9,10-Phenanthrenequinone at the 5.0 x 10(-8)-5.0 x 10(-6)M level can be determined at a rate of 20 samples/hr. The detection limit is 1.0 x 10(-8)M (40 pg in a 10-microl injection).

  10. Biogasoline Production from Palm Oil Via Catalytic Hydrocracking over Gamma-Alumina Catalyst

    OpenAIRE

    Anondho Wijanarko; Dadi Mawardi; Mohammad Nasikin

    2010-01-01

    Bio gasoline conversion from palm oil is an alternative energy resources method which can be substituted fossil fuel base energy utilization. Previous research resulted that palm oil can be converted into hydrocarbon by catalytic cracking reaction with γ-alumina catalyst. In this research, catalytic cracking reaction of palm oil by γ-alumina catalyst is done in  a stirrer batch reactor with the oil/catalyst weight ratio variation of 100:1, 75:1, and 50:1; at suhue variation of 260 to 340...

  11. Synthesis gas production via catalytic partial oxidation reforming of liquid fuels

    Energy Technology Data Exchange (ETDEWEB)

    Cheekatamarla, P.K.; Finnerty, C.M. [NanoDynamics Energy Inc., 901 Fuhrmann Boulevard, Buffalo, NY 14203 (United States)

    2008-10-15

    This work deals with the performance of waterless catalytic partial oxidation (CPOX)-based catalytic reformer system fed by different liquid fuels including ethanol, isooctane, hexadecane, synthetic JP8, kerosene and diesel for solid oxide fuel cell applications. The effect of different fuel components on product composition was studied and the operational parameters were optimized to provide a stable reforming performance. The system provided negligible pressure drop combined with the simpler system design due to the lack of water requirement making the POX reformer an attractive choice. (author)

  12. Catalytic Enhancement of Carbon Black and Coal-Fueled Hybrid Direct Carbon Fuel Cells

    DEFF Research Database (Denmark)

    Deleebeeck, Lisa; Ippolito, Davide; Kammer Hansen, Kent

    2015-01-01

    , Ce1-xREExO2-δ (REE = Pr, Sm)) and metal oxides (LiMn2O4, Ag2O). Materials showing the highest activity in carbon black (Mn2O3, CeO2, Ce0.6Pr0.4O2-δ, Ag2O) were subsequently tested for catalytic activity toward bituminous coal, as revealed by both I-V-P curves and electrochemical impedance...... spectroscopy (EIS). Catalytic activity was evaluated as a function of various physical characteristics of doped ceria and manganese-based materials....

  13. Catalytic [1,3] O-to-C Rearrangement: Rapid Access to Bridged Bicyclic System.

    Science.gov (United States)

    Zhu, Shifa; Zhang, Jiantao; Liao, Zhehui; Chen, Lianfen; Jiang, Huanfeng

    2018-03-05

    A catalytic [1,3] O-to-C rearrangement from enyne-ether was developed for the rapid synthesis of diverse bridged bicyclic systems. In this reaction, a vinyl oxonium intermediate, generated in situ from enyne-ether, was the precursor for the [1,3] O-to-C rearrangement. This versatile protocol represents the first example of catalytic [1,3] O-to-C rearrangement based on ring-expansion strategy, enabling efficient access to bridged bicyclic scaffolds. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    International Nuclear Information System (INIS)

    Li, Yan; Chang, Jie; Ouyang, Yong; Zheng, Xianwei

    2014-01-01

    High value-added aromatic aldehydes (e. g. vanillin and syringaldehyde) were produced from heavy fraction of bio-oil (HFBO) via catalytic oxidation. The concept is based on the use of metalloporphyin as catalyst and hydrogen peroxide (H 2 O 2 ) as oxidant under alkaline condition. The biomimetic catalyst cobalt(II)-sulfonated tetraphenylporphyrin (Co(TPPS 4 )) was prepared and characterized. It exhibited relative high activity in the catalytic oxidation of HFBO. 4.57 wt % vanillin and 1.58 wt % syringaldehyde were obtained from catalytic oxidation of HFBO, compared to 2.6 wt % vanillin and 0.86 wt % syringaldehyde without Co(TPPS 4 ). Moreover, a possible mechanism of HFBO oxidation using Co(TPPS 4 )/H 2 O 2 was proposed by the research of model compounds. The results showed that this is a promising and environmentally friendly method for production of aromatic aldehydes from HFBO under Co(TPPS 4 )/H 2 O 2 system

  15. The ab initio study of the catalytic hydrogenation of the oxirene

    Directory of Open Access Journals (Sweden)

    J.B. Mensah

    2008-04-01

    Full Text Available The oxirene is an unsaturated heterocyclic molecule with one oxygen atom and two carbon atoms. Its hydrogenation has been performed on two catalytic site based on molybdenum disulfide (MoS2 and tungsten disulfide (WS2 of MoS3H3+ and WS3H3+ type, respectively. The calculations were carried out using the SCF and MP2 methods and B3LYP functional calculations. The results obtained showed that the hydrogenation of the oxirene is possible on these two kinds of catalytic sites on the one hand, and the reaction product is the acetaldehyde molecule, on the other hand. The reaction process study that led to the results showed that the catalytic hydrogenation of the oxirene is a dissociative process. On the basis of the variation of some parameters during the process, a mechanism of the reaction has been proposed.

  16. Real life experimental determination of platinum group metals content in automotive catalytic converters

    Science.gov (United States)

    Yakoumis, I.; Moschovi, A. M.; Giannopoulou, I.; Panias, D.

    2018-03-01

    The real life experimental protocol for the preparation of spent automobile catalyst samples for elemental analysis is thoroughly described in the following study. Collection, sorting and dismantling, homogenization and sample preparation for X-Ray fluorescence spectroscopy and Atomic Adsorption Spectroscopy combined with Inductive coupled plasma mass spectrometry are discussed in detail for both ceramic and metallic spent catalysts. The concentrations of Platinum Group Metals (PGMs) in spent catalytic converters are presented based on typical consignments of recycled converters (more than 45,000 pieces) from the Greek Market. The conclusions clearly denoted commercial metallic catalytic foil contains higher PGMs loading than ceramic honeycombs. On the other hand, the total PGMs loading in spent ceramic catalytic converters has been found higher than the corresponding value for the metallic ones.

  17. One-pot environmentally friendly approach toward highly catalytically active bimetal-nanoparticle-graphene hybrids.

    Science.gov (United States)

    Liu, Chang-Hai; Chen, Xiao-Qi; Hu, Yong-Feng; Sham, Tsun-Kong; Sun, Qi-Jun; Chang, Jian-Bing; Gao, Xu; Sun, Xu-Hui; Wang, Sui-Dong

    2013-06-12

    A one-pot universal approach with simple metal sputtering onto room temperature ionic liquids has been developed to prepare bimetal-nanoparticle (NP)-graphene hybrids, and the process is environmentally friendly and completely free of additives and byproducts. The graphene-supported bimetallic NPs have an Ag-based core and an Au/Pd-rich shell, demonstrated by the scanning transmission electron microscopy. The X-ray absorption near-edge spectroscopy using synchrotron radiation reveals the occurrence of charge redistribution at both the Ag@Au and Ag@Pd core-shell interfaces. The as-prepared Ag@Au and Ag@Pd bimetal-NP-graphene hybrids are highly catalytically active for reduction of 4-nitrophenol, whose catalytic activity is superior to the corresponding monometallic hybrids. The catalytic superiority is ascribed to the electronic structure modification and morphological irregularity of the graphene-supported bimetallic NPs.

  18. Advances in solid-catalytic and non-catalytic technologies for biodiesel production

    International Nuclear Information System (INIS)

    Islam, Aminul; Taufiq-Yap, Yun Hin; Chan, Eng-Seng; Moniruzzaman, M.; Islam, Saiful; Nabi, Md. Nurun

    2014-01-01

    Highlights: • The recent technologies for promoting biodiesel synthesis were elucidated. • The design of catalyst consideration of biodiesel production was proposed. • The recent advances and remaining difficulties in biodiesel synthesis were outlined. • The future research trend in biodiesel synthesis was highlighted. - Abstract: The insecure supply of fossil fuel coerces the scientific society to keep a vision to boost investments in the renewable energy sector. Among the many renewable fuels currently available around the world, biodiesel offers an immediate impact in our energy. In fact, a huge interest in related research indicates a promising future for the biodiesel technology. Heterogeneous catalyzed production of biodiesel has emerged as a preferred route as it is environmentally benign needs no water washing and product separation is much easier. The number of well-defined catalyst complexes that are able to catalyze transesterification reactions efficiently has been significantly expanded in recent years. The activity of catalysts, specifically in application to solid acid/base catalyst in transesterification reaction depends on their structure, strength of basicity/acidity, surface area as well as the stability of catalyst. There are various process intensification technologies based on the use of alternate energy sources such as ultrasound and microwave. The latest advances in research and development related to biodiesel production is represented by non-catalytic supercritical method and focussed exclusively on these processes as forthcoming transesterification processes. The latest developments in this field featuring highly active catalyst complexes are outlined in this review. The knowledge of more extensive research on advances in biofuels will allow a deeper insight into the mechanism of these technologies toward meeting the critical energy challenges in future

  19. Catalytic Reduction of NO and NOx Content in Tobacco Smoke

    Directory of Open Access Journals (Sweden)

    Cvetkovic N

    2014-12-01

    Full Text Available In order to reduce the nitric oxide (NO and nitrogen oxides (NO content in mainstream tobacco smoke, a new class of catalyst based on Cu-ZSM-5 zeolite has been synthesized. The effectiveness of the new catalyst (degree of reduction and specific catalytic ability was tested both by adding Cu-ZSM-5 zeolite directly to the tobacco blend and by addition to the filter. We have determined that adding the catalyst to the tobacco blend does not cause any changes in the physical, chemical or organoleptic properties of the cigarette blend. But, the addition reduces the yield of nitrogen oxides while having no influence on nicotine and “tar” content in the tobacco smoke of the modified blend. The catalyst addition increases the static burning rate (SBR. The changes in the quantity of NO and NOmay be explained by changes in burning conditions due to the increase of Oobtained from catalytic degradation of NO and NO, and adsorptive and diffusive properties of the catalyst. The changes in mainstream smoke analytes are also given on a puff-by-puff basis.

  20. Enhanced catalytic activity of lipase encapsulated in PCL nanofibers.

    Science.gov (United States)

    Song, Jie; Kahveci, Derya; Chen, Menglin; Guo, Zheng; Xie, Erqing; Xu, Xuebing; Besenbacher, Flemming; Dong, Mingdong

    2012-04-10

    Use of biocatalysis for industrial synthetic chemistry is on the verge of significant growth. Enzyme immobilization as an effective strategy for improving the enzyme activity has emerged from developments especially in nanoscience and nanotechnology. Here, lipase from Burkholderia cepacia (LBC), as an example of the luxuriant enzymes, was successfully encapsulated in polycaprolactone (PCL) nanofibers, proven by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Evaluated in both organic and aqueous medium, the activation factor of the encapsulated enzymes in the hydrolysis reaction was generally higher than that in the transesterification reaction. Enhanced catalytic activities were found when 5-20 w/w % of LBC was loaded. The effect of different solvents pretreatment on the activity of immobilized LBC was also investigated. The highest activation factor was found up to 14 for the sample containing acetone-treated LBC/PCL (10 w/w %). The encapsulated lipase reserved 50% of its original activity after the 10th run in the transesterification reaction in hexane medium. The mechanism of activation of lipase catalytic ability based on active PCL nanofiberous matrix is proposed. © 2012 American Chemical Society

  1. Catalytic synthesis of long-chained alcohols from syngas

    DEFF Research Database (Denmark)

    Christensen, Jakob Munkholt

    for the production of gasoline additives/replacements from biomass via a gasification process. It is observed that the sulfide catalyst is able to operate both with and without a sulfur source in the syngas feed, but the presence of a sulfur source like H2S can exert a significant influence on the catalytic....... Various catalysts based upon the bulk carbides Mo2C, WC and NbC have been synthesized and evaluated with respect to the catalytic behavior in highpressure CO hydrogenation. NbC is largely inactive, and K2CO3/WC produces mainly methanol and methane with a low activity, while K2CO3/Mo2C produces a mixture...... is qualitatively similar, although K provides a markedly better activity (31 % at 300 °C, 100 bar, 5000 h-1) and a better selectivity at identical conditions. At 275 °C an Li(CH3COO) promoted catalyst is very active and produces only hydrocarbons. If the effect of the different alkali promoters is compared...

  2. Studies Relevent to Catalytic Activation Co & other small Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Ford, Peter C

    2005-02-22

    Detailed annual and triannual reports describing the progress accomplished during the tenure of this grant were filed with the Program Manager for Catalysis at the Office of Basic Energy Sciences. To avoid unnecessary duplication, the present report will provide a brief overview of the research areas that were sponsored by this grant and list the resulting publications and theses based on this DOE supported research. The scientific personnel participating in (and trained by) this grant's research are also listed. Research carried out under this DOE grant was largely concerned with the mechanisms of the homogeneous catalytic and photocatalytic activation of small molecules such as carbon monoxide, dihydrogen and various hydrocarbons. Much of the more recent effort has focused on the dynamics and mechanisms of reactions relevant to substrate carbonylations by homogeneous organometallic catalysts. A wide range of modern investigative techniques were employed, including quantitative fast reaction methodologies such as time-resolved optical (TRO) and time-resolved infrared (TRIR) spectroscopy and stopped flow kinetics. Although somewhat diverse, this research falls within the scope of the long-term objective of applying quantitative techniques to elucidate the dynamics and understand the principles of mechanisms relevant to the selective and efficient catalytic conversions of fundamental feedstocks to higher value materials.

  3. Catalytic steam reforming of ethanol for hydrogen production: Brief status

    Directory of Open Access Journals (Sweden)

    Bineli Aulus R.R.

    2016-01-01

    Full Text Available Hydrogen represents a promising fuel since it is considered as a cleanest energy carrier and also because during its combustion only water is emitted. It can be produced from different kinds of renewable feedstocks, such as ethanol, in this sense hydrogen could be treated as biofuel. Three chemical reactions can be used to achieve this purpose: the steam reforming (SR, the partial oxidation (POX and the autothermal reforming (ATR. In this study, the catalysts implemented in steam reforming of ethanol were reviewed. A wide variety of elements can be used as catalysts for this reaction, such as base metals (Ni, Cu and Co or noble metals (Rh, Pt and Ru usually deposited on a support material that increases surface area and improves catalytic function. The use of Rh, Ni and Pt supported or promoted with CeO2, and/or La2O3 shows excellent performance in ethanol SR catalytic process. The ratio of water to ethanol, reaction temperatures, catalysts loadings, selectivity and activity are also discussed as they are extremely important for high hydrogen yields.

  4. Cytochromes P450: History, Classes, Catalytic Mechanism, and Industrial Application.

    Science.gov (United States)

    Cook, D J; Finnigan, J D; Cook, K; Black, G W; Charnock, S J

    Cytochromes P450, a family of heme-containing monooxygenases that catalyze a diverse range of oxidative reactions, are so-called due to their maximum absorbance at 450nm, ie, "Pigment-450nm," when bound to carbon monoxide. They have appeal both academically and commercially due to their high degree of regio- and stereoselectivity, for example, in the area of active pharmaceutical ingredient synthesis. Despite this potential, they often exhibit poor stability, low turnover numbers and typically require electron transport protein(s) for catalysis. P450 systems exist in a variety of functional domain architectures, organized into 10 classes. P450s are also divided into families, each of which is based solely on amino acid sequence homology. Their catalytic mechanism employs a very complex, multistep catalytic cycle involving a range of transient intermediates. Mutagenesis is a powerful tool for the development of improved biocatalysts and has been used extensively with the archetypal Class VIII P450, BM3, from Bacillus megaterium, but with the increasing scale of genomic sequencing, a huge resource is now available for the discovery of novel P450s. © 2016 Elsevier Inc. All rights reserved.

  5. Catalytic inhibition of topoisomerase II by a novel rationally designed ATP-competitive purine analogue.

    Science.gov (United States)

    Chène, Patrick; Rudloff, Joëlle; Schoepfer, Joseph; Furet, Pascal; Meier, Peter; Qian, Zhiyan; Schlaeppi, Jean-Marc; Schmitz, Rita; Radimerski, Thomas

    2009-01-07

    Topoisomerase II poisons are in clinical use as anti-cancer therapy for decades and work by stabilizing the enzyme-induced DNA breaks. In contrast, catalytic inhibitors block the enzyme before DNA scission. Although several catalytic inhibitors of topoisomerase II have been described, preclinical concepts for exploiting their anti-proliferative activity based on molecular characteristics of the tumor cell have only recently started to emerge. Topoisomerase II is an ATPase and uses the energy derived from ATP hydrolysis to orchestrate the movement of the DNA double strands along the enzyme. Thus, interfering with ATPase function with low molecular weight inhibitors that target the nucleotide binding pocket should profoundly affect cells that are committed to undergo mitosis. Here we describe the discovery and characterization of a novel purine diamine analogue as a potent ATP-competitive catalytic inhibitor of topoisomerase II. Quinoline aminopurine compound 1 (QAP 1) inhibited topoisomerase II ATPase activity and decatenation reaction at sub-micromolar concentrations, targeted both topoisomerase II alpha and beta in cell free assays and, using a quantitative cell-based assay and a chromosome segregation assay, displayed catalytic enzyme inhibition in cells. In agreement with recent hypothesis, we show that BRCA1 mutant breast cancer cells have increased sensitivity to QAP 1. The results obtained with QAP 1 demonstrate that potent and selective catalytic inhibition of human topoisomerase II function with an ATP-competitive inhibitor is feasible. Our data suggest that further drug discovery efforts on ATP-competitive catalytic inhibitors are warranted and that such drugs could potentially be developed as anti-cancer therapy for tumors that bear the appropriate combination of molecular alterations.

  6. Catalytic inhibition of topoisomerase II by a novel rationally designed ATP-competitive purine analogue

    Directory of Open Access Journals (Sweden)

    Schlaeppi Jean-Marc

    2009-01-01

    Full Text Available Abstract Background Topoisomerase II poisons are in clinical use as anti-cancer therapy for decades and work by stabilizing the enzyme-induced DNA breaks. In contrast, catalytic inhibitors block the enzyme before DNA scission. Although several catalytic inhibitors of topoisomerase II have been described, preclinical concepts for exploiting their anti-proliferative activity based on molecular characteristics of the tumor cell have only recently started to emerge. Topoisomerase II is an ATPase and uses the energy derived from ATP hydrolysis to orchestrate the movement of the DNA double strands along the enzyme. Thus, interfering with ATPase function with low molecular weight inhibitors that target the nucleotide binding pocket should profoundly affect cells that are committed to undergo mitosis. Results Here we describe the discovery and characterization of a novel purine diamine analogue as a potent ATP-competitive catalytic inhibitor of topoisomerase II. Quinoline aminopurine compound 1 (QAP 1 inhibited topoisomerase II ATPase activity and decatenation reaction at sub-micromolar concentrations, targeted both topoisomerase II alpha and beta in cell free assays and, using a quantitative cell-based assay and a chromosome segregation assay, displayed catalytic enzyme inhibition in cells. In agreement with recent hypothesis, we show that BRCA1 mutant breast cancer cells have increased sensitivity to QAP 1. Conclusion The results obtained with QAP 1 demonstrate that potent and selective catalytic inhibition of human topoisomerase II function with an ATP-competitive inhibitor is feasible. Our data suggest that further drug discovery efforts on ATP-competitive catalytic inhibitors are warranted and that such drugs could potentially be developed as anti-cancer therapy for tumors that bear the appropriate combination of molecular alterations.

  7. Catalytic Enantioselective Synthesis of Naturally Occurring Butenolides via Hetero-Allylic Alkylation and Ring Closing Metathesis

    NARCIS (Netherlands)

    Mao, Bin; Geurts, Koen; Fañanás-Mastral, Martín; Zijl, Anthoni W. van; Fletcher, Stephen P.; Minnaard, Adriaan J.; Feringa, Bernard

    2011-01-01

    An efficient catalytic asymmetric synthesis of chiral γ-butenolides was developed based on the hetero-allylic asymmetric alkylation (h-AAA) in combination with ring closing metathesis (RCM). The synthetic potential of the h-AAA-RCM protocol was illustrated with the facile synthesis of (-)-whiskey

  8. Catalytic enantioselective synthesis of naturally occurring butenolides via hetero-allylic alkylation and ring closing metathesis.

    Science.gov (United States)

    Mao, Bin; Geurts, Koen; Fañanás-Mastral, Martín; van Zijl, Anthoni W; Fletcher, Stephen P; Minnaard, Adriaan J; Feringa, Ben L

    2011-03-04

    An efficient catalytic asymmetric synthesis of chiral γ-butenolides was developed based on the hetero-allylic asymmetric alkylation (h-AAA) in combination with ring closing metathesis (RCM). The synthetic potential of the h-AAA-RCM protocol was illustrated with the facile synthesis of (-)-whiskey lactone, (-)-cognac lactone, (-)-nephrosteranic acid, and (-)-roccellaric acid.

  9. Practical catalytic arylation of C–H bonds by iron/phenanthroline systems

    NARCIS (Netherlands)

    Huang, Y.

    2015-01-01

    In Chapter 1, an overview is given of the current status of the field of non-precious metal catalyzed/mediated direct arylation reactions. Reports on direct arylations catalyzed by Fe, Co, Ni and Cu are mainly demonstrated and discussed. Chapter 2 described a pre-made iron-based catalytic system

  10. Catalytic signal amplification using [Fe(III)(biuret-amide)]-mesoporous silica nanoparticles: visual cyanide detection.

    Science.gov (United States)

    Panda, Chakadola; Dhar, Basab B; Malvi, Bharmana; Bhattacharjee, Yudhajit; Gupta, Sayam Sen

    2013-03-18

    Catalytic signal amplification was used for the colorimetric detection of CN(-) in aqueous media by using the enzyme catalase in tandem with mesoporous silica nanoparticle based synthetic HRP enzyme mimic Fe-MSNs. Signal amplification up to a maximum of eight fold was observed for the reporter "oxidized TMB" with respect to the added CN(-) ion.

  11. Catalytic Mechanism and Mode of Action of the Periplasmic Alginate Epimerase AlgG

    NARCIS (Netherlands)

    Wolfram, Francis; Kitova, Elena N.; Robinson, Howard; Walvoort, Marthe T. C.; Codee, Jeroen D. C.; Klassen, John S.; Howell, P. Lynne

    2014-01-01

    Background: The alginate epimerase AlgG converts mannuronate to its C5 epimer guluronate at the polymer level. Results: The structure of Pseudomonas syringae AlgG has been determined, and the protein has been functionally characterized. Conclusion: His(319) acts as the catalytic base, whereas

  12. Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion

    Energy Technology Data Exchange (ETDEWEB)

    Pozan, Gulin Selda, E-mail: gpozan@istanbul.edu.tr [Istanbul University, Faculty of Engineering, Chemical Engineering Department, Avcilar 34320, Istanbul (Turkey)

    2012-06-30

    Highlights: Black-Right-Pointing-Pointer {alpha}-Al{sub 2}O{sub 3}, obtained from Bohmite, as a support for enhancing of the activity. Black-Right-Pointing-Pointer The support material for catalytic oxidation. Black-Right-Pointing-Pointer The manganese state and oxygen species effect on the catalytic combustion reaction. - Abstract: The aim of this work was to study combustion of toluene (1000 ppm) over MnO{sub 2} modified with different supports. {alpha}-Al{sub 2}O{sub 3} and {gamma}-Al{sub 2}O{sub 3} obtained from Boehmite, {gamma}-Al{sub 2}O{sub 3} (commercial), SiO{sub 2}, TiO{sub 2} and ZrO{sub 2} were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO{sub 2} was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO{sub 2}/{alpha}-Al{sub 2}O{sub 3}(B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289 Degree-Sign C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity.

  13. Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion

    International Nuclear Information System (INIS)

    Pozan, Gulin Selda

    2012-01-01

    Highlights: ► α-Al 2 O 3 , obtained from Bohmite, as a support for enhancing of the activity. ► The support material for catalytic oxidation. ► The manganese state and oxygen species effect on the catalytic combustion reaction. - Abstract: The aim of this work was to study combustion of toluene (1000 ppm) over MnO 2 modified with different supports. α-Al 2 O 3 and γ-Al 2 O 3 obtained from Boehmite, γ-Al 2 O 3 (commercial), SiO 2 , TiO 2 and ZrO 2 were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO 2 was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO 2 /α-Al 2 O 3 (B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289 °C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity.

  14. Method For Selective Catalytic Reduction Of Nitrogen Oxides

    Science.gov (United States)

    Mowery-Evans, Deborah L.; Gardner, Timothy J.; McLaughlin, Linda I.

    2005-02-15

    A method for catalytically reducing nitrogen oxide compounds (NO.sub.x, defined as nitric oxide, NO, +nitrogen dioxide, NO.sub.2) in a gas by a material comprising a base metal consisting essentially of CuO and Mn, and oxides of Mn, on an activated metal hydrous metal oxide support, such as HMO:Si. A promoter, such as tungsten oxide or molybdenum oxide, can be added and has been shown to increase conversion efficiency. This method provides good conversion of NO.sub.x to N.sub.2, good selectivity, good durability, resistance to SO.sub.2 aging and low toxicity compared with methods utilizing vanadia-based catalysts.

  15. Studies of coupled chemical and catalytic coal conversion methods

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.

    1990-01-01

    This report concerns our research on base-catalyzed coal solubilization and a new approach for hydrogen addition. The work on base-catalyzed, chemical solubilization is continuing. this report is focused on the hydrogenation research. Specifically it deals with the use of arene chromium carbonyl complexes as reagents for the addition of dideuterium to coal molecules. In one phase of the work, he has established that the aromatic hydrocarbons in a representative coal liquid can be converted in very good yield to arene chromium carbonyl compounds. In a second phase of the work directly related to our objective of improved methods for catalytic hydrogenation, he has established that the aromatic constituents of the same coal liquid add dideuterium in the presence of added napththalene chromium carbonyl.

  16. 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

  17. Advanced treatment of biologically pretreated coal gasification wastewater by a novel integration of heterogeneous catalytic ozonation and biological process.

    Science.gov (United States)

    Zhuang, Haifeng; Han, Hongjun; Jia, Shengyong; Hou, Baolin; Zhao, Qian

    2014-08-01

    Advanced treatment of biologically pretreated coal gasification wastewater (CGW) was investigated employing heterogeneous catalytic ozonation integrated with anoxic moving bed biofilm reactor (ANMBBR) and biological aerated filter (BAF) process. The results indicated that catalytic ozonation with the prepared catalyst (i.e. MnOx/SBAC, sewage sludge was converted into sludge based activated carbon (SBAC) which loaded manganese oxides) significantly enhanced performance of pollutants removal by generated hydroxyl radicals. The effluent of catalytic ozonation process was more biodegradable and less toxic than that in ozonation alone. Meanwhile, ANMBBR-BAF showed efficient capacity of pollutants removal in treatment of the effluent of catalytic ozonation at a shorter reaction time, allowing the discharge limits to be met. Therefore, the integrated process with efficient, economical and sustainable advantages was suitable for advanced treatment of real biologically pretreated CGW. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Probing the Catalytic Mechanism of S-Ribosylhomocysteinase (LuxS) with Catalytic Intermediates and Substrate Analogues

    Energy Technology Data Exchange (ETDEWEB)

    Gopishetty, Bhaskar; Zhu, Jinge; Rajan, Rakhi; Sobczak, Adam J.; Wnuk, Stanislaw F.; Bell, Charles E.; Pei, Dehua; (OSU); (FIU)

    2009-05-12

    S-Ribosylhomocysteinase (LuxS) cleaves the thioether bond in S-ribosylhomocysteine (SRH) to produce homocysteine (Hcys) and 4,5-dihydroxy-2,3-pentanedione (DPD), the precursor of the type II bacterial quorum sensing molecule (AI-2). The catalytic mechanism of LuxS comprises three distinct reaction steps. The first step involves carbonyl migration from the C1 carbon of ribose to C2 and the formation of a 2-ketone intermediate. The second step shifts the C=O group from the C2 to C3 position to produce a 3-ketone intermediate. In the final step, the 3-ketone intermediate undergoes a {beta}-elimination reaction resulting in the cleavage of the thioether bond. In this work, the 3-ketone intermediate was chemically synthesized and shown to be chemically and kinetically competent in the LuxS catalytic pathway. Substrate analogues halogenated at the C3 position of ribose were synthesized and reacted as time-dependent inhibitors of LuxS. The time dependence was caused by enzyme-catalyzed elimination of halide ions. Examination of the kinetics of halide release and decay of the 3-ketone intermediate catalyzed by wild-type and mutant LuxS enzymes revealed that Cys-84 is the general base responsible for proton abstraction in the three reaction steps, whereas Glu-57 likely facilitates substrate binding and proton transfer during catalysis.

  19. Probing the Catalytic Mechanism of S-Ribosylhomocysteinase (LuxS) with Catalytic Intermediates and Substrate Analogues

    International Nuclear Information System (INIS)

    Gopishetty, Bhaskar; Zhu, Jinge; Rajan, Rakhi; Sobczak, Adam J.; Wnuk, Stanislaw F.; Bell, Charles E.; Pei, Dehua

    2009-01-01

    S-Ribosylhomocysteinase (LuxS) cleaves the thioether bond in S-ribosylhomocysteine (SRH) to produce homocysteine (Hcys) and 4,5-dihydroxy-2,3-pentanedione (DPD), the precursor of the type II bacterial quorum sensing molecule (AI-2). The catalytic mechanism of LuxS comprises three distinct reaction steps. The first step involves carbonyl migration from the C1 carbon of ribose to C2 and the formation of a 2-ketone intermediate. The second step shifts the C=O group from the C2 to C3 position to produce a 3-ketone intermediate. In the final step, the 3-ketone intermediate undergoes a β-elimination reaction resulting in the cleavage of the thioether bond. In this work, the 3-ketone intermediate was chemically synthesized and shown to be chemically and kinetically competent in the LuxS catalytic pathway. Substrate analogues halogenated at the C3 position of ribose were synthesized and reacted as time-dependent inhibitors of LuxS. The time dependence was caused by enzyme-catalyzed elimination of halide ions. Examination of the kinetics of halide release and decay of the 3-ketone intermediate catalyzed by wild-type and mutant LuxS enzymes revealed that Cys-84 is the general base responsible for proton abstraction in the three reaction steps, whereas Glu-57 likely facilitates substrate binding and proton transfer during catalysis.

  20. Biogasoline Production from Palm Oil Via Catalytic Hydrocracking over Gamma-Alumina Catalyst

    Directory of Open Access Journals (Sweden)

    Anondho Wijanarko

    2010-10-01

    Full Text Available Bio gasoline conversion from palm oil is an alternative energy resources method which can be substituted fossil fuel base energy utilization. Previous research resulted that palm oil can be converted into hydrocarbon by catalytic cracking reaction with γ-alumina catalyst. In this research, catalytic cracking reaction of palm oil by γ-alumina catalyst is done in  a stirrer batch reactor with the oil/catalyst weight ratio variation of 100:1, 75:1, and 50:1; at suhue variation of 260 to 340oC and reaction time variation of 1 to 2 hour. Post cracking reaction, bio gasoline yield could be obtained after 2 steps batch distillation. Physical property test result such as density and viscosity of this cracking reaction product and commercial gasoline tended a closed similarity. According to result of the cracking product's density, viscosity and FTIR, it  can conclude that optimum yield of the palm oil catalytic cracking reaction could be occurred when oil/catalyst weight  ratio 100:1 at 340 oC in 1.5 hour and base on this bio gasoline's FTIR, GC and GC-MS identification results, its  hydrocarbons content was resembled to the commercial  gasoline. This palm oil catalytic cracking reaction shown 11.8% (v/v in yield and 28.0% (v/v in conversion concern to feed palm oil base and produced a 61.0 octane number's biogasoline.

  1. Identification of Catalytic Residues Using a Novel Feature that Integrates the Microenvironment and Geometrical Location Properties of Residues

    Science.gov (United States)

    Han, Lei; Zhang, Yong-Jun; Song, Jiangning; Liu, Ming S.; Zhang, Ziding

    2012-01-01

    Enzymes play a fundamental role in almost all biological processes and identification of catalytic residues is a crucial step for deciphering the biological functions and understanding the underlying catalytic mechanisms. In this work, we developed a novel structural feature called MEDscore to identify catalytic residues, which integrated the microenvironment (ME) and geometrical properties of amino acid residues. Firstly, we converted a residue's ME into a series of spatially neighboring residue pairs, whose likelihood of being located in a catalytic ME was deduced from a benchmark enzyme dataset. We then calculated an ME-based score, termed as MEscore, by summing up the likelihood of all residue pairs. Secondly, we defined a parameter called Dscore to measure the relative distance of a residue to the center of the protein, provided that catalytic residues are typically located in the center of the protein structure. Finally, we defined the MEDscore feature based on an effective nonlinear integration of MEscore and Dscore. When evaluated on a well-prepared benchmark dataset using five-fold cross-validation tests, MEDscore achieved a robust performance in identifying catalytic residues with an AUC1.0 of 0.889. At a ≤10% false positive rate control, MEDscore correctly identified approximately 70% of the catalytic residues. Remarkably, MEDscore achieved a competitive performance compared with the residue conservation score (e.g. CONscore), the most informative singular feature predominantly employed to identify catalytic residues. To the best of our knowledge, MEDscore is the first singular structural feature exhibiting such an advantage. More importantly, we found that MEDscore is complementary with CONscore and a significantly improved performance can be achieved by combining CONscore with MEDscore in a linear manner. As an implementation of this work, MEDscore has been made freely accessible at http://protein.cau.edu.cn/mepi/. PMID:22829945

  2. 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. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

    Mantzaras, I.; Schneider, A.

    2006-03-15

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

  4. Microwave-induced carbon nanotubes catalytic degradation of organic pollutants in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jing; Xue, Shuang; Song, Youtao; Shen, Manli [School of Environment Science, Liaoning University, Shenyang 110036 (China); Zhang, Zhaohong, E-mail: lnuhjhx@163.com [School of Environment Science, Liaoning University, Shenyang 110036 (China); Yuan, Tianxin; Tian, Fangyuan [School of Environment Science, Liaoning University, Shenyang 110036 (China); Dionysiou, Dionysios D., E-mail: dionysios.d.dionysiou@uc.edu [Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, OH 45221-0012 (United States)

    2016-06-05

    Highlights: • Microwave-induced CNTs-based catalytic degradation technology is developed. • Microwave catalytic activities of CNTs with different diameters are compared. • Organic pollutants with different structure can be degraded in MW/CNTs system. • The 10–20 nm CNTs shows the higher catalytic activity under MW irradiation. - Abstract: In this study, a new catalytic degradation technology using microwave induced carbon nanotubes (MW/CNTs) was proposed and applied in the treatment of organic pollutants in aqueous solution. The catalytic activity of three CNTs of 10–20 nm, 20–40 nm, and 40–60 nm diameters were compared. The results showed that organic pollutants such as methyl orange (MO), methyl parathion (MP), sodium dodecyl benzene sulfonate (SDBS), bisphenol A (BPA), and methylene blue (MB) in aqueous solution could be degraded effectively and rapidly in MW/CNTs system. CNTs with diameter of 10–20 nm exhibited the highest catalytic activity of the three CNTs under MW irradiation. Further, complete degradation was obtained using 10–20 nm CNTs within 7.0 min irradiation when 25 mL MO solution (25 mg/L), 1.2 g/L catalyst dose, 450 W, 2450 MHz, and pH = 6.0 were applied. The rate constants (k) for the degradation of SDBS, MB, MP, MO and BPA using 10–20 nm CNTs/MW system were 0.726, 0.679, 0.463, 0.334 and 0.168 min{sup −1}, respectively. Therefore, this technology may have potential application for the treatment of targeted organic pollutants in wastewaters.

  5. Catalytic oxidation of soot over alkaline niobates

    International Nuclear Information System (INIS)

    Pecchi, G.; Cabrera, B.; Buljan, A.; Delgado, E.J.; Gordon, A.L.; Jimenez, R.

    2013-01-01

    Highlights: ► No previous reported studies about alkaline niobates as catalysts for soot oxidation. ► NaNbO 3 and KNbO 3 perovskite-type oxides show lower activation energy than other lanthanoid perovskite-type oxides. ► The alkaline niobate does not show deactivation by metal loss. - Abstract: The lack of studies in the current literature about the assessment of alkaline niobates as catalysts for soot oxidation has motivated this research. In this study, the synthesis, characterization and assessment of alkaline metal niobates as catalysts for soot combustion are reported. The solids MNbO 3 (M = Li, Na, K, Rb) are synthesized by a citrate method, calcined at 450 °C, 550 °C, 650 °C, 750 °C, and characterized by AAS, N 2 adsorption, XRD, O 2 -TPD, FTIR and SEM. All the alkaline niobates show catalytic activity for soot combustion, and the activity depends basically on the nature of the alkaline metal and the calcination temperature. The highest catalytic activity, expressed as the temperature at which combustion of carbon black occurs at the maximum rate, is shown by KNbO 3 calcined at 650 °C. At this calcination temperature, the catalytic activity follows an order dependent on the atomic number, namely: KNbO 3 > NaNbO 3 > LiNbO 3 . The RbNbO 3 solid do not follow this trend presumably due to the perovskite structure was not reached. The highest catalytic activity shown by of KNbO 3 , despite the lower apparent activation energy of NaNbO 3 , stress the importance of the metal nature and suggests the hypothesis that K + ions are the active sites for soot combustion. It must be pointed out that alkaline niobate subjected to consecutive soot combustion cycles does not show deactivation by metal loss, due to the stabilization of the alkaline metal inside the perovskite structure.

  6. 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...

  7. 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...

  8. Methane combustion in catalytic premixed burners

    International Nuclear Information System (INIS)

    Cerri, I.; Saracco, G.; Specchia, V.

    1999-01-01

    Catalytic premixed burners for domestic boiler applications were developed with the aim of achieving a power modularity from 10 to 100% and pollutant emissions limited to NO x 2 , where the combustion took place entirely inside the burner heating it to incandescence and allowing a decrease in the flame temperature and NO x emissions. Such results were confirmed through further tests carried out in a commercial industrial-scale boiler equipped with the conical panels. All the results, by varying the excess air and the heat power employed, are presented and discussed [it

  9. Tritium stripping by a catalytic exchange stripper

    International Nuclear Information System (INIS)

    Heung, L.K.; Gibson, G.W.; Ortman, M.S.

    1991-01-01

    A catalytic exchange process for stripping elemental tritium from gas streams has been demonstrated. The process uses a catalyzed isotopic exchange reaction between tritium in the gas phase and protium or deuterium in the solid phase on alumina. The reaction is catalyzed by platinum deposited on the alumina. The process has been tested with both tritium and deuterium. Decontamination factors (ration of inlet and outlet tritium concentrations) as high as 1000 have been achieved, depending on inlet concentration. The test results and some demonstrated applications are presented

  10. Direct catalytic hydrothermal liquefaction of spirulina to biofuels with hydrogen

    Science.gov (United States)

    Zeng, Qin; Liao, Hansheng; Zhou, Shiqin; Li, Qiuping; Wang, Lu; Yu, Zhihao; Jing, Li

    2018-01-01

    We report herein on acquiring biofuels from direct catalytic hydrothermal liquefaction of spirulina. The component of bio-oil from direct catalytic hydrothermal liquefaction was similar to that from two independent processes (including liquefaction and upgrading of biocrude). However, one step process has higher carbon recovery, due to the less loss of carbons. It was demonstrated that the yield and HHV of bio-oil from direct catalytic algae with hydrothermal condition is higher than that from two independent processes.

  11. 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....

  12. Nanostructured Catalytic Reactors for Air Purification, Phase I

    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...

  13. Nanostructured Catalytic Reactors for Air Purification, Phase II

    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...

  14. 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.

  15. Microwave Catalytic Oxidation of Hydrocarbons in Aqueous Solutions

    National Research Council Canada - National Science Library

    Cha, Chang

    2003-01-01

    .... A sufficient amount of experimental work has been completed evaluating the performance of the microwave catalytic oxidation process and determining the effect of different operating parameters...

  16. Study of catalytic phenomena in radiation chemistry

    International Nuclear Information System (INIS)

    Dran, J.C.

    1965-01-01

    Two phenomena have been studied: the action of γ rays from radio-cobalt on the adsorption and catalytic properties of ZnO and NiO in. relationship with the heterogeneous oxidation of CO, and the homogeneous catalysis by OsO 4 of the oxidation of various aqueous phase solutes by the same radiation. The prior irradiation of ZnO and of NiO does not modify their catalytic activity but generally increases the adsorption energy of -the gases CO and O 2 . The influence of the radiations appears to be connected with the presence of traces of water on ZnO and of an excess of oxygen on NiO. Osmium tetroxide which is not degraded by irradiation in acid solution, accelerates the radiolytic oxidation of certain compounds (Te IV , Pt 11 , As 111 ) in the presence of oxygen, as a result of its sensitizing effect on the oxidation by H 2 O 2 . In the case of phosphites on the other hand, OsO 4 has a protecting action under certain conditions of acidity and may suppress entirely the chain reaction which characterizes the oxidation of this solute byγ rays. A general mechanism is proposed for these phenomena. The rate constant for the OsO 4 + HO 2 reaction is calculated to be 5.7 x 10 5 l.mol -1 . sec -1 . (author) [fr

  17. Catalytic reactor for low-Btu fuels

    Science.gov (United States)

    Smith, Lance; Etemad, Shahrokh; Karim, Hasan; Pfefferle, William C.

    2009-04-21

    An improved catalytic reactor includes a housing having a plate positioned therein defining a first zone and a second zone, and a plurality of conduits fabricated from a heat conducting material and adapted for conducting a fluid therethrough. The conduits are positioned within the housing such that the conduit exterior surfaces and the housing interior surface within the second zone define a first flow path while the conduit interior surfaces define a second flow path through the second zone and not in fluid communication with the first flow path. The conduit exits define a second flow path exit, the conduit exits and the first flow path exit being proximately located and interspersed. The conduits define at least one expanded section that contacts adjacent conduits thereby spacing the conduits within the second zone and forming first flow path exit flow orifices having an aggregate exit area greater than a defined percent of the housing exit plane area. Lastly, at least a portion of the first flow path defines a catalytically active surface.

  18. Rational design of ornithine decarboxylase with high catalytic activity for the production of putrescine.

    Science.gov (United States)

    Choi, Hyang; Kyeong, Hyun-Ho; Choi, Jung Min; Kim, Hak-Sung

    2014-09-01

    Putrescine finds wide industrial applications in the synthesis of polymers, pharmaceuticals, agrochemicals, and surfactants. Owing to economic and environmental concerns, the microbial production of putrescine has attracted a great deal of attention, and ornithine decarboxylase (ODC) is known to be a key enzyme in the biosynthetic pathway. Herein, we present the design of ODC from Escherichia coli with high catalytic efficiency using a structure-based rational approach. Through a substrate docking into the model structure of the enzyme, we first selected residues that might lead to an increase in catalytic activity. Of the selected residues that are located in the α-helix and the loops constituting the substrate entry site, a mutational analysis of the single mutants identified two key residues, I163 and E165. A combination of two single mutations resulted in a 62.5-fold increase in the catalytic efficiency when compared with the wild-type enzyme. Molecular dynamics simulations of the best mutant revealed that the substrate entry site becomes more flexible through mutations, while stabilizing the formation of the dimeric interface of the enzyme. Our approach can be applied to the design of other decarboxylases with high catalytic efficiency for the production of various chemicals through bio-based processes.

  19. A Hybrid Catalytic Route to Fuels from Biomass Syngas

    Energy Technology Data Exchange (ETDEWEB)

    Harmon, Laurel [LanzaTech, Inc.; Hallen, Richard [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lilga, Michael [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Heijstra, Bjorn [LanzaTech, Inc.; Palou-Rivera, Ignasi [LanzaTech, Inc.; Handler, Robert [Michigan Technological Univ., Houghton, MI (United States)

    2017-12-31

    LanzaTech partnered with the Pacific Northwest National Laboratory (PNNL), Imperium Aviation Fuels, InEnTec, Orochem Technologies, the University of Delaware, Michigan Technological University, the National Renewable Energy Laboratory, and The Boeing Company, to develop a cost-effective hybrid conversion technology for catalytic upgrading of biomass-derived syngas to sustainable alternative jet fuel (SAJF) meeting the price, quality and environmental requirements of the aviation industry. Alternative “synthetic paraffinic kerosene” (SPK) blendstock produced from syngas via “Fischer-Tropsch” (F-T) or from lipids via “hydroprocessing of esters and fatty acids” (HEFA) are currently being used in commercial jet fuel blends containing at least 50% petroleum-based fuel. This project developed an alternative route to SAJF from ethanol, a type of “alcohol to jet” (ATJ) SPK. The project objective was to demonstrate a pathway that combines syngas fermentation to ethanol with catalytic upgrading of ethanol to sustainable alternative jet fuel and shows attractive overall system economics to drive down the price of biomass-derived jet fuel. The hybrid pathway was to be demonstrated on three biomass feedstocks: corn stover, woody biomass, and third biomass feedstock, cellulosic residues. The objective also included the co-production of chemicals, exemplified by 2,3-Butanediol (2,3-BDO), which can be converted to key chemical intermediates. The team successfully demonstrated that biomass syngas fermentation followed by catalytic conversion is a viable alternative to the Fischer-Tropsch process and produces a fuel with properties comparable to F-T and HEFA SPKs. Plasma gasification and gas fermentation were successfully integrated and demonstrated in continuous fermentations on waste wood, corn stover, and cellulosic bagasse. Gas fermentation was demonstrated to produce ethanol suitable for catalytic upgrading, isolating the upgrading from variations in biomass

  20. 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. Copyright © 2016, American Association for the Advancement of Science.

  1. Triggering activity of catalytic rod-like supramolecular polymers.

    Science.gov (United States)

    Huerta, Elisa; van Genabeek, Bas; Lamers, Brigitte A G; Koenigs, Marcel M E; Meijer, E W; Palmans, Anja R A

    2015-02-23

    Supramolecular polymers based on benzene-1,3,5-tricarboxamides (BTAs) functionalized with an L- or D-proline moiety display high catalytic activity towards aldol reactions in water. High turnover frequencies (TOF) of up to 27×10(-4) s(-1) and excellent stereoselectivities (up to 96% de, up to 99% ee) were observed. In addition, the catalyst could be reused and remained active at catalyst loadings and substrate concentrations as low as 0.1 mol % and 50 mM, respectively. A temperature-induced conformational change in the supramolecular polymer triggers the high activity of the catalyst. The supramolecular polymer's helical sense in combination with the configuration of the proline (L- or D-) is responsible for the observed selectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Computational enzyme design: transitioning from catalytic proteins to enzymes.

    Science.gov (United States)

    Mak, Wai Shun; Siegel, Justin B

    2014-08-01

    The widespread interest in enzymes stem from their ability to catalyze chemical reactions under mild and ecologically friendly conditions with unparalleled catalytic proficiencies. While thousands of naturally occurring enzymes have been identified and characterized, there are still numerous important applications for which there are no biological catalysts capable of performing the desired chemical transformation. In order to engineer enzymes for which there is no natural starting point, efforts using a combination of quantum chemistry and force-field based protein molecular modeling have led to the design of novel proteins capable of catalyzing chemical reactions not catalyzed by naturally occurring enzymes. Here we discuss the current status and potential avenues to pursue as the field of computational enzyme design moves forward. Published by Elsevier Ltd.

  3. Catalytic activity of nuclease P1: Experiment and theory

    International Nuclear Information System (INIS)

    Miller, J.H.; Falcone, J.M.; Shibata, M.; Box, H.C.

    1994-10-01

    Nuclease P1 from Penicillium citrinum is a zinc dependent glyco-enzyme that recognizes single stranded DNA and RNA as substrates and hydrolyzes the phosphate ester bond. Nuclease Pl seems to recognize particular conformations of the phosphodiester backbone and shows significant variation in the rate of hydrolytic activity depending upon which nucleosides are coupled by the phosphodiester bond. The efficiency of nuclease Pl in hydrolyzing the phosphodiester bonds of a substrate can be altered by modifications to one of the substrate bases induced by ionizing radiation or oxidative stress. Measurements have been made of the effect of several radiation induced lesions on the catalytic rate of nuclease Pl. A model of the structure of the enzyme has been constructed in order to better understand the binding and activity of this enzyme on various ssDNA substrates

  4. Catalytic combustion in gas stoves - Phase II

    Energy Technology Data Exchange (ETDEWEB)

    Hjelm, Anna-Karin [CATATOR AB, Lund (Sweden)

    2003-06-01

    Several independent studies show that gas stoves to some degree contribute to the indoor emissions of NO{sub x} especially in situations were the ventilation flow is poor. The peak-NO{sub x} concentrations can reach several hundred ppb but the integral concentration seldom exceeds about 20 - 50 ppb, which corresponds to an indoor-outdoor ratio of about 1 - 2.5. Epidemiological studies indicate increasing problems with respiratory symptoms in sensitive people at concentrations as low as 15 ppb of NO{sub 2}. Consequently, the NO{sub x}-concentration in homes where gas stoves are used is high enough to cause health effects. However, in situations where the ventilation flow is high (utilisation of ventilation hoods) the NO{sub x}-emissions are not likely to cause any health problems. This study has been aimed at investigating the possibilities to reduce the NO{sub x} emissions from gas stoves by replacing the conventional flame combustion with catalytic combustion. The investigation is requested by Swedish Gas Center, and is a following-up work of an earlier conducted feasibility study presented in April-2002. The present investigation reports on the possibility to use cheap and simple retro-fit catalytic design suggestions for traditional gas stoves. Experiments have been conducted with both natural and town gas, and parameters such as emissions of NO{sub x}, CO and unburned fuel gas and thermal efficiency, etc, have been examined and are discussed. The results show that it is possible to reduce the NO{sub x} emissions up to 80% by a simple retro-fit installation, without decreasing the thermal efficiency of the cooking plate. The measured source strengths correspond to indoor NO{sub x} concentrations that are below or equal to the average outdoor concentration, implying that no additional detrimental health effects are probable. The drawback of the suggested installations is that the concentration of CO and in some cases also CH{sub 4} are increased in the flue gases

  5. Modelling and Simulation of Packed Bed Catalytic Converter for Oxidation of Soot in Diesel Powered Vehicles Flue Gas

    Directory of Open Access Journals (Sweden)

    Mohammad Nasikin

    2010-10-01

    Full Text Available Diesel vehicle is used in Indonesia in very big number. This vehicle exhausts pollutants especially diesel soot that can be reduces by using a catalytic converter to convert the soot to CO2. To obtain the optimal dimension of catalytic converter it is needed a model that can represent the profile of soot weight, temperature and pressure along the catalytic converter. In this study, a model is developed for packed bed catalytic converter in an adiabatic condition based on a kinetic study that has been  reported previously. Calculation of developed equations in this model uses Polymath 5.X solver with Range Kutta Method. The simulation result shows that temperature profile along catalytic converter increases with the decrease of soot weight,  while pressure profile decreases. The increase of soot weight in entering gas increases the needed converter length. On the other hand, the increase of catalyst diameter does not affect to soot weight along converter and temperature profile, but results a less pressure drop. For 2.500 c diesel engine, packed bed catalytic converter with ellipse's cross sectional of 14,5X7,5 cm diagonal and 0,8 cm catalyst particle diameter, needs 4,1 cm length.

  6. Performance of new generation TWC catalytic systems working under different conditions in order to reduce the emission of a global warming gas: N{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Mac-Beath, I.; Castillo, S.; Camposeco, R.; Moran-Pineda, M. [Instituto Mexicano del Petroleo, Mexico, D.F. (Mexico). Programa de Ingenieria Molecular

    2010-07-01

    In this work, three-way catalytic systems (TWC-K, TWC-M and TWC-P) were prepared and tested experimentally in order to analyze N{sub 2}O emissions. Various types and quantities of precious metals (Pt-Pd-Rh), and different mixed oxides (CexBayLazMgwO{sub 2}-Al{sub 2}O{sub 3}) to prepare the supports were used. The catalytic tests were carried out by using common exhaust gases from a gasoline engine under different oxidizing conditions. The TWC catalytic compositions were based on catalytic converters used in retrofitting programs in the Metropolitan Area in Mexico City. Fresh and aged TWC catalytic samples were tested; in both conditions, the catalytic compositions were characterized by BET, TEM-EDS and XRD in order to analyze the efficiency of the catalytic behavior. Due to the fact that the 4{sup th} TWC generation (Pd-Only TWC) has Pd as main active metal, the tested TWC catalytic samples were synthesized by having Pd in a higher proportion with regard to Pt and Rh used as complements with some differences in support composition. (orig.)

  7. Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant.

    Science.gov (United States)

    Islamoglu, Timur; Ortuño, Manuel A; Proussaloglou, Emmanuel; Howarth, Ashlee J; Vermeulen, Nicolaas A; Atilgan, Ahmet; Asiri, Abdullah M; Cramer, Christopher J; Farha, Omar K

    2018-02-12

    Amino-functionalized zirconium-based metal-organic frameworks (MOFs) have shown unprecedented catalytic activity compared to non-functionalized analogues for hydrolysis of organophosphonate-based toxic chemicals. Importantly, the effect of the amino group on the catalytic activity is significantly higher in the case of UiO-66-NH 2 , where the amino groups reside near the node, compared to UiO-67-m-NH 2 , where they are directed away from the node. Herein, we show that the proximity of the amino group is crucial for fast catalytic activity towards hydrolysis of organophosphonate-based nerve agents. The generality of the observed amine-proximity-dictated catalytic activity has been tested on two different MOF systems which have different topology. DFT calculations reveal that amino groups on all the MOFs studied are not acting as Brønsted bases; instead they control the microsolvation environment at the Zr 6 -node active site and therefore increase the overall catalytic rates. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Catalytic surface promotion of highly active La0.85Sr0.15Cr0.8Ni0.2O3-δ anodes for La5.6WO11.4-δ based proton conducting fuel cells

    DEFF Research Database (Denmark)

    Solis, C.; Balaguer, M.; Bozza, Francesco

    2014-01-01

    to the widely used NiO. Under typical anode reducing conditions, Ni is segregated from the LSCN lattice on the grain surface as metallic Ni nanoparticles, which are proved to be compatible with LWO in reducing conditions. These Ni nanoparticles become the catalytic active sites for the H-2 oxidation reaction......, the R-p, values achieved for LSCN infiltrated with Ni, e.g. 0.47 Omega cm(2) at 700 degrees C, suggest the practical application of this kind of anodes in proton conducting solid oxide fuel cells (PC-SOFC). (C) 2013 Elsevier B.V. All rights reserved.......La0.85Sr0.15CrO3-delta (LSC), La0.85Sr0.15Cr0.8Ni0.2O3-delta (LSCN) and LSCN infiltrated with Ni nanoparticles were tested as anodes for symmetrical cells based on La5.6WO11.4-delta (LWO) protonic electrolyte. These chromite-based electrode materials are compatible with LWO material, in contrast...

  9. Facile synthesis and catalytic properties of silver colloidal ...

    Indian Academy of Sciences (India)

    Administrator

    obtained with high dispersion (2–3 nm), which has high catalytic activity on reduction of 4-nitrobenzoic acid to 4-aminobenzoic acid. Keywords. Silver colloidal nanoparticles; SDBS; catalytic reduction; 4-nitrobenzoic acid. 1. Introduction. Silver colloidal nanoparticles (AgCNPs) have been studied extensively in catalysis ...

  10. Green synthesis and catalytic application of curcumin stabilized ...

    Indian Academy of Sciences (India)

    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) ...

  11. Microscale Synthesis of Chiral Alcohols via Asymmetric Catalytic Transfer Hydrogenation

    Science.gov (United States)

    Peeters, Christine M.; Deliever, Rik; De Vos, Dirk

    2009-01-01

    Synthesis of pure enantiomers is a key issue in industry, especially in areas connected to life sciences. Catalytic asymmetric synthesis has emerged as a powerful and practical tool. Here we describe an experiment on racemic reduction and asymmetric reduction via a catalytic hydrogen transfer process. Acetophenone and substituted acetophenones are…

  12. Magnetic, catalytic, EPR and electrochemical studies on binuclear ...

    Indian Academy of Sciences (India)

    Unknown

    prepared. Spectral, catalytic, magnetic, EPR and electrochemical studies have been carried out. A catecholase activity study indicates that only HL1 complexes have efficient catalytic activity due to a less sterically hindered methyl group and enhanced planarity (larger –2J values) with respect to the oxidation of 3 ...

  13. 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...

  14. Platinum recovery from used auto catalytic converters in electrorefining process

    Directory of Open Access Journals (Sweden)

    A. Fornalczyk

    2013-04-01

    Full Text Available This paper presents possibility of removing platinum from the used catalytic converters applying copper as a metal collector in pyrometallurgical methods. The catalytic converter carrier was grinded and melted with copper. During the research obtained Cu-Pt alloy was casted as an anode. Such anode was electrically refined in order to recover platinum. Obtained results were discussed.

  15. Plant Protochlorophyllide Oxidoreductases A and B: CATALYTIC EFFICIENCY AND INITIAL REACTION STEPS.

    Science.gov (United States)

    Garrone, Alessio; Archipowa, Nataliya; Zipfel, Peter F; Hermann, Gudrun; Dietzek, Benjamin

    2015-11-20

    The enzyme protochlorophyllide oxidoreductase (POR, EC 1.3.1.33) has a key role in plant development. It catalyzes one of the later steps in chlorophyll synthesis, the light-induced reduction of protochlorophyllide (PChlide) into chlorophyllide (Chlide) in the presence of NADPH. Two isozymes of plant POR, POR A and POR B from barley, which differ in their function during plant life, are compared with respect to their substrate binding affinity, catalytic efficiency, and catalytic mechanism. POR B as compared with POR A shows an 5-fold higher binding affinity for PChlide and an about 6-fold higher catalytic efficiency measured as kcat/Km. Based on the reaction intermediates, which can be trapped at low temperatures the same reaction mechanism operates in both POR A and POR B. In contrast to results reported for POR enzymes from cyanobacteria, the initial light-driven step, which occurs at temperatures below 180 K already involves the full chemistry of the photoreduction and yields the reaction product, Chlide, in an enzyme-bound form. The subsequent dark reactions, which include cofactor (NADP(+)) release and cofactor (NADPH) rebinding, show different temperature dependences for POR A and POR B and suggest a higher conformational flexibility of POR B in the surrounding active center. Both the higher substrate binding affinity and well adapted enzyme dynamics are held responsible for the increased catalytic activity of POR B as compared with POR A. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  16. Simulation and calculation of three-reactor system of catalytic reforming

    International Nuclear Information System (INIS)

    Rikalovska, Tatjana; Markovska, Liljana; Meshko, Vera; Poposka, Filimena

    1999-01-01

    The process of catalytic reforming has been operated for quite a long time, one can not always find real data for the kinetics and thermodynamics of the reactions that take place during the catalytic reforming process in order to facilitate the designing of reactor system or its simulation in a wide:ran e of process parameters. Kinetic and thermodynamic data have been collected for the reactions that take place during the catalytic reforming process. The stress has been pointed on four major reactions: dehydrogenation of naphthenes (aromatization), dehydrocyclization of paraffins and hydrocracking of naphthenes and paraffins. On the base of such a kinetic model, the reforming process has been described with a system of differential equations. For the purpose of solving these equations computer programs for simulation of a three-reactor system for adiabatic operation of the reactors. The computer simulation of the mathematical model of this three-reactor system has been accomplished by use of the ISIM-dynamic simulator. The results obtained out of the simulation agree very good with the data of the real process of catalytic reforming in OKTA Crude Oil Refinery in Skopje, Macedonia. (Author)

  17. A highly sensitive technique for detecting catalytically active nanoparticles against a background of general workplace aerosols

    International Nuclear Information System (INIS)

    Neubauer, N; Weis, F; Seipenbusch, M; Kasper, G; Binder, A

    2011-01-01

    A new measurement technique was studied using catalysis to specifically detect airborne nanoparticles in presence of background particles in the workplace air. Catalytically active nanoparticles produced by spark discharge were used as aerosol catalysts. According to these particles suitable catalytic test reactions were chosen and investigated by two different approaches: catalysis on airborne nanoparticles and catalysis on deposited nanoparticles. The results indicate that catalysis is applicable for the specific measurement of nanoparticles in the workplace air. Catalysis on airborne particles is suitable for the specific detection of very active nanoparticles, e.g. platinum or nickel, at high concentrations of about 10 7 /cm 3 . The approach of catalysis on deposited particles is better suited for nanoparticle aerosols at low concentrations, for slow catalytic reactions or less active nanoparticles like iron oxide (Fe 2 O 3 ). On the basis of the experimental results detection limits in the range of μg or even ng were calculated which assure the good potential of catalysis for the specific detection of nanoparticles in the workplace air based on their catalytic activity.

  18. Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

    International Nuclear Information System (INIS)

    Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun

    2012-01-01

    The ruthenium(II) complex [Ru(bpy) 2 -(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus

  19. Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

    Energy Technology Data Exchange (ETDEWEB)

    Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun [Pusan National University, Busan (Korea, Republic of)

    2012-01-15

    The ruthenium(II) complex [Ru(bpy){sub 2}-(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus.

  20. Smoke emissions from a catalytic wood stove

    International Nuclear Information System (INIS)

    Cowburn, D.A.; Stephens, N.P.J.

    1994-01-01

    The work reported here was concerned with testing a catalytic wood burning stove (roomheater) following the most applicable UK procedures. The identical stove has also been tested in several other nations to their individual procedures. The results will be submitted to the International Energy Agency (IEA) such that appropriate comparisons can be made. The results comprised: burning rate; an indicative appliance efficiency; heat output; carbon dioxide emissions; carbon monoxide emissions; and smoke emissions. These results were determined with the appliance at three nominal burning rates (high, medium and low). Comparing the results with those obtained in other countries indicates good agreement except when the appliance was operated at low burning rates, under which conditions the UK results indicate significantly worse smoke emissions than those measured by other researchers. (author)

  1. Contact structure for use in catalytic distillation

    Science.gov (United States)

    Jones, Jr., Edward M.

    1984-01-01

    A method for conducting catalytic chemical reactions and fractionation of the reaction mixture comprising feeding reactants into a distillation column reactor contracting said reactant in liquid phase with a fixed bed catalyst in the form of a contact catalyst structure consisting of closed porous containers containing the catatlyst for the reaction and a clip means to hold and support said containers, which are disposed above, i.e., on the distillation trays in the tower. The trays have weir means to provide a liquid level on the trays to substantially cover the containers. In other words, the trays function in their ordinary manner with the addition thereto of the catalyst. The reaction mixture is concurrently fractionated in the column.

  2. Catalytic steam reforming of bio-oil

    DEFF Research Database (Denmark)

    Trane, R.; Dahl, S.; Skjøth-Rasmussen, M.S.

    2012-01-01

    Hydrogen and synthesis gas can be produced in an environmentally friendly and sustainable way through steam reforming (SR) of bio-oil and this review presents the state-of-the-art of SR of bio-oil and model compounds hereof. The possible reactions, which can occur in the SR process and the influe......Hydrogen and synthesis gas can be produced in an environmentally friendly and sustainable way through steam reforming (SR) of bio-oil and this review presents the state-of-the-art of SR of bio-oil and model compounds hereof. The possible reactions, which can occur in the SR process...... and the influence of operating conditions will be presented along with the catalysts and processes investigated in the literature.Several catalytic systems with Ni, Ru, or Rh can achieve good performance with respect to initial conversion and yield of hydrogen, but the main problem is that the catalysts...

  3. Radiant non-catalytic recuperative reformer

    Energy Technology Data Exchange (ETDEWEB)

    Khinkis, Mark J.; Kozlov, Aleksandr P.

    2017-10-31

    A radiant, non-catalytic recuperative reformer has a flue gas flow path for conducting hot exhaust 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 positioned adjacent to the flue gas flow path to permit heat transfer from the hot exhaust 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, a portion of the reforming mixture flow path is positioned outside of flue gas flow path for a relatively large residence time.

  4. Flame assisted synthesis of catalytic ceramic membranes

    DEFF Research Database (Denmark)

    Johansen, Johnny; Mosleh, Majid; Johannessen, Tue

    2004-01-01

    Membranes consisting of one or more metal oxides can be synthesized by flame pyrolysis. The general principle behind flame pyrolysis is the decomposition and oxidation of evaporated organo-metallic precursors in a flame, thereby forming metal oxide monomers. Because of the extreme supersaturation...... 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......, membranes with pore sizes below 5 nm have been produced by this continuous filtration of nano-particles. In this way, top-layers with Knudsen separation have been achieved by a reduction of the pore size of three orders of magnitude within an hour. It has previously been shown that it also is possible...

  5. Make the most of catalytic hydrogenations

    Energy Technology Data Exchange (ETDEWEB)

    Landert, J.P.; Scubla, T. [Biazzi S.A., Chailly-Montreux (Switzerland)

    1995-03-01

    Liquid-phase catalytic hydrogenation is one of the most useful and versatile reactions available for organic synthesis. Because it is environmentally clean, it has replaced other reduction processes, such as the Bechamp reaction, and zinc and sulfide reductions. Moreover, the economics are favorable, provided that raw materials free of catalyst poisons are used. The hydrogenation reaction is very selective with appropriate catalysts and can often be carried out without a solvent. Applications include reduction of unsaturated carbon compounds to saturated derivatives (for example, in vegetable-oil processing), carbonyl compounds to alcohols (such as sorbitol), and nitrocompounds to amines. the reactions are usually run in batch reactors to rapidly reach complete conversion and allow quick change-over of products. The paper describes the basics of hydrogenation; steering clear of process hazards; scale-up and optimization; and system design in practice.

  6. Computational Modeling of the Catalytic Cycle of Glutathione Peroxidase Nanomimic.

    Science.gov (United States)

    Kheirabadi, Ramesh; Izadyar, Mohammad

    2016-12-29

    To elucidate the role of a derivative of ebselen as a mimic of the antioxidant selenoenzyme glutathione peroxidase, density functional theory and solvent-assisted proton exchange (SAPE) were applied to model the reaction mechanism in a catalytic cycle. This mimic plays the role of glutathione peroxidase through a four-step catalytic cycle. The first step is described as the oxidation of 1 in the presence of hydrogen peroxide, while selenoxide is reduced by methanthiol at the second step. In the third step of the reaction, the reduction of selenenylsulfide occurs by methanthiol, and the selenenic acid is dehydrated at the final step. Based on the kinetic parameters, step 4 is the rate-determining step (RDS) of the reaction. The bond strength of the atoms involved in the RDS is discussed with the quantum theory of atoms in molecules (QTAIM). Low value of electron density, ρ(r), and positive Laplacian values are the evidence for the covalent nature of the hydrogen bonds rupture (O 30 -H 31 , O 33 -H 34 ). A change in the sign of the Laplacian, L(r), from the positive value in the reactant to a negative character at the transition state indicates the depletion of the charge density, confirming the N 5 -H 10 and O 11 -Se 1 bond breaking. The analysis of electron location function (ELF) and localized orbital locator (LOL) of the Se 1 -N 5 and Se 1 -O 11 bonds have been done by multi-WFN program. High values of ELF and LOL at the transition state regions between the Se, N, and O atoms display the bond formation. Finally, the main donor-acceptor interaction energies were analyzed using the natural bond orbital analysis for investigation of their stabilization effects on the critical bonds at the RDS.

  7. Catalytic transformation of methyl benzenes over zeolite catalysts

    KAUST Repository

    Al-Khattaf, S.

    2011-02-01

    Catalytic transformation of three methyl benzenes (toluene, m-xylene, and 1,2,4-trimethyl benzene) has been investigated over ZSM-5, TNU-9, mordenite and SSZ-33 catalysts in a novel riser simulator at different operating conditions. Catalytic experiments were carried out in the temperature range of 300-400 °C to understand the transformation of these alkyl benzenes over large pore (mordenite and SSZ-33) in contrast to medium-pore (ZSM-5 and TNU-9) zeolite-based catalysts. The effect of reaction conditions on the isomerization to disproportionation product ratio, distribution of trimethylbenzene (TMB) isomers, and p-xylene/o-xylene ratios are reported. The sequence of reactivity of the three alkyl benzenes depends upon the pore structure of zeolites. The zeolite structure controls primarily the diffusion of reactants and products while the acidity of these zeolites is of a secondary importance. In the case of medium pore zeolites, the order of conversion was m-xylene > 1,2,4-TMB > toluene. Over large pore zeolites the order of reactivity was 1,2,4-TMB > m-xylene > toluene for SSZ-33 catalyst, and m-xylene ∼ 1,2,4-TMB > toluene over mordenite. Significant effect of pore size between ZSM-5 and TNU-9 was observed; although TNU-9 is also 3D 10-ring channel system, its slightly larger pores compared with ZSM-5 provide sufficient reaction space to behave like large-pore zeolites in transformation of aromatic hydrocarbons. We have also carried out kinetic studies for these reactions and activation energies for all three reactants over all zeolite catalysts under study have been calculated. © 2011 Elsevier B.V.

  8. 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.)

  9. Catalytic Three-Component Machinery: Control of Catalytic Activity by Machine Speed.

    Science.gov (United States)

    Paul, Indrajit; Goswami, Abir; Mittal, Nikita; Schmittel, Michael

    2018-01-02

    Three supramolecular slider-on-deck systems DS1-DS3 were obtained as two-component aggregates from the sliders S1-S3 and deck D with its three zinc porphyrin (ZnPor) binding sites. The binding of the two-footed slider to the deck varies with the donor qualities of and the steric hindrance at the pyridine/pyrimidine (pyr) feet, and was effected by two N pyr →ZnPor interactions. Accordingly, the sliders move over the three zinc porphyrins in the deck at different speeds, namely with 32.2, 220, and 440 kHz at room temperature. The addition of N-methylpyrrolidine as an organocatalyst to DS1-DS3 generates catalytic three-component machineries. By using a conjugate addition as a probe reaction, we observed a correlation between the operating speed of the slider-on-deck systems and the yields of the catalytic reaction. As the thermodynamic binding of the slider decreases, both the frequency of the sliding motion and the yield of the catalytic reaction increase. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Synthesis, characterization and catalytic activity of nanosized Ni complexed aminoclay

    Science.gov (United States)

    Ranchani, A. Amala Jeya; Parthasarathy, V.; Devi, A. Anitha; Meenarathi, B.; Anbarasan, R.

    2017-11-01

    A novel Ni complexed aminoclay (AC) catalyst was prepared by complexation method followed by reduction reaction. Various analytical techniques such as FTIR spectroscopy, UV-visible spectroscopy, DSC, TGA, SEM, HRTEM, EDX, XPS and WCA measurement are used to characterize the synthesized material. The AC-Ni catalyst system exhibited improved thermal stability and fiber-like morphology. The XPS results declared the formation of Ni nanoparticles. Thus, synthesized catalyst was tested towards the Schiff base formation reaction between various bio-medical polymers and aniline under air atmosphere at 85 °C for 24 h. The catalytic activity of the catalyst was studied by varying the % weight loading of the AC-Ni system towards the Schiff base formation. The Schiff base formation was quantitatively calculated by the 1H-NMR spectroscopy. While increasing the % weight loading of the AC-Ni catalyst, the % yield of Schiff base was also increased. The k app and Ti values were determined for the reduction of indole and α-terpineol in the presence of AC-Ni catalyst system. The experimental results were compared with the literature report.

  11. Catalytic Deoxydehydration of Carbohydrates and Polyols to Chemicals and Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Nicholas, Kenneth M. [Univ. of Oklahoma, Norman, OK (United States)

    2016-01-15

    As the world's fossil fuel resources are being depleted and their costs increase, there is an urgent need to discover and develop new processes for the conversion of renewable, biomass resources into fuels and chemical feedstocks. Research and development in this area have been given high priority by both governmental agencies and industry. To increase the energy content and decrease the boiling points of biomass-derived carbohydrates and polyols to the useful liquid range it is necessary to chemically remove water (dehydrate) and, preferably, oxygen (deoxygenate/reduce). The poly-hydroxylic nature of carbohydrates is attractive for their use as functionalized chemical building blocks, but it presents a daunting challenge for their selective conversion to single product chemicals or fuels. The long term, practical objective of this project is to develop catalytic processes for the deoxydehydration (DODH) of biomass-derived carbohydrates and polyols to produce unsaturated alcohols and hydrocarbons of value as chemical feedstocks and fuels; DODH: polyol + reductant --(LMOx catalyst)--> unsaturate + oxidized reductant + H2O. Limited prior studies have established the viability of the DODH process with expensive phosphine reductants and rhenium-catalysts. Initial studies in the PI's laboratory have now demonstrated: 1) the moderately efficient conversion of glycols to olefins by the economical sulfite salts is catalyzed by MeReO3 and Z+ReO4-; 2) effective phosphine-based catalytic DODH of representative glycols to olefins by cheap LMoO2 complexes; and 3) computational studies (with K. Houk, UCLA) have identified several Mo-, W-, and V-oxo complexes that are likely to catalyze glycol DODH. Seeking practically useful DODH reactions of complex polyols and new understanding of the reactivity of polyoxo-metal species with biomass-oxygenates we will employ a two-pronged approach: 1) investigate experimentally the reactivity, both stoichiometric and catalytic, of

  12. Radiofrequency treatment enhances the catalytic function of an immobilized nanobiohybrid catalyst

    Science.gov (United States)

    San, Boi Hoa; Ha, Eun-Ju; Paik, Hyun-Jong; Kim, Kyeong Kyu

    2014-05-01

    Biocatalysis, the use of enzymes in chemical transformation, has undergone intensive development for a wide range of applications. As such, maximizing the functionality of enzymes for biocatalysis is a major priority to enable industrial use. To date, many innovative technologies have been developed to address the future demand of enzymes for these purposes, but maximizing the catalytic activity of enzymes remains a challenge. In this study, we demonstrated that the functionality of a nanobiocatalyst could be enhanced by combining immobilization and radiofrequency (RF) treatment. Aminopeptidase PepA-encapsulating 2 nm platinum nanoparticles (PepA-PtNPs) with the catalytic activities of hydrolysis and hydrogenation were employed as multifunctional nanobiocatalysts. Immobilizing the nanobiocatalysts in a hydrogel using metal chelation significantly enhanced their functionalities, including catalytic power, thermal-stability, pH tolerance, organic solvent tolerance, and reusability. Most importantly, RF treatment of the hydrogel-immobilized PepA-PtNPs increased their catalytic power by 2.5 fold greater than the immobilized PepA. Our findings indicate that the catalytic activities and functionalities of PepA-PtNPs are greatly enhanced by the combination of hydrogel-immobilization and RF treatment. Based on our findings, we propose that RF treatment of nanobiohybrid catalysts immobilized on the bulk hydrogel represents a new strategy for achieving efficient biocatalysis.Biocatalysis, the use of enzymes in chemical transformation, has undergone intensive development for a wide range of applications. As such, maximizing the functionality of enzymes for biocatalysis is a major priority to enable industrial use. To date, many innovative technologies have been developed to address the future demand of enzymes for these purposes, but maximizing the catalytic activity of enzymes remains a challenge. In this study, we demonstrated that the functionality of a nanobiocatalyst

  13. Synthesis, characterization and crystal structure determination of a new vanadium(IV) Schiff base complex (VOL.sub.2./sub.) and investigation of its catalytic activity in the epoxidation of cyclooctene

    Czech Academy of Sciences Publication Activity Database

    Grivani, G.; Tahmasebi, V.; Khalaji, A.D.; Fejfarová, Karla; Dušek, Michal

    2013-01-01

    Roč. 51, č. 1 (2013), s. 54-60 ISSN 0277-5387 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : vanadium (IV) * Schiff base * single crystal * structure determination * catalysis * epoxidation Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.047, year: 2013

  14. Experimental investigation on emission reduction in neem oil biodiesel using selective catalytic reduction and catalytic converter techniques.

    Science.gov (United States)

    Viswanathan, Karthickeyan

    2018-03-01

    In the present study, non-edible seed oil namely raw neem oil was converted into biodiesel using transesterification process. In the experimentation, two biodiesel blends were prepared namely B25 (25% neem oil methyl ester with 75% of diesel) and B50 (50% neem oil methyl ester with 50% diesel). Urea-based selective catalytic reduction (SCR) technique with catalytic converter (CC) was fixed in the exhaust tail pipe of the engine for the reduction of engine exhaust emissions. Initially, the engine was operated with diesel as a working fluid and followed by refilling of biodiesel blends B25 and B50 to obtain the baseline readings without SCR and CC. Then, the same procedure was repeated with SCR and CC technique for emission reduction measurement in diesel, B25 and B50 sample. The experimental results revealed that the B25 blend showed higher break thermal efficiency (BTE) and exhaust gas temperature (EGT) with lower break-specific fuel consumption (BSFC) than B50 blend at all loads. On comparing with biodiesel blends, diesel experiences increased BTE of 31.9% with reduced BSFC of 0.29 kg/kWh at full load. A notable emission reduction was noticed for all test fuels in SCR and CC setup. At full load, B25 showed lower carbon monoxide (CO) of 0.09% volume, hydrocarbon (HC) of 24 ppm, and smoke of 14 HSU and oxides of nitrogen (NOx) of 735 ppm than diesel and B50 in SCR and CC setup. On the whole, the engine with SCR and CC setup showed better performance and emission characteristics than standard engine operation.

  15. Modulation of catalytic activity in multi-domain protein tyrosine phosphatases.

    Directory of Open Access Journals (Sweden)

    Lalima L Madan

    Full Text Available Signaling mechanisms involving protein tyrosine phosphatases govern several cellular and developmental processes. These enzymes are regulated by several mechanisms which include variation in the catalytic turnover rate based on redox stimuli, subcellular localization or protein-protein interactions. In the case of Receptor Protein Tyrosine Phosphatases (RPTPs containing two PTP domains, phosphatase activity is localized in their membrane-proximal (D1 domains, while the membrane-distal (D2 domain is believed to play a modulatory role. Here we report our analysis of the influence of the D2 domain on the catalytic activity and substrate specificity of the D1 domain using two Drosophila melanogaster RPTPs as a model system. Biochemical studies reveal contrasting roles for the D2 domain of Drosophila Leukocyte antigen Related (DLAR and Protein Tyrosine Phosphatase on Drosophila chromosome band 99A (PTP99A. While D2 lowers the catalytic activity of the D1 domain in DLAR, the D2 domain of PTP99A leads to an increase in the catalytic activity of its D1 domain. Substrate specificity, on the other hand, is cumulative, whereby the individual specificities of the D1 and D2 domains contribute to the substrate specificity of these two-domain enzymes. Molecular dynamics simulations on structural models of DLAR and PTP99A reveal a conformational rationale for the experimental observations. These studies reveal that concerted structural changes mediate inter-domain communication resulting in either inhibitory or activating effects of the membrane distal PTP domain on the catalytic activity of the membrane proximal PTP domain.

  16. Probing the Catalytic Mechanism of Vibrio harveyi GH20 β-N-Acetylglucosaminidase by Chemical Rescue.

    Directory of Open Access Journals (Sweden)

    Piyanat Meekrathok

    Full Text Available Vibrio harveyi GH20 β-N-acetylglucosaminidase (VhGlcNAcase is a chitinolytic enzyme responsible for the successive degradation of chitin fragments to GlcNAc monomers, activating the onset of the chitin catabolic cascade in marine Vibrios.Two invariant acidic pairs (Asp303-Asp304 and Asp437-Glu438 of VhGlcNAcase were mutated using a site-directed mutagenesis strategy. The effects of these mutations were examined and the catalytic roles of these active-site residues were elucidated using a chemical rescue approach. Enhancement of the enzymic activity of the VhGlcNAcase mutants was evaluated by a colorimetric assay using pNP-GlcNAc as substrate.Substitution of Asp303, Asp304, Asp437 or Glu438 with Ala/Asn/Gln produced a dramatic loss of the GlcNAcase activity. However, the activity of the inactive D437A mutant was recovered in the presence of sodium formate. Our kinetic data suggest that formate ion plays a nucleophilic role by mimicking the β-COO-side chain of Asp437, thereby stabilizing the reaction intermediate during both the glycosylation and the deglycosylation steps.Chemical rescue of the inactive D437A mutant of VhGlcNAcase by an added nucleophile helped to identify Asp437 as the catalytic nucleophile/base, and hence its acidic partner Glu438 as the catalytic proton donor/acceptor.Identification of the catalytic nucleophile of VhGlcNAcases supports the proposal of a substrate-assisted mechanism of GH20 GlcNAcases, requiring the catalytic pair Asp437-Glu438 for catalysis. The results suggest the mechanistic basis of the participation of β-N-acetylglucosaminidase in the chitin catabolic pathway of marine Vibrios.

  17. X-ray, neutron and NMR studies of the catalytic mechanism of aspartic proteinases.

    Science.gov (United States)

    Coates, Leighton; Erskine, Peter T; Mall, Sanjay; Gill, Raj; Wood, Steve P; Myles, Dean A A; Cooper, Jonathan B

    2006-09-01

    Current proposals for the catalytic mechanism of aspartic proteinases are largely based on X-ray structures of bound oligopeptide inhibitors possessing non-hydrolysable analogues of the scissile peptide bond. Until recent years, the positions of protons on the catalytic aspartates and the ligand in these complexes had not been determined with certainty due to the inadequate resolution of these analyses. There has been much interest in locating the catalytic protons at the active site of aspartic proteinases since this has major implications for detailed understanding of the mechanism of action and the design of improved transition state mimics for therapeutic applications. In this review we discuss the results of studies which have shed light on the locations of protons at the catalytic centre. The first direct determination of the proton positions stemmed from neutron diffraction data collected from crystals of the fungal aspartic proteinase endothiapepsin bound to a transition state analogue (H261). The neutron structure of the complex at a resolution of 2.1 A provided evidence that Asp 215 is protonated and that Asp 32 is the negatively charged residue in the transition state complex. Atomic resolution X-ray studies of inhibitor complexes have corroborated this finding. A similar study of the native enzyme established that it, unexpectedly, has a dipeptide bound at the catalytic site which is consistent with classical reports of inhibition by short peptides and the ability of pepsins to catalyse transpeptidation reactions. Studies by NMR have confirmed the findings of low-barrier and single-well hydrogen bonds in the complexes with transition state analogues.

  18. On the study of catalytic membrane reactor for water detritiation: Modeling approach

    Energy Technology Data Exchange (ETDEWEB)

    Liger, Karine, E-mail: karine.liger@cea.fr [CEA, DEN, DTN/SMTA/LIPC Cadarache, Saint Paul-lez-Durance F-13108 (France); Mascarade, Jérémy [CEA, DEN, DTN/SMTA/LIPC Cadarache, Saint Paul-lez-Durance F-13108 (France); Joulia, Xavier; Meyer, Xuan-Mi [Université de Toulouse, INPT, UPS, Laboratoire de Génie Chimique, 4, Allée Emile Monso, Toulouse F-31030 (France); CNRS, Laboratoire de Génie Chimique, Toulouse F-31030 (France); Troulay, Michèle; Perrais, Christophe [CEA, DEN, DTN/SMTA/LIPC Cadarache, Saint Paul-lez-Durance F-13108 (France)

    2016-11-01

    Highlights: • Experimental results for the conversion of tritiated water (using deuterium as a simulant of tritium) by means of a catalytic membrane reactor in view of tritium recovery. • Phenomenological 2D model to represent catalytic membrane reactor behavior including the determination of the compositions of gaseous effluents. • Good agreement between the simulation results and experimental measurements performed on the dedicated facility. • Explanation of the unexpected behavior of the catalytic membrane reactor by the modeling results and in particular the gas composition estimation. - Abstract: In the framework of tritium recovery from tritiated water, efficiency of packed bed membrane reactors have been successfully demonstrated. Thanks to protium isotope swamping, tritium bonded water can be recovered under the valuable Q{sub 2} form (Q = H, D or T) by means of isotope exchange reactions occurring on catalyst surface. The use of permselective Pd-based membrane allows withdrawal of reactions products all along the reactor, and thus limits reverse reaction rate to the benefit of the direct one (shift effect). The reactions kinetics, which are still little known or unknown, are generally assumed to be largely greater than the permeation ones so that thermodynamic equilibriums of isotope exchange reactions are generally assumed. This paper proposes a new phenomenological 2D model to represent catalytic membrane reactor behavior with the determination of gas effluents compositions. A good agreement was obtained between the simulation results and experimental measurements performed on a dedicated facility. Furthermore, the gas composition estimation permits to interpret unexpected behavior of the catalytic membrane reactor. In the next future, further sensitivity analysis will be performed to determine the limits of the model and a kinetics study will be conducted to assess the thermodynamic equilibrium of reactions.

  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. Enhanced catalytic activity over MIL-100(Fe) loaded ceria catalysts for the selective catalytic reduction of NOx with NH3 at low temperature

    International Nuclear Information System (INIS)

    Wang, Peng; Sun, Hong; Quan, Xie; Chen, Shuo

    2016-01-01

    Highlights: • Nano-ceria was successfully encapsulated into MIL-100(Fe) for the SCR of NO x . • The incorporated ceria in MIL-100(Fe) showed high content of chemisorbed oxygen. • The added ceria into MIL-100(Fe) improved the formation of adsorbed NO 2 species. • The addition of ceria into MIL-100(Fe) enhanced SCR activity at low temperature. - Abstract: The development of catalysts for selective catalytic reduction (SCR) reactions that are highly active at low temperatures and show good resistance to SO 2 and H 2 O is still a challenge. In this study, we have designed and developed a high-performance SCR catalyst based on nano-sized ceria encapsulated inside the pores of MIL-100(Fe) that combines excellent catalytic power with a metal organic framework architecture synthesized by the impregnation method (IM). Transmission electron microscopy (TEM) revealed the encapsulation of ceria in the cavities of MIL-100(Fe). The prepared IM-CeO 2 /MIL-100(Fe) catalyst shows improved catalytic activity both at low temperatures and throughout a wide temperature window. The temperature window for 90% NO x conversion ranges from 196 to 300 °C. X-ray photoelectron spectroscopy (XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) analysis indicated that the nano-sized ceria encapsulated inside MIL-100(Fe) promotes the production of chemisorbed oxygen on the catalyst surface, which greatly enhances the formation of the NO 2 species responsible for fast SCR reactions.

  1. Structures of the human poly (ADP-ribose glycohydrolase catalytic domain confirm catalytic mechanism and explain inhibition by ADP-HPD derivatives.

    Directory of Open Access Journals (Sweden)

    Julie A Tucker

    Full Text Available Poly(ADP-ribose glycohydrolase (PARG is the only enzyme known to catalyse hydrolysis of the O-glycosidic linkages of ADP-ribose polymers, thereby reversing the effects of poly(ADP-ribose polymerases. PARG deficiency leads to cell death whilst PARG depletion causes sensitisation to certain DNA damaging agents, implicating PARG as a potential therapeutic target in several disease areas. Efforts to develop small molecule inhibitors of PARG activity have until recently been hampered by a lack of structural information on PARG. We have used a combination of bio-informatic and experimental approaches to engineer a crystallisable, catalytically active fragment of human PARG (hPARG. Here, we present high-resolution structures of the catalytic domain of hPARG in unliganded form and in complex with three inhibitors: ADP-ribose (ADPR, adenosine 5'-diphosphate (hydroxymethylpyrrolidinediol (ADP-HPD and 8-n-octyl-amino-ADP-HPD. Our structures confirm conservation of overall fold amongst mammalian PARG glycohydrolase domains, whilst revealing additional flexible regions in the catalytic site. These new structures rationalise a body of published mutational data and the reported structure-activity relationship for ADP-HPD based PARG inhibitors. In addition, we have developed and used biochemical, isothermal titration calorimetry and surface plasmon resonance assays to characterise the binding of inhibitors to our PARG protein, thus providing a starting point for the design of new inhibitors.

  2. Long-time experience in catalytic flue gas cleaning and catalytic NO{sub x} reduction in biofueled boilers

    Energy Technology Data Exchange (ETDEWEB)

    Ahonen, M. [Tampella Power Inc., Tampere (Finland)

    1996-12-31

    NO emissions are reduced by primary or secondary methods. Primary methods are based on NO reduction in the combustion zone and secondary methods on flue gas cleaning. The most effective NO reduction method is selective catalytic reduction (SCR). It is based on NO reduction by ammonia on the surface of a catalyst. Reaction products are water and nitrogen. A titanium-dioxide-based catalyst is very durable and selective in coal-fired power plants. It is not poisoned by sulphur dioxide and side reactions with ammonia and sulphur dioxide hardly occur. The long time experience and suitability of a titanium-dioxide-based catalyst for NO reduction in biofuel-fired power plants was studied. The biofuels were: peat, wood and bark. It was noticed that deactivation varied very much due to the type of fuel and content of alkalinities in fuel ash. The deactivation in peat firing was moderate, close to the deactivation noticed in coal firing. Wood firing generally had a greater deactivation effect than peat firing. Fuel and fly ash were analyzed to get more information on the flue gas properties. The accumulation of alkali and alkaline earth metals and sulphates was examined together with changes in the physical composition of the catalysts. In the cases where the deactivation was the greatest, the amount of alkali and alkaline earth metals in fuels and fly ashes and their accumulation were very significant. (author) (3 refs.)

  3. IVIg treatment reduces catalytic antibody titers of renal transplanted patients.

    Directory of Open Access Journals (Sweden)

    Ankit Mahendra

    Full Text Available Catalytic antibodies are immunoglobulins endowed with enzymatic activity. Catalytic IgG has been reported in several human autoimmune and inflammatory diseases. In particular, low levels of catalytic IgG have been proposed as a prognostic marker for chronic allograft rejection in patients undergoing kidney transplant. Kidney allograft is a treatment of choice for patients with end-stage renal failure. Intravenous immunoglobulins, a therapeutic pool of human IgG, is used in patients with donor-specific antibodies, alone or in conjunction with other immunosuppressive treatments, to desensitize the patients and prevent the development of acute graft rejection. Here, we followed for a period of 24 months the levels of catalytic IgG towards the synthetic peptide Pro-Phe-Arg-methylcoumarinimide in a large cohort of patients undergoing kidney transplantation. Twenty-four percent of the patients received IVIg at the time of transplantation. Our results demonstrate a marked reduction in levels of catalytic antibodies in all patients three months following kidney transplant. The decrease was significantly pronounced in patients receiving adjunct IVIg therapy. The results suggests that prevention of acute graft rejection using intravenous immunoglobulins induces a transient reduction in the levels of catalytic IgG, thus potentially jeopardizing the use of levels of catalytic antibodies as a prognosis marker for chronic allograft nephropathy.

  4. IVIg Treatment Reduces Catalytic Antibody Titers of Renal Transplanted Patients

    Science.gov (United States)

    Mahendra, Ankit; Peyron, Ivan; Dollinger, Cécile; Gilardin, Laurent; Sharma, Meenu; Wootla, Bharath; Padiolleau-Lefevre, Séverine; Friboulet, Alain; Boquet, Didier; Legendre, Christophe; Kaveri, Srinivas V.

    2013-01-01

    Catalytic antibodies are immunoglobulins endowed with enzymatic activity. Catalytic IgG has been reported in several human autoimmune and inflammatory diseases. In particular, low levels of catalytic IgG have been proposed as a prognostic marker for chronic allograft rejection in patients undergoing kidney transplant. Kidney allograft is a treatment of choice for patients with end-stage renal failure. Intravenous immunoglobulins, a therapeutic pool of human IgG, is used in patients with donor-specific antibodies, alone or in conjunction with other immunosuppressive treatments, to desensitize the patients and prevent the development of acute graft rejection. Here, we followed for a period of 24 months the levels of catalytic IgG towards the synthetic peptide Pro-Phe-Arg-methylcoumarinimide in a large cohort of patients undergoing kidney transplantation. Twenty-four percent of the patients received IVIg at the time of transplantation. Our results demonstrate a marked reduction in levels of catalytic antibodies in all patients three months following kidney transplant. The decrease was significantly pronounced in patients receiving adjunct IVIg therapy. The results suggests that prevention of acute graft rejection using intravenous immunoglobulins induces a transient reduction in the levels of catalytic IgG, thus potentially jeopardizing the use of levels of catalytic antibodies as a prognosis marker for chronic allograft nephropathy. PMID:23967092

  5. 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.

  6. Catalytic oxidation of NO to NO2 on activated carbon

    International Nuclear Information System (INIS)

    Zhancheng Guo; Yusheng Xie

    2001-01-01

    Catalytic oxidation of NO to NO 2 over activated carbons PAN-ACF, pitch-ACF and coconut-AC at room temperature (30 o C) were studied to develop a method based on oxidative removal of NO from flue gases. For a dry gas, under the conditions of a gas space flow rate 1500 h -1 in the presence of oxygen of 2-20% in volume concentration, the activated coconut carbon with a surface area 1200 m 2 /g converted about 81-94% of NO with increasing oxygen concentration, the pitch based activated carbon fiber with a surface area 1000 m 2 /g about 44-75%, and the polyacrylonitrile-based activated carbon fiber with a surface area 1810 m 2 /g about 25-68%. The order of activity of the activated carbons was PAN-ACF c P NO P O2 β (F/W), where β is 0.042, 0.16, 0.31 for the coconut-AC, the pitch-ACF and the PAN-ACF respectively, and k c is 0.94 at 30 o C. (author)

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

    Directory of Open Access Journals (Sweden)

    Maciel Adeilton

    2008-01-01

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

  8. Catalytic transformation of carbon dioxide and methane into syngas over ruthenium and platinum supported hydroxyapatites

    Science.gov (United States)

    Rêgo De Vasconcelos, Bruna; Zhao, Lulu; Sharrock, Patrick; Nzihou, Ange; Pham Minh, Doan

    2016-12-01

    This work focused on the catalytic transformation of methane (CH4) and carbon dioxide (CO2) into syngas (mixture of CO and H2). Ruthenium- and platinum-based catalysts were prepared using hydroxyapatite (HAP) as catalyst support. Different methods for metal deposition were used including incipient wetness impregnation (IWI), excess liquid phase impregnation (LIM), and cationic exchange (CEX). Metal particle size varied in large range from less than 1 nm to dozens nm. All catalysts were active at 400-700 °C but only Pt catalyst prepared by IWI method (Pt/HAP IWI) was found stable. The catalytic performance of Pt/HAP IWI could be comparable with the literature data on noble metal-based catalysts, prepared on metal oxide supports. For the first time, water was experimentally quantified as a by-product of the reaction. This helped to correctly buckle the mass balance of the process.

  9. Hydrocarbon conversion with an attenuated superactive multimetallic catalytic composite

    International Nuclear Information System (INIS)

    Antos, G.J.

    1981-01-01

    Hydrocarbons are converted by contacting them at hydrocarbon conversion conditions with a novel attenuated superactive multimetallic catalytic composite comprising a combination of a catalytically effective amount of a pyrolyzed rhenium carbonyl component with a porous carrier material containing a uniform dispersion of catalytically effective amounts of a platinum group component, which is maintained in the elemental metallic state during the incorporation and pyrolysis of the rhenium carbonyl component, and of an iron component. In a highly preferred embodiment, this novel catalytic composite also contains a catalytically effective amount of a halogen component. The platinum group component, pyrolyzed rhenium carbonyl component, iron component and optional halogen component are preferably present in the multimetallic catalytic composite in amounts, calculated on an elemental basis, corresponding to about 0.01 to about 2 wt. % platinum group metal, about 0.01 to about 5 wt. % rhenium, about 0.005 to about 4 wt. % iron and about 0.1 to about 5 wt. % halogen. A key feature associated with the preparation of the subject catalytic composite is reaction of a rhenium carbonyl complex with a porous carrier material containing a uniform dispersion of an iron component and of a platinum group component maintained in the elemental state, whereby the interaction of the rhenium moiety with the platinum group moiety is maximized due to the platinophilic (i.e., platinum-seeking) propensities of the carbon monoxide ligands associated with the rhenium reagent. A specific example of the type of hydrocarbon conversion process disclosed herein is a process for the catalytic reforming of a low octane gasoline fraction wherein the gasoline fraction and a hydrogen stream are contacted with the attenuated superactive multimetallic catalytic composite at reforming conditions

  10. Cationic metallocene polymerization catalysts based on tetrakis(pentafluorophenyl)borate and its derivatives. Probing the limits of anion `noncoordination` via a synthetic, solution dynamic, structural, and catalytic olefin polymerization study

    Energy Technology Data Exchange (ETDEWEB)

    Jia, L.; Yang, X.; Stern, C.L.; Marks, T.J. [Northwestern Univ., Evanston, IL (United States)

    1997-03-04

    The silyl-functionalized/protected derivatives of the tetrakis(perfluoroaryl)borate anions, B(C{sub 6}F{sub 4}TBS){sub 4}{sup -} and B(C{sub 6}F{sub 4}TIPS){sub 4}{sup -} (TBS = tert-butyldimethylsilyl and TIPS = triisopropylsilyl) have been synthesized, and a series of stable, highly reactive Zr and Th ion-paired methyl and hydride catalysts have been isolated using these anions. In contrast, the analogous B(C{sub 6}F{sub 5}){sub 4}{sup -}-based zirconocene methyl complexes are not stable at room temperature; however, B(C{sub 6}F{sub 5}){sub 4}{sup -}-based zirconocene hydride complexes can be isolated. The relative coordinative ability of the series of fluoroarylborates with respect to metallocene cations has been evaluated on the basis of spectroscopic and reactivity data. The polymerization activity of the zirconocene catalysts reaches a maximum when B(C{sub 6}F{sub 4}TBS){sub 4}{sup -} and B(C{sub 6}F{sub 4}TIPS){sub 4}{sup -} are counteranions, and the polymerization activity of the Zr constrained geometry catalyst reaches a maximum in aromatic solvents due to arene coordination when B(C{sub 6}F{sub 5}){sub 4}{sup -} is the counteranion. 37 refs., 5 figs., 7 tabs.

  11. Improvements in or relating to catalysts and catalytic burners

    International Nuclear Information System (INIS)

    Cairns, J.A.

    1977-01-01

    A catalyst is described that consists of a fibrous kaolin substrate which supports a sputtered coating of catalytic material in the form of a monatomic layer or atomic dispersion and hence in a highly active form. The kaolin comprises 43 to 47% Al 2 O 3 and 50 to 54% SiO 2 , with traces of Fe 2 O 3 and TiO 2 , and the catalytic material is a Pt group metal or alloy. The method of preparation of such a catalyst is described. An application is for the catalytic oxidation of hydrocarbons. See also BP 1 455248. (U.K.)

  12. Surface composition of carburized tungsten trioxide and its catalytic activity

    International Nuclear Information System (INIS)

    Nakazawa, M.; Okamoto, H.

    1985-01-01

    The surface composition and electronic structure of carburized tungsten trioxide are investigated using x-ray photoelectron spectroscopy (XPS). The relationship between the surface composition and the catalytic activity for methanol electro-oxidation is clarified. The tungsten carbide concentration in the surface layer increases with the carburization time. The formation of tungsten carbide enhances the catalytic activity. On the other hand, the presence of free carbon or tungsten trioxide in the surface layer reduces the activity remarkably. It is also shown that, the higher the electronic density of states near the Fermi level, the higher the catalytic activity

  13. Catalytic Metallodrugs: Substrate-Selective Metal Catalysts as Therapeutics.

    Science.gov (United States)

    Yu, Zhen; Cowan, James A

    2017-10-12

    Metal complexes that catalyze inactivation and degradation of biomolecular targets can be developed into novel therapeutics (catalytic metallodrugs) against a variety of diseases. Despite recent advances in the field, a lack of substrate selectivity is a major hindrance to the development of catalytic metallodrugs for application in clinical practice. Improved targeting can minimize nonselective activity and the potential for side effects. Herein, we focus on recent developments toward novel metal catalysts that exhibit substrate selectivity against a variety of therapeutically relevant biomolecules. Design strategies for developing selective catalytic metallodrugs are also highlighted. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. IDENTIFICATION OF CATALYTIC METAL ION LIGANDS IN RIBOZYMES

    Science.gov (United States)

    Frederiksen, John K.; Piccirilli, Joseph A.

    2012-01-01

    Site-bound metal ions participate in the catalytic mechanisms of many ribozymes. Understanding these mechanisms therefore requires knowledge of the specific ligands on both substrate and ribozyme that coordinate these catalytic metal ions. A number of different structural and biochemical strategies have been developed and refined for identifying metal ion binding sites within ribozymes, and for assessing the catalytic contributions of the metal ions bound at those sites. We review these approaches and provide examples of their application, focusing in particular on metal ion rescue experiments and their roles in the construction of the transition state models for the Tetrahymena group I and RNase P ribozymes. PMID:19651216

  15. 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.)

  16. Combined hydrothermal liquefaction and catalytic hydrothermal gasification system and process for conversion of biomass feedstocks

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, Douglas C.; Neuenschwander, Gary G.; Hart, Todd R.

    2017-09-12

    A combined hydrothermal liquefaction (HTL) and catalytic hydrothermal gasification (CHG) system and process are described that convert various biomass-containing sources into separable bio-oils and aqueous effluents that contain residual organics. Bio-oils may be converted to useful bio-based fuels and other chemical feedstocks. Residual organics in HTL aqueous effluents may be gasified and converted into medium-BTU product gases and directly used for process heating or to provide energy.

  17. Catalytic spectrophotometric determination of trace amounts of copper (II) with isonicotonic acid hydrazide

    International Nuclear Information System (INIS)

    Latif, K.; Hanif, M.; Qureshi, E.A.; Ajmal, A.I.

    1992-01-01

    A very sensitive catalytic spectrophotometric method for the determination of copper (II) in concentration as low as 0.01 ng/ml has been described. This method is based on the oxidation of iso nicotinic acid hydrazide by hydrogen peroxide in ammoniacal medium, catalysed by copper (II). various metal interferences have been studied and are reported in this study. Structure of the oxidation product is not known. (author)

  18. Catalytic enantioselective N-nitroso aldol reaction of γ,δ-unsaturated δ-lactones.

    Science.gov (United States)

    Yanagisawa, Akira; Fujinami, Takeo; Oyokawa, Yu; Sugita, Takuya; Yoshida, Kazuhiro

    2012-05-18

    A catalytic asymmetric N-nitroso aldol reaction of γ,δ-didehydro-δ-lactones with nitrosoarenes was achieved using chiral tin dibromide as the chiral precatalyst and sodium ethoxide as the base precatalyst in the presence of ethanol. Optically active α-hydroxyamino ketones with up to 99% ee were regioselectively obtained in moderate to high yields from various δ-aryl-substituted γ,δ-didehydro-δ-valerolactones and o-substituted nitrosoarenes.

  19. Catalytic Asymmetric Nitro-Mannich Reactions with a Yb/K Heterobimetallic Catalyst

    Directory of Open Access Journals (Sweden)

    Tatsuya Nitabaru

    2010-03-01

    Full Text Available A catalytic asymmetric nitro-Mannich (aza-Henry reaction with rare earth metal/alkali metal heterobimetallic catalysts is described. A Yb/K heterobimetallic catalyst assembled by an amide-based ligand promoted the asymmetric nitro-Mannich reaction to afford enantioenriched anti-b-nitroamines in up to 86% ee. Facile reduction of the nitro functionality allowed for efficient access to optically active 1,2-diamines.

  20. Catalytic extraction processing of contaminated scrap metal

    International Nuclear Information System (INIS)

    Griffin, T.P.; Johnston, J.E.

    1994-01-01

    The contract was conceived to establish the commercial capability of Catalytic Extraction Processing (CEP) to treat contaminated scrap metal in the DOE inventory. In so doing, Molten Metal Technology, Inc. (MMT), pursued the following objectives: demonstration of the recycling of ferrous and non-ferrous metals--to establish that radioactively contaminated scrap metal can be converted to high-grade, ferrous and non-ferrous alloys which can be reused by DOE or reintroduced into commerce; immobilize radionuclides--that CEP will concentrate the radionuclides in a dense vitreous phase, minimize secondary waste generation and stabilize and reduce waste volume; destroy hazardous organics--that CEP will convert hazardous organics to valuable industrial gases, which can be used as feed gases for chemical synthesis or as an energy source; recovery volatile heavy metals--that CEP's off-gas treatment system will capture volatile heavy metals, such as mercury and lead; and establish that CEP is economical for processing contaminated scrap metal in the DOE inventory--that CEP is a more cost-effective and, complete treatment and recycling technology than competing technologies for processing contaminated scrap. The process and its performance are described

  1. Plasma-catalytic decomposition of TCE

    Energy Technology Data Exchange (ETDEWEB)

    Vandenbroucke, A.; Morent, R.; De Geyter, N.; Leys, C. [Ghent Univ., Ghent (Belgium). Dept. of Applied Physics; Tuan, N.D.M.; Giraudon, J.M.; Lamonier, J.F. [Univ. des Sciences et Technologies de Lille, Villeneuve (France). Dept. de Catalyse et Chimie du Solide

    2010-07-01

    Volatile organic compounds (VOCs) are gaseous pollutants that pose an environmental hazard due to their high volatility and their possible toxicity. Conventional technologies to reduce the emission of VOCs have their advantages, but they become cost-inefficient when low concentrations have to be treated. In the past 2 decades, non-thermal plasma technology has received growing attention as an alternative and promising remediation method. Non-thermal plasmas are effective because they produce a series of strong oxidizers such as ozone, oxygen radicals and hydroxyl radicals that provide a reactive chemical environment in which VOCs are completely oxidized. This study investigated whether the combination of NTP and catalysis could improve the energy efficiency and the selectivity towards carbon dioxide (CO{sub 2}). Trichloroethylene (TCE) was decomposed by non-thermal plasma generated in a DC-excited atmospheric pressure glow discharge. The production of by-products was qualitatively investigated through FT-IR spectrometry. The results were compared with those from a catalytic reactor. The removal rate of TCE reached a maximum of 78 percent at the highest input energy. The by-products of TCE decomposition were CO{sub 2}, carbon monoxide (CO) hydrochloric acid (HCl) and dichloroacetylchloride. Combining the plasma system with a catalyst located in an oven downstream resulted in a maximum removal of 80 percent, at an energy density of 300 J/L, a catalyst temperature of 373 K and a total air flow rate of 2 slm. 14 refs., 6 figs.

  2. Catalytic Reactor For Oxidizing Mercury Vapor

    Science.gov (United States)

    Helfritch, Dennis J.

    1998-07-28

    A catalytic reactor (10) for oxidizing elemental mercury contained in flue gas is provided. The catalyst reactor (10) comprises within a flue gas conduit a perforated corona discharge plate (30a, b) having a plurality of through openings (33) and a plurality of projecting corona discharge electrodes (31); a perforated electrode plate (40a, b, c) having a plurality of through openings (43) axially aligned with the through openings (33) of the perforated corona discharge plate (30a, b) displaced from and opposing the tips of the corona discharge electrodes (31); and a catalyst member (60a, b, c, d) overlaying that face of the perforated electrode plate (40a, b, c) opposing the tips of the corona discharge electrodes (31). A uniformly distributed corona discharge plasma (1000) is intermittently generated between the plurality of corona discharge electrode tips (31) and the catalyst member (60a, b, c, d) when a stream of flue gas is passed through the conduit. During those periods when corona discharge (1000) is not being generated, the catalyst molecules of the catalyst member (60a, b, c, d) adsorb mercury vapor contained in the passing flue gas. During those periods when corona discharge (1000) is being generated, ions and active radicals contained in the generated corona discharge plasma (1000) desorb the mercury from the catalyst molecules of the catalyst member (60a, b, c, d), oxidizing the mercury in virtually simultaneous manner. The desorption process regenerates and activates the catalyst member molecules.

  3. Catalytic Polymerization of Acrylonitrile by Khulays Bentonite

    Directory of Open Access Journals (Sweden)

    Matar M. Al-Esaimi

    2007-04-01

    Full Text Available The aqueous polymerization of acrylonitrile (AN catalyzed with exchanged Khulays bentonite . The influence of various polymerization parameters ( e.g., concentrations of Potassium Persulfate (K2S2O8 and monomer , various of organic solvents, and different temperature has been investigated. It was found that the rate of polymerization of AN was found to be dependent on monomer concentration, initiator and temperature. The activation energy of polymerization was calculated .Thermal properties of the polymer were studied by TGA and DSC techniques. © 2007 CREC UNDIP. All rights reserved.Received: 5 February 2007; Received in revised: 19 April 2007; Accepted: 7 May 2007[How to Cite: M. M. Al-Esaimi. (2007. Catalytic Polymerization of Acrylonitrile by Khulays Bentonite. Bulletin of Chemical Reaction Engineering and Catalysis, 2 (2-3: 32-36.  doi:10.9767/bcrec.2.1.4.6-10][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.2.1.4.6-10 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/4] 

  4. Catalytic glycerol steam reforming for hydrogen production

    International Nuclear Information System (INIS)

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

    2015-01-01

    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 H 2 . In this work we present the results obtained in the process of steam reforming of glycerol on Ni/Al 2 O 3 . The catalyst was prepared by wet impregnation method and characterized through different methods: N 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 2 , CH 4 , CO, CO 2 . The optimum reaction conditions as resulted from this study are: temperature 550°C, Gly:H 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%

  5. Process for catalytic flue gas denoxing

    International Nuclear Information System (INIS)

    Woldhuis, A.; Goudriaan, F.; Groeneveld, M.; Samson, R.

    1991-01-01

    With the increasing concern for the environment, stringency of legislation and industry's awareness of its own environmental responsibility, the demand for the reduction of emission levels of nitrogen oxides is becoming increasingly urgent. This paper reports that Shell has developed a low temperature catalytic deNOx system for deep removal of nitrogen oxides, which includes a low-pressure-drop reactor. This process is able to achieve over 90% removal of nitrogen oxides and therefore can be expected to meet legislation requirements for the coming years. The development of a low-temperature catalyst makes it possible to operate at temperatures as low as 120 degrees C, compared to 300-400 degrees C for the conventional honeycomb and plate-type catalysts. This allows an add-on construction, which is most often a more economical solution than the retrofits in the hot section required with conventional deNOx catalysts. The Lateral Flow Reactor (LFR), which is used for dust-free flue gas applications, and the Parallel Passage Reactor (PPR) for dust-containing flue gas applications, have been developed to work with pressure drops below 10 mbar

  6. Substrate-Directed Catalytic Selective Chemical Reactions.

    Science.gov (United States)

    Sawano, Takahiro; Yamamoto, Hisashi

    2018-03-06

    The development of highly efficient reactions at only the desired position is one of the most important subjects in organic chemistry. Most of the reactions in current organic chemistry are reagent- or catalyst-controlled reactions, and the regio- and stereoselectivity of the reactions are determined by the inherent nature of the reagent or catalyst. In sharp contrast, substrate-directed reaction determines the selectivity of the reactions by the functional group on the substrate and can strictly distinguish sterically and electronically similar multiple reaction sites in the substrate. In this Perspective, three topics of substrate-directed reaction are mainly reviewed: (1) directing group-assisted epoxidation of alkenes, (2) ring-opening reactions of epoxides by various nucleophiles, and (3) catalytic peptide synthesis. Our newly developed synthetic methods with new ligands including hydroxamic acid derived ligands realized not only highly efficient reactions but also pinpointed reactions at the expected position, demonstrating the substrate-directed reaction as a powerful method to achieve the desired regio- and stereoselective functionalization of molecules from different viewpoints of reagent- or catalyst-controlled reactions.

  7. Radioisotope applications on fluidized catalytic cracking units

    International Nuclear Information System (INIS)

    Charlton, J.S.

    1997-01-01

    Radioisotopes are used to trace the flow of all the phases of Fluidized Catalytic Cracking process in oil refineries. The gaseous phases, steam, hydrocarbon vapour and air, are generally traced using a noble-gas isotope, 41 Ar, 79 Kr or 85 Kr. An appropriate tracer for the catalyst is produced by irradiating a catalyst sample in a nuclear reactor. The activation products, 140 La and 24 Na provide appropriate radioactive 'labels' for the catalyst, which is reinjected into the FCC. An advantage of this approach is that it facilitates the study of the behaviour of different particle size fractions. Radioisotopes as sealed sources of gamma radiation are used to measure catalyst density variations and density distributions in critical parts of the unit. An important trend in radioisotope applications is the increasing use of the information they produce as inputs to or as validation of, mathematical process models. In line with the increasing sophistication of the models, the technology is undergoing continuous refinement. Developments include the investigation of more efficient, more convenient tracers, the introduction of systems to facilitate more rapid and comprehensive data acquisition and software refinements for enhanced data analysis

  8. 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.

  9. 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.

  10. 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.

  11. 3-Nitropropionic Acid is a Suicide Inhibitor of MitochondrialRespiration that, Upon Oxidation by Complex II, Forms a Covalent AdductWith a Catalytic Base Arginine in the Active Site of the Enzyme

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Li-shar; Sun, Gang; Cobessi, David; Wang, Andy C.; Shen,John T.; Tung, Eric Y.; Anderson, Vernon E.; Berry, Edward A.

    2005-12-01

    We report three new structures of mitochondrial respiratory Complex II (succinate ubiquinone oxidoreductase, E.C. 1.3.5.1) at up to 2.1 {angstrom} resolution, with various inhibitors. The structures define the conformation of the bound inhibitors and suggest the residues involved in substrate binding and catalysis at the dicarboxylate site. In particular they support the role of Arg297 as a general base catalyst accepting a proton in the dehydrogenation of succinate. The dicarboxylate ligand in oxaloacetate-containing crystals appears to be the same as that reported for Shewanella flavocytochrome c treated with fumarate. The plant and fungal toxin 3-nitropropionic acid, an irreversible inactivator of succinate dehydrogenase, forms a covalent adduct with the side chain of Arg297. The modification eliminates a trypsin cleavage site in the flavoprotein, and tandem mass spectroscopic analysis of the new fragment shows the mass of Arg 297 to be increased by 83 Da and to have potential of losing 44 Da, consistent with decarboxylation, during fragmentation.

  12. Incorporation of Pendant Bases into Rh(diphosphine)2 Complexes: Synthesis, Thermodynamic Studies, And Catalytic CO2 Hydrogenation Activity of [Rh(P2N2)2](+) Complexes.

    Science.gov (United States)

    Lilio, Alyssia M; Reineke, Mark H; Moore, Curtis E; Rheingold, Arnold L; Takase, Michael K; Kubiak, Clifford P

    2015-07-01

    A series of five [Rh(P2N2)2](+) complexes (P2N2 = 1,5-diaza-3,7-diphosphacyclooctane) have been synthesized and characterized: [Rh(P(Ph)2N(Ph)2)2](+) (1), [Rh(P(Ph)2N(Bn)2)2](+) (2), [Rh(P(Ph)2N(PhOMe)2)2](+) (3), [Rh(P(Cy)2N(Ph)2)2](+) (4), and [Rh(P(Cy)2N(PhOMe)2)2](+) (5). Complexes 1-5 have been structurally characterized as square planar rhodium bis-diphosphine complexes with slight tetrahedral distortions. The corresponding hydride complexes 6-10 have also been synthesized and characterized, and X-ray diffraction studies of HRh(P(Ph)2N(Bn)2)2 (7), HRh(P(Ph)2N(PhOMe)2)2 (8) and HRh(P(Cy)2N(Ph)2)2 (9) show that the hydrides have distorted trigonal bipyramidal geometries. Equilibration of complexes 2-5 with H2 in the presence of 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo[3,3,3]undecane (Verkade's base) enabled the determination of the hydricities and estimated pKa's of the Rh(I) hydride complexes using the appropriate thermodynamic cycles. Complexes 1-5 were active for CO2 hydrogenation under mild conditions, and their relative rates were compared to that of [Rh(depe)2](+), a nonpendant-amine-containing complex with a similar hydricity to the [Rh(P2N2)2](+) complexes. It was determined that the added steric bulk of the amine groups on the P2N2 ligands hinders catalysis and that [Rh(depe)2](+) was the most active catalyst for hydrogenation of CO2 to formate.

  13. Porous Core-Shell Nanostructures for Catalytic Applications

    Science.gov (United States)

    Ewers, Trevor David

    Porous core-shell nanostructures have recently received much attention for their enhanced thermal stability. They show great potential in the field of catalysis, as reactant gases can diffuse in and out of the porous shell while the core particle is protected from sintering, a process in which particles coalesce to form larger particles. Sintering is a large problem in industry and is the primary cause of irreversible deactivation. Despite the obvious advantages of high thermal stability, porous core-shell nanoparticles can be developed to have additional interactive properties from the combination of the core and shell together, rather than just the core particle alone. This dissertation focuses on developing new porous core-shell systems in which both the core and shell take part in catalysis. Two types of systems are explored; (1) yolk-shell nanostructures with reducible oxide shells formed using the Kirkendall effect and (2) ceramic-based porous oxide shells formed using sol-gel chemistry. Of the Kirkendall-based systems, Au FexOy and Cu CoO were synthesized and studied for catalytic applications. Additionally, ZnO was explored as a potential shelling material. Sol-gel work focused on optimizing synthetic methods to allow for coating of small gold particles, which remains a challenge today. Mixed metal oxides were explored as a shelling material to make dual catalysts in which the product of a reaction on the core particle becomes a reactant within the shell.

  14. Rice Cellulose SynthaseA8 Plant-Conserved Region Is a Coiled-Coil at the Catalytic Core Entrance

    Energy Technology Data Exchange (ETDEWEB)

    Rushton, Phillip S.; Olek, Anna T.; Makowski, Lee; Badger, John; Steussy, C. Nicklaus; Carpita, Nicholas C.; Stauffacher, Cynthia V. (NEU); (Purdue)

    2016-11-22

    The crystallographic structure of a rice (Oryza sativa) cellulose synthase, OsCesA8, plant-conserved region (P-CR), one of two unique domains in the catalytic domain of plant CesAs, was solved to 2.4 Å resolution. Two antiparallel α-helices form a coiled-coil domain linked by a large extended connector loop containing a conserved trio of aromatic residues. The P-CR structure was fit into a molecular envelope for the P-CR domain derived from small-angle X-ray scattering data. The P-CR structure and molecular envelope, combined with a homology-based chain trace of the CesA8 catalytic core, were modeled into a previously determined CesA8 small-angle X-ray scattering molecular envelope to produce a detailed topological model of the CesA8 catalytic domain. The predicted position for the P-CR domain from the molecular docking models places the P-CR connector loop into a hydrophobic pocket of the catalytic core, with the coiled-coil aligned near the entrance of the substrate UDP-glucose into the active site. In this configuration, the P-CR coiled-coil alone is unlikely to regulate substrate access to the active site, but it could interact with other domains of CesA, accessory proteins, or other CesA catalytic domains to control substrate delivery.

  15. An Evaluation of the Vapor Phase Catalytic Ammonia Removal Process for Use in a Mars Transit Vehicle

    Science.gov (United States)

    Flynn, Michael; Borchers, Bruce

    1998-01-01

    An experimental program has been developed to evaluate the potential of the Vapor Phase Catalytic Ammonia Reduction (VPCAR) technology for use as a Mars Transit Vehicle water purification system. Design modifications which will be required to ensure proper operation of the VPCAR system in reduced gravity are also evaluated. The VPCAR system is an integrated wastewater treatment technology that combines a distillation process with high temperature catalytic oxidation. The distillation portion of the system utilizes a vapor compression distillation process to provide an energy efficient phase change separation. This portion of the system removes any inorganic salts and large molecular weight, organic contaminates, i.e., non-volatile, from the product water stream and concentrates these contaminates into a byproduct stream. To oxidize the volatile organic compounds and ammonia, a vapor phase, high temperature catalytic oxidizer is used. This catalytic system converts these compounds along with the aqueous product into CO2, H2O, and N2O. A secondary catalytic bed can then be used to reduce the N2O to nitrogen and oxygen (although not evaluated in this study). This paper describes the design specification of the VPCAR process, the relative benefits of its utilization in a Mars Transit Vehicle, and the design modification which will be required to ensure its proper operation in reduced gravity. In addition, the results of an experimental evaluation of the processors is presented. This evaluation presents the processors performance based upon product water purity, water recovery rates, and power.

  16. Relationship between surface property and catalytic application of amorphous NiP/Hβ catalyst for n-hexane isomerization

    Science.gov (United States)

    Chen, Jinshe; Duan, Zunbin; Song, Zhaoyang; Zhu, Lijun; Zhou, Yulu; Xiang, Yuzhi; Xia, Daohong

    2017-12-01

    The amorphous NiP nanoparticles were synthesized and a novel amorphous NiP/Hβ catalyst was prepared successfully further. Due to the superior surface property of amorphous NiP/Hβ catalyst, it exhibited good catalytic application for n-hexane isomerization. The catalytic activity of amorphous NiP/Hβ catalyst was close to that of the prepared Pt/Hβ sample, and better than that of commercial catalyst and crystalline Ni2P/Hβ catalyst. What's more, the amorphous NiP/Hβ catalyst shows high resistance to different sulfur compounds and water on account of its unique surface property. The effect of loading amounts on surface property and catalytic performance was investigated, and the structure-function relationship among them was studied ulteriorly. The results demonstrate that loading amounts have effect on textural property and surface acid property, which further affect the catalytic performance. The 10 wt.% NiP/Hβ sample has appropriate pore structure and acid property with uniformly dispersed NiP nanoparticles on surface, which is helpful for providing suitable synergistic effect. The effects of reaction conditions on surface reactions and the mechanism for n-hexane isomerization were investigated further. Based on these results, the amorphous NiP/Hβ catalyst with superior surface property probably pavesa way to overcome the drawbacks of traditional noble metal catalyst, which shows good catalytic application prospects.

  17. Catalytic Flash Pyrolysis of Biomass Using Different Types of Zeolite and Online Vapor Fractionation

    Directory of Open Access Journals (Sweden)

    Ali Imran

    2016-03-01

    Full Text Available Bio-oil produced from conventional flash pyrolysis has poor quality and requires expensive upgrading before it can be used as a transportation fuel. In this work, a high quality bio-oil has been produced using a novel approach where flash pyrolysis, catalysis and fractionation of pyrolysis vapors using two stage condensation are combined in a single process unit. A bench scale unit of 1 kg/h feedstock capacity is used for catalytic pyrolysis in an entrained down-flow reactor system equipped with two-staged condensation of the pyrolysis vapor. Zeolite-based catalysts are investigated to study the effect of varying acidities of faujasite Y zeolites, zeolite structures (ZSM5, different catalyst to biomass ratios and different catalytic pyrolysis temperatures. Low catalyst/biomass ratios did not show any significant improvements in the bio-oil quality, while high catalyst/biomass ratios showed an effective deoxygenation of the bio-oil. The application of zeolites decreased the organic liquid yield due to the increased production of non-condensables, primarily hydrocarbons. The catalytically produced bio-oil was less viscous and zeolites were effective at cracking heavy molecular weight compounds in the bio-oil. Acidic zeolites, H-Y and H-ZSM5, increased the desirable chemical compounds in the bio-oil such as phenols, furans and hydrocarbon, and reduced the undesired compounds such as acids. On the other hand reducing the acidity of zeolites reduced some of the undesired compounds in the bio-oil such as ketones and aldehydes. The performance of H-Y was superior to that of the rest of zeolites studied: bio-oil of high chemical and calorific value was produced with a high organic liquid yield and low oxygen content. H-ZSM5 was a close competitor to H-Y in performance but with a lower yield of bio-oil. Online fractionation of catalytic pyrolysis vapors was employed by controlling the condenser temperature and proved to be a successful process parameter

  18. Catalytic Flash Pyrolysis of Biomass Using Different Types of Zeolite and Online Vapor Fractionation

    KAUST Repository

    Imran, Ali

    2016-03-11

    Bio-oil produced from conventional flash pyrolysis has poor quality and requires expensive upgrading before it can be used as a transportation fuel. In this work, a high quality bio-oil has been produced using a novel approach where flash pyrolysis, catalysis and fractionation of pyrolysis vapors using two stage condensation are combined in a single process unit. A bench scale unit of 1 kg/h feedstock capacity is used for catalytic pyrolysis in an entrained down-flow reactor system equipped with two-staged condensation of the pyrolysis vapor. Zeolite-based catalysts are investigated to study the effect of varying acidities of faujasite Y zeolites, zeolite structures (ZSM5), different catalyst to biomass ratios and different catalytic pyrolysis temperatures. Low catalyst/biomass ratios did not show any significant improvements in the bio-oil quality, while high catalyst/biomass ratios showed an effective deoxygenation of the bio-oil. The application of zeolites decreased the organic liquid yield due to the increased production of non-condensables, primarily hydrocarbons. The catalytically produced bio-oil was less viscous and zeolites were effective at cracking heavy molecular weight compounds in the bio-oil. Acidic zeolites, H-Y and H-ZSM5, increased the desirable chemical compounds in the bio-oil such as phenols, furans and hydrocarbon, and reduced the undesired compounds such as acids. On the other hand reducing the acidity of zeolites reduced some of the undesired compounds in the bio-oil such as ketones and aldehydes. The performance of H-Y was superior to that of the rest of zeolites studied: bio-oil of high chemical and calorific value was produced with a high organic liquid yield and low oxygen content. H-ZSM5 was a close competitor to H-Y in performance but with a lower yield of bio-oil. Online fractionation of catalytic pyrolysis vapors was employed by controlling the condenser temperature and proved to be a successful process parameter to tailor the

  19. In situ and operando transmission electron microscopy of catalytic materials

    DEFF Research Database (Denmark)

    Crozier, Peter A.; Hansen, Thomas Willum

    2015-01-01

    Catalytic nanomaterials play a major role in chemical conversions and energy transformations. Understanding how materials control and regulate surface reactions is a major objective for fundamental research on heterogeneous catalysts. In situ environmental transmission electron microscopy (ETEM...

  20. Towards chiral diamines as chiral catalytic precursors for the borane ...

    Indian Academy of Sciences (India)

    2)-2-anilinomethylpiperidine (2) have been employed as chiral catalytic sources in the borane-mediated asymmetric reduction of prochiral ketones thus providing the resulting secondary alcohols in good enantiomeric purities (up to 81% ) ...