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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...... solutions. Furthermore, durability results from base metal/Pd coated DPFs installed on operating taxis and related tests cycle data is given....

  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)

    Fajardo, J Eduardo; Fiser, Andras

    2013-02-22

    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. 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. 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 reference databases.

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

    KAUST Repository

    Al-Khattaf, Sulaiman

    2008-01-01

    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

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

    KAUST Repository

    Imran, Ali; Bramer, Eddy A.; Seshan, Kulathuiyer; Brem, Gerrit

    2015-01-01

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

  6. 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.

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

    NARCIS (Netherlands)

    Ali Imran, A.; Bramer, Eduard A.; Seshan, Kulathuiyer; Brem, Gerrit

    2016-01-01

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

  8. 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.

  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. Optimization of Cholinesterase-Based Catalytic Bioscavengers Against Organophosphorus Agents.

    Science.gov (United States)

    Lushchekina, Sofya V; Schopfer, Lawrence M; Grigorenko, Bella L; Nemukhin, Alexander V; Varfolomeev, Sergei D; Lockridge, Oksana; Masson, Patrick

    2018-01-01

    Organophosphorus agents (OPs) are irreversible inhibitors of acetylcholinesterase (AChE). OP poisoning causes major cholinergic syndrome. Current medical counter-measures mitigate the acute effects but have limited action against OP-induced brain damage. Bioscavengers are appealing alternative therapeutic approach because they neutralize OPs in bloodstream before they reach physiological targets. First generation bioscavengers are stoichiometric bioscavengers. However, stoichiometric neutralization requires administration of huge doses of enzyme. Second generation bioscavengers are catalytic bioscavengers capable of detoxifying OPs with a turnover. High bimolecular rate constants ( k cat / K m > 10 6 M -1 min -1 ) are required, so that low enzyme doses can be administered. Cholinesterases (ChE) are attractive candidates because OPs are hemi-substrates. Moderate OP hydrolase (OPase) activity has been observed for certain natural ChEs and for G117H-based human BChE mutants made by site-directed mutagenesis. However, before mutated ChEs can become operational catalytic bioscavengers their dephosphylation rate constant must be increased by several orders of magnitude. New strategies for converting ChEs into fast OPase are based either on combinational approaches or on computer redesign of enzyme. The keystone for rational conversion of ChEs into OPases is to understand the reaction mechanisms with OPs. In the present work we propose that efficient OP hydrolysis can be achieved by re-designing the configuration of enzyme active center residues and by creating specific routes for attack of water molecules and proton transfer. Four directions for nucleophilic attack of water on phosphorus atom were defined. Changes must lead to a novel enzyme, wherein OP hydrolysis wins over competing aging reactions. Kinetic, crystallographic, and computational data have been accumulated that describe mechanisms of reactions involving ChEs. From these studies, it appears that introducing

  11. Optimization of Cholinesterase-Based Catalytic Bioscavengers Against Organophosphorus Agents

    Directory of Open Access Journals (Sweden)

    Sofya V. Lushchekina

    2018-03-01

    Full Text Available Organophosphorus agents (OPs are irreversible inhibitors of acetylcholinesterase (AChE. OP poisoning causes major cholinergic syndrome. Current medical counter-measures mitigate the acute effects but have limited action against OP-induced brain damage. Bioscavengers are appealing alternative therapeutic approach because they neutralize OPs in bloodstream before they reach physiological targets. First generation bioscavengers are stoichiometric bioscavengers. However, stoichiometric neutralization requires administration of huge doses of enzyme. Second generation bioscavengers are catalytic bioscavengers capable of detoxifying OPs with a turnover. High bimolecular rate constants (kcat/Km > 106 M−1min−1 are required, so that low enzyme doses can be administered. Cholinesterases (ChE are attractive candidates because OPs are hemi-substrates. Moderate OP hydrolase (OPase activity has been observed for certain natural ChEs and for G117H-based human BChE mutants made by site-directed mutagenesis. However, before mutated ChEs can become operational catalytic bioscavengers their dephosphylation rate constant must be increased by several orders of magnitude. New strategies for converting ChEs into fast OPase are based either on combinational approaches or on computer redesign of enzyme. The keystone for rational conversion of ChEs into OPases is to understand the reaction mechanisms with OPs. In the present work we propose that efficient OP hydrolysis can be achieved by re-designing the configuration of enzyme active center residues and by creating specific routes for attack of water molecules and proton transfer. Four directions for nucleophilic attack of water on phosphorus atom were defined. Changes must lead to a novel enzyme, wherein OP hydrolysis wins over competing aging reactions. Kinetic, crystallographic, and computational data have been accumulated that describe mechanisms of reactions involving ChEs. From these studies, it appears that

  12. Determination of organic bases in non-aqueous solvents by catalytic thermometric titration.

    Science.gov (United States)

    Vajgand, V J; Kiss, T A; Gaál, F F; Zsigrai, I J

    1968-07-01

    Catalytic thermometric titrations have been developed for bases (brucine, diethylaniline, potassium acetate and triethylamine) in acetic acid by continuous and discontinuous addition of the standard solution and automatic temperature recording. The determination of weak bases, e.g., antipyrine, unsuccessful in acetic acid by catalytic thermometric titration, has been achieved by using nitromethane or acetic anhydride as solvent. Catalytic thermometric titrations were also performed by coulometric generation of hydrogen ions for the determination of micro amounts of weak bases in a mixture of acetic anhyride and acetic acid.

  13. Green technology for conversion of renewable hydrocarbon based on plasma-catalytic approach

    Science.gov (United States)

    Fedirchyk, Igor; Nedybaliuk, Oleg; Chernyak, Valeriy; Demchina, Valentina

    2016-09-01

    The ability to convert renewable biomass into fuels and chemicals is one of the most important steps on our path to green technology and sustainable development. However, the complex composition of biomass poses a major problem for established conversion technologies. The high temperature of thermochemical biomass conversion often leads to the appearance of undesirable byproducts and waste. The catalytic conversion has reduced yield and feedstock range. Plasma-catalytic reforming technology opens a new path for biomass conversion by replacing feedstock-specific catalysts with free radicals generated in the plasma. We studied the plasma-catalytic conversion of several renewable hydrocarbons using the air plasma created by rotating gliding discharge. We found that plasma-catalytic hydrocarbon conversion can be conducted at significantly lower temperatures (500 K) than during the thermochemical ( 1000 K) and catalytic (800 K) conversion. By using gas chromatography, we determined conversion products and found that conversion efficiency of plasma-catalytic conversion reaches over 85%. We used obtained data to determine the energy yield of hydrogen in case of plasma-catalytic reforming of ethanol and compared it with other plasma-based hydrogen-generating systems.

  14. 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...... precursors. Cross-catalytic product formation followed product inhibited kinetics, but approximately two replication rounds were observed. Analogous but less efficient replication was found for a similar tetrameric system. These results demonstrate that simpler nucleobase replication systems than natural...

  15. A QM/MM–Based Computational Investigation on the Catalytic Mechanism of Saccharopine Reductase

    OpenAIRE

    Almasi, Joel N.; Bushnell, Eric A.C.; Gauld, James W.

    2011-01-01

    Saccharopine reductase from Magnaporthe grisea, an NADPH-containing enzyme in the α-aminoadipate pathway, catalyses the formation of saccharopine, a precursor to L-lysine, from the substrates glutamate and α-aminoadipate-δ-semialdehyde. Its catalytic mechanism has been investigated using quantum mechanics/molecular mechanics (QM/MM) ONIOM-based approaches. In particular, the overall catalytic pathway has been elucidated and the effects of electron correlation and the anisotropic polar protein...

  16. 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

  17. 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.

  18. 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......–energy dispersive X-ray spectroscopy (SEM–EDX) and NH3-temperature programmed desorption (NH3-TPD). 95% deactivation was observed for the V2O5–WO3–TiO2 catalyst, while the Cu–HZSM5 and Cu–HMOR catalysts deactivated only 58% and 48%, respectively, after 1200 h KCl exposure. SEM analysis of the KCl aerosol exposed...... catalysts revealed that the potassium salt not only deposited on the catalyst surface, but also penetrated into the catalyst wall. Thus, the K/M ratio (M = V or Cu) was high on V2O5–WO3–TiO2 catalyst and comparatively less on Cu–HZSM5 and Cu–HMOR catalysts. NH3-TPD revealed that the KCl exposed Cu–HZSM5...

  19. 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.

  20. 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.)

  1. 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...

  2. 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

  3. Autonomous micromotor based on catalytically pneumatic behavior of balloon-like MnO(x)-graphene crumples.

    Science.gov (United States)

    Chen, Xueli; Wu, Guan; Lan, Tian; Chen, Wei

    2014-07-11

    A novel autonomous micromotor, based on catalytically pneumatic behaviour of balloon-like MnOx-graphene crumples, has been synthesized via an ultrasonic spray pyrolysis method. Through catalytic decomposition of H2O2 into O2, the gas accumulated in a confined space and was released to generate a strong force to push the micromotor.

  4. 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

  5. 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.

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

    International Nuclear Information System (INIS)

    Pavlidis, Ioannis V.; Vorhaben, Torge; Gournis, Dimitrios; Papadopoulos, George K.; Bornscheuer, Uwe T.; Stamatis, Haralambos

    2012-01-01

    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.

  7. 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.

  8. Catalytic reduction of hexaminecobalt(III) by pitch-based spherical activated carbon (PBSAC)

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yu; Mao, Yan-Peng; Zhu, Hai-Song; Cheng, Jing-Yi; Long, Xiang-Li; Yuan, Wei-Kang [State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai (China)

    2010-07-15

    The wet ammonia (NH{sub 3}) desulfurization process can be retrofitted to remove nitric oxide (NO) and sulfur dioxide (SO{sub 2}) simultaneously by adding soluble cobalt(II) salt into the aqueous ammonia solution. Activated carbon is used as a catalyst to regenerate hexaminecobalt(II), Co(NH{sub 3}){sub 6}{sup 2+}, so that NO removal efficiency can be maintained at a high level for a long time. In this study, the catalytic performance of pitch-based spherical activated carbon (PBSAC) in the simultaneous removal of NO and SO{sub 2} with this wet ammonia scrubbing process has been studied systematically. Experiments have been performed in a batch stirred cell to test the catalytic characteristics of PBSAC in the catalytic reduction of hexaminecobalt(III), Co(NH{sub 3}){sub 6}{sup 3+}. The experimental results show that PBSAC is a much better catalyst in the catalytic reduction of Co(NH{sub 3}){sub 6}{sup 3+} than palm shell activated carbon (PSAC). The Co(NH{sub 3}){sub 6}{sup 3+} reduction reaction rate increases with PBSAC when the PBSAC dose is below 7.5 g/L. The Co(NH{sub 3}){sub 6}{sup 3+} reduction rate increases with its initial concentration. Best Co(NH{sub 3}){sub 6}{sup 3+} conversion is gained at a pH range of 2.0-6.0. A high temperature is favorable to such reaction. The intrinsic activation energy of 51.00 kJ/mol for the Co(NH{sub 3}){sub 6}{sup 3+} reduction catalyzed by PBSAC has been obtained. The experiments manifest that the simultaneous elimination of NO and SO{sub 2} by the hexaminecobalt solution coupled with catalytic regeneration of hexaminecobalt(II) can maintain a NO removal efficiency of 90% for a long time. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  9. 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

  10. Catalytic Enzyme-Based Methods for Water Treatment and Water Distribution System Decontamination. 1. Literature Survey

    Science.gov (United States)

    2006-06-01

    best examples of this is glucose isomerase, which has been used in the commercial production of high fructose corn syrup (HFCS) since 1967.230 Most...EDGEWOOD CHEMICAL BIOLOGICAL CENTER U.S. ARMY RESEARCH, DEVELOPMENT AND ENGINEERING COMMAND ECBC-TR-489 CATALYTIC ENZYME-BASED METHODS FOR WATER ...TREATMENT AND WATER DISTRIBUTION SYSTEM DECONTAMINATION 1. LITERATURE SURVEY Joseph J. DeFrank RESEARCH AND TECHNOLOGY DIRECTORATE June 2006 Approved for

  11. A QM/MM–Based Computational Investigation on the Catalytic Mechanism of Saccharopine Reductase

    Directory of Open Access Journals (Sweden)

    James W. Gauld

    2011-10-01

    Full Text Available Saccharopine reductase from Magnaporthe grisea, an NADPH-containing enzyme in the α-aminoadipate pathway, catalyses the formation of saccharopine, a precursor to L-lysine, from the substrates glutamate and α-aminoadipate-δ-semialdehyde. Its catalytic mechanism has been investigated using quantum mechanics/molecular mechanics (QM/MM ONIOM-based approaches. In particular, the overall catalytic pathway has been elucidated and the effects of electron correlation and the anisotropic polar protein environment have been examined via the use of the ONIOM(HF/6-31G(d:AMBER94 and ONIOM(MP2/6-31G(d//HF/6-31G(d:AMBER94 methods within the mechanical embedding formulism and ONIOM(MP2/6-31G(d//HF/6-31G(d:AMBER94 and ONIOM(MP2/6-311G(d,p//HF/6-31G(d:AMBER94 within the electronic embedding formulism. The results of the present study suggest that saccharopine reductase utilises a substrate-assisted catalytic pathway in which acid/base groups within the cosubstrates themselves facilitate the mechanistically required proton transfers. Thus, the enzyme appears to act most likely by binding the three required reactant molecules glutamate, α-aminoadipate-δ-semialdehyde and NADPH in a manner and polar environment conducive to reaction.

  12. Low temperature catalytic combustion of propane over Pt-based catalyst with inverse opal microstructure in microchannel reactor

    NARCIS (Netherlands)

    Guan, G.; Zapf, R.; Kolb, G.A.; Men, Y.; Hessel, V.; Löwe, H.; Ye, J.; Zentel, R.

    2007-01-01

    novel Pt-based catalyst with highly regular, periodic inverse opal microstructure was fabricated in a microchannel reactor, and catalytic testing revealed excellent conversion and stable activity for propane combustion at low temperatures

  13. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-04-15

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

  15. 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

  16. 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.

  17. 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.

  18. Solid strong base K-Pt/NaY zeolite nano-catalytic system for completed elimination of formaldehyde at room temperature

    Science.gov (United States)

    Song, Shaoqing; Wu, Xi; Lu, Changhai; Wen, Meicheng; Le, Zhanggao; Jiang, Shujuan

    2018-06-01

    Solid strong base nano-catalytic system of K-modification NaY zeolite supported 0.08% Pt (K-Pt/NaY) were constructed for eliminating HCHO at room temperature. In the catalytic process, activation energy over K-Pt/NaY nano-catalytic system was greatly decreased along with the enhanced reaction rate. Characterization and catalytic tests revealed the surface electron structure of K-Pt/NaY was improved, as reflected by the enhanced HCHO adsorption capability, high sbnd OH concentration, and low-temperature reducibility. Therefore, the optimal K-Pt/NaY showed high catalytic efficiency and strong H2O tolerance for HCHO elimination by directly promoting the reaction between active sbnd OH and formate species. These results may suggest a new way for probing the advanced solid strong base nano-catalytic system for the catalytic elimination of indoor HCHO.

  19. Process systems engineering studies for catalytic production of bio-based platform molecules from lignocellulosic biomass

    International Nuclear Information System (INIS)

    Han, Jeehoon

    2017-01-01

    Highlights: • A process-systems engineering study for production of bio-based platform molecules to is presented. • Experimentally verified catalysis studies for biomass conversion are investigated. • New separations for effective recovery of bio-based platform molecules are developed. • Separations are integrated with catalytic biomass conversions. • Proposed process can compete economically with the current production approaches. - Abstract: This work presents a process-system engineering study of an integrated catalytic conversion strategy to produce bio-based platform molecules (levulinic acid (LA), furfural (FF), and propyl guaiacol (PG)) from hemicellulose (C_5), cellulose (C_6), and lignin fractions of lignocellulosic biomass. A commercial-scale process based on the strategy produces high numerical carbon yields (overall yields: 35.2%; C_6-to-LA: 20.4%, C_5-to-FF: 69.2%, and Lignin-to-PG: 13.3%) from a dilute concentration of solute (1.3–30.0 wt.% solids), but a high recovery of these molecules requires an efficient separation system with low energy requirement. A heat exchanger network significantly reduced the total energy requirements of the process. An economic analysis showed that the minimum selling price of LA as the highest value-added product (42.3 × 10"3 t of LA/y using 700 × 10"3 dry t/y of corn stover) is US$1707/t despite using negative economic parameters, and that this system can be cost-competitive with current production approaches.

  20. An electrochemical methanol sensor based on a Pd-Ni/SiNWs catalytic electrode

    International Nuclear Information System (INIS)

    Tao Bairui; Zhang Jian; Hui Shichao; Chen Xuejiao; Wan Lijuan

    2010-01-01

    A novel electrochemical methanol sensor based on a catalytic electrode of palladium-nickel/silicon nanowires (Pd-Ni/SiNWs) is presented in this paper. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and electrochemical methods are employed to investigate the Pd-Ni/SiNWs electrode materials. These nanocomposite materials exhibit a highly ordered, wire-like structure with a wire length of ∼50 μm and a wire diameter ranging from 100 to 300 nm. The substrate has good electrocatalytic activity towards the oxidation of methanol in alkaline solutions. The performances of the prototype sensor are characterized by cyclic voltammetry and fixed potential amperometry techniques. In a 1 mol L -1 KOH solution containing different methanol concentrations, the sensor exhibits a good sensitivity of 1.96 mA mmol -1 L cm -2 with R 2 = 0.99 and the corresponding detection limit of 18 μmol L -1 (signal-to-noise ratio = 3, S/N = 3) for cyclic voltammetry. Meanwhile, the electrode also displays a sensitivity of 0.48 mA mmol -1 L cm -2 with R 2 = 0.98 and the corresponding detection limit of 25 μmol L -1 (S/N = 3) for a fixed potential amperometry at -0.3 V versus an Ag/AgCl reference electrode. The results demonstrate that the Pd-Ni/SiNWs catalytic electrode has potential as an efficient and integrated sensor for methanol detection.

  1. Microlith-Based Catalytic Reactor for Air Quality and Trace Contaminant Control Applications

    Science.gov (United States)

    Vilekar, Saurabh; Hawley, Kyle; Junaedi, Christian; Crowder, Bruce; Prada, Julian; Mastanduno, Richard; Perry, Jay L.; Kayatin, Matthew J.

    2015-01-01

    Traditionally, gaseous compounds such as methane, carbon monoxide, and trace contaminants have posed challenges for maintaining clean air in enclosed spaces such as crewed spacecraft cabins as they are hazardous to humans and are often difficult to remove by conventional adsorption technology. Catalytic oxidizers have provided a reliable and robust means of disposing of even trace levels of these compounds by converting them into carbon dioxide and water. Precision Combustion, Inc. (PCI) and NASA - Marshall (MSFC) have been developing, characterizing, and optimizing high temperature catalytic oxidizers (HTCO) based on PCI's patented Microlith® technology to meet the requirements of future extended human spaceflight explorations. Current efforts have focused on integrating the HTCO unit with a compact, simple recuperative heat exchanger to reduce the overall system size and weight while also reducing its energy requirements. Previous efforts relied on external heat exchangers to recover the waste heat and recycle it to the oxidizer to minimize the system's power requirements; however, these units contribute weight and volume burdens to the overall system. They also result in excess heat loss due to the separation of the HTCO and the heat recuperator, resulting in lower overall efficiency. Improvements in the recuperative efficiency and close coupling of HTCO and heat recuperator lead to reductions in system energy requirements and startup time. Results from testing HTCO units integrated with heat recuperators at a variety of scales for cabin air quality control and heat melt compactor applications are reported and their benefits over previous iterations of the HTCO and heat recuperator assembly are quantified in this paper.

  2. 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.

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

    NARCIS (Netherlands)

    Buurmans, I.L.C.; Soulimani, F.; Ruiz Martinez, J.; van der Bij, H.E.; Weckhuysen, B.M.

    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

  4. L-proline-based deep eutectic solvents (DESs) for deep catalytic oxidative desulfurization (ODS) of diesel.

    Science.gov (United States)

    Hao, Lingwan; Wang, Meiri; Shan, Wenjuan; Deng, Changliang; Ren, Wanzhong; Shi, Zhouzhou; Lü, Hongying

    2017-10-05

    A series of L-proline-based DESs was prepared through an atom economic reaction between L-proline (L-Pro) and four different kinds of organic acids. The DESs were characterized by Fourier transform infrared spectroscopy (FT-IR), H nuclear magnetic resonance ( 1 HNMR), cyclic voltammogram (CV) and the Hammett method. The synthesized DESs were used for the oxidative desulfurization and the L-Pro/p-toluenesultonic acid (L-Pro/p-TsOH) system shows the highest catalytic activity that the removal of dibenzothiophene (DBT) reached 99% at 60°C in 2h, which may involve the dual activation of the L-Pro/p-TsOH. The acidity of four different L-proline-based DESs was measured and the results show that it could not simply conclude that the correlation between the acidity of DESs and desulfurization capability was positive or negative. The electrochemical measurements evidences and recycling experiment indicate a good stability performance of L-Pro/p-TsOH in desulfurization. This work will provide a novel and potential method for the deep oxidation desulfurization. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Catalytic pyrolysis of Tetraselmis and Isochrysis microalgae by nickel ceria based catalysts for hydrocarbon production

    International Nuclear Information System (INIS)

    Aysu, Tevfik; Abd Rahman, Nur Adilah; Sanna, Aimaro

    2016-01-01

    The catalytic pyrolysis of Tetraselmis sp. and Isochrysis sp. was carried out over ceria based catalysts in a fixed bed reactor. There was a clear effect of the catalysts on the product yields and quality, with the catalysts able to recover a large fraction of the starting microalgae energy (67–77%) in the bio-oils. Bio-oil yield was found to be higher in presence of Ni–Ce/Al_2O_3 and Ni–Ce/ZrO_2 (26 wt.%). The produced bio-oils had HHVs (higher heating values) of 34–35 MJ/kg and suffered strong deoxygenation, with O level decreased from 40–41% in the starting microalgae to 9–15%. Also, 15–20% N removal was obtained using the ceria based catalysts. The oxygen contents in the bio-oils were remarkably lower than those previously obtained using ZSM-5 (25%) and other species without catalyst (17–24%). "1H NMR and GC–MS analysis showed that the bio-oils were enriched in aliphatics and depleted in N-compounds and water using the ceria based catalysts. - Highlights: • Nickel-ceria based catalysts were evaluated for the in-situ conversion of Tetraselmis and Isochrysis microalgae. • Catalysts recovered 72–77% of the starting microalgae energy in bio-oils. • Bio-oils suffered strong deoxygenation, with O level decreased from 40–41% in the starting microalgae to 9–15%. • Bio-oils were enriched in aliphatics and depleted in N-compounds.

  6. 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.).

  7. 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

  8. alpha,beta-unsaturated 2-acyl imidazoles as a practical class of dienophiles for the DNA-Based catalytic asymmetric diels-alder reaction in water

    NARCIS (Netherlands)

    Boersma, A.J.; Feringa, B.L.; Roelfes, G.

    2007-01-01

    alpha,beta-Unsaturated 2-acyl imidazoles are a novel and practical class of dienophiles for the DNA-based catalytic asymmetric Diels-Alder reaction in water. The Diels-Alder products are obtained with very high diastereoselectivities and enantioselectivities in the range of 83-98%. The catalytic

  9. Dual Role of Water in Heterogeneous Catalytic Hydrolysis of Sarin by Zirconium-Based Metal-Organic Frameworks.

    Science.gov (United States)

    Momeni, Mohammad R; Cramer, Christopher J

    2018-05-22

    Recent experimental studies on Zr IV -based metal-organic frameworks (MOFs) have shown the extraordinary effectiveness of these porous materials for the detoxification of phosphorus-based chemical warfare agents (CWAs). However, pressing challenges remain with respect to characterizing these catalytic processes both at the molecular and crystalline levels. We here use theory to compare the reactivity of different zirconium-based MOFs for the catalytic hydrolysis of the CWA sarin, using both periodic and cluster modeling. We consider both hydrated and dehydrated secondary building units, as well as linker functionalized MOFs, to more fully understand and rationalize available experimental findings as well as to enable concrete predictions for achieving higher activities for the decomposition of CWAs.

  10. 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.)

  11. Controlling cation segregation in perovskite-based electrodes for high electro-catalytic activity and durability.

    Science.gov (United States)

    Li, Yifeng; Zhang, Wenqiang; Zheng, Yun; Chen, Jing; Yu, Bo; Chen, Yan; Liu, Meilin

    2017-10-16

    Solid oxide cell (SOC) based energy conversion systems have the potential to become the cleanest and most efficient systems for reversible conversion between electricity and chemical fuels due to their high efficiency, low emission, and excellent fuel flexibility. Broad implementation of this technology is however hindered by the lack of high-performance electrode materials. While many perovskite-based materials have shown remarkable promise as electrodes for SOCs, cation enrichment or segregation near the surface or interfaces is often observed, which greatly impacts not only electrode kinetics but also their durability and operational lifespan. Since the chemical and structural variations associated with surface enrichment or segregation are typically confined to the nanoscale, advanced experimental and computational tools are required to probe the detailed composition, structure, and nanostructure of these near-surface regions in real time with high spatial and temporal resolutions. In this review article, an overview of the recent progress made in this area is presented, highlighting the thermodynamic driving forces, kinetics, and various configurations of surface enrichment and segregation in several widely studied perovskite-based material systems. A profound understanding of the correlation between the surface nanostructure and the electro-catalytic activity and stability of the electrodes is then emphasized, which is vital to achieving the rational design of more efficient SOC electrode materials with excellent durability. Furthermore, the methodology and mechanistic understanding of the surface processes are applicable to other materials systems in a wide range of applications, including thermo-chemical photo-assisted splitting of H 2 O/CO 2 and metal-air batteries.

  12. A flameless catalytic combustion-based thermoelectric generator for powering electronic instruments on gas pipelines

    International Nuclear Information System (INIS)

    Xiao, Heng; Qiu, Kuanrong; Gou, Xiaolong; Ou, Qiang

    2013-01-01

    Highlights: ► MPPT is used to improve the feature that TEG output is sensitive to load variation. ► The improved feature makes TEG suitable to power electronic device on gas pipeline. ► Test shows heat transfer uniformity plays an important role in improving TEG output. ► It can get an optimized TEG by uniformly filling a thermal insulation material. - Abstract: This paper presents a flameless catalytic combustion-based thermoelectric power generator that uses commercial thermoelectric modules. The structure of the thermoelectric generator (TEG) is introduced and the power performance is measured based on a designed circuit system. The open circuit voltage of the TEG is about 7.3 V. The maximum power output can reach up to 6.5 W when the load resistance matches the TEG internal resistance. However, the system output is sensitive to load variation. To improve this characteristic, maximum power point tracking technique is used and results in an open circuit voltage of 13.8 V. The improved characteristic makes the TEG system a good charger to keep the lead acid battery fully charged so as to meet the needs of electronic instruments on gas pipelines. In addition, the combustion features have been investigated based on the temperature measurement. Test results show that the uniformity of combustion heat transfer process and the combustion chamber structure play important roles in improving system power output. It can get an optimized TEG system (maximum power output: 8.3 W) by uniformly filling a thermal insulation material (asbestos) to avoid a non-uniform combustion heat transfer process

  13. Energy Efficient Microlith-Based Catalytic Reactor and Recuperator for Air Quality Control Applications

    Science.gov (United States)

    Vilekar, Saurabh A.; Hawley, Kyle; Junaedi, Christian; Crowder, Bruce; Prada, Julian; Mastanduno, Richard; Perry, Jay L.; Kayatin, Matthew J.

    2017-01-01

    Precision Combustion, Inc. (PCI) and NASA’s Marshall Space Flight Center (MSFC) have been developing, characterizing, and optimizing high temperature catalytic oxidizers (HTCO) based on PCI’s patented Microlith technology to meet the requirements of future extended human spaceflight explorations. Previous efforts focused on integrating PCI’s HTCO unit with a compact, simple recuperative heat exchanger to reduce the overall system size and weight. Significant improvement was demonstrated over traditional approaches of integrating the HTCO with an external recuperative heat exchanger. While the critical target performance metrics were achieved, the thermal effectiveness of PCI’s recuperator remained a potential area of improvement to further reduce the energy requirements of the integrated system. Using the same material combinations and an improved recuperator design, the redesigned prototype has experimentally demonstrated 20 – 30% reduction (flow dependent) in steady state power consumption compared to the earlier prototype without compromising the destruction efficiency of methane and volatile organic compounds (VOCs). Moreover, design modifications and improvements allow our redesigned prototype to be more easily manufactured compared to traditional brazed plate-fin recuperator designs. The redesigned prototype was delivered to MSFC for validation testing. Here, we report and discuss the performance of the improved prototype HTCO unit with a high efficiency recuperative heat exchanger based on testing at PCI and MSFC. The device is expected to provide a reliable and robust means of disposing of trace levels of methane and VOCs by oxidizing them into carbon dioxide and water in order to maintain clean air in enclosed spaces, such as crewed spacecraft cabins.

  14. 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

  15. Ultrasensitive colorimetric detection of Cu2+ ion based on catalytic oxidation of L-cysteine.

    Science.gov (United States)

    Yin, Kun; Li, Bowei; Wang, Xiaochun; Zhang, Weiwei; Chen, Lingxin

    2015-02-15

    As an essential element, copper ion (Cu(2+)) plays important roles in human beings for its participation in diverse metabolic processes as a cofactor and/or a structural component of enzymes. However, excessive uptake of Cu(2+) ion gives rise to the risk of certain diseases. So, it is important to develop simple ways to monitor and detect Cu(2+) ion. In this study, a simple, facile colorimetric sensor for the ultrasensitive determination of Cu(2+) ion was developed based on the following principle: L-cysteine and 1-chloro-2,4-dinitrobenzene (CDNB) could be conjugated to form the yellow product 2,4-dinitrophenylcysteine (DNPC), which was measurable at 355nm; however, upon addition of Cu(2+) ion, the absorbance of DNPC would be decreased owing to the Cu(2+) ion catalytic oxidation of L-cysteine to L-cystine in the presence of O2. Thus, the colorimetric detection of Cu(2+) ion could be achieved. The optimal pH, buffer, temperature and incubation time for the colorimetric sensor were obtained of pH 6.8 in 0.1M HEPES solution, 90 °C and 50 min, respectively. A good linearity within the range of 0.8-10 nM (r = 0.996) was attained, with a high detectability up to 0.5nM. Analyses of Cu(2+) ion in drinking water, lake water, seawater and biological samples were carried out and the method performances were found to agree well with that obtained by ICP-MS. The developed simple colorimetric sensor proved applicable for Cu(2+) ion determination in real samples with high sensitivity and selectivity. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. 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

  17. The activity of catalytic systems based on zero-valent nickel complexes in propene dimerization

    Energy Technology Data Exchange (ETDEWEB)

    Shmidt, F.K.; Mironova, L.V.; Proidakov, A.G.; Kalabin, G.A.; Ratovskii, G.V.; Dmitrieva, T.V.

    1978-01-01

    Catalytic systems consisting of Ni(PPh/sub 3/) or Ni(P(OEt)/sub 3/)/sub 4/, Lewis acids BF/sub 3/ or BF/sub 3/.OEt/sub 2/, and Broensted acids HF, H/sub 2/SO/sub 4/, EtOH, or H/sub 2/O (even in trace amounts), but not HCl, showed high catalytic activities (i.e., hexene yields of 1200-1600 g-mole per g-atom Ni per hour) with 67-84% methylpentenes. In the absence of Lewis acids, the catalytic activity decreased and linear hexenes were favored (up to 65%). The activity of the systems containing no Broensted additives (i.e., when the solvents were thoroughly dehydrated and evacuated) was very low (50 g-mole hexene per g-atom Ni per hour). Proton, phosphorus-31, and fluorine-19 NMR studies identified nickel hydride complexes (NHC) with PF(OEt)/sub 2/ ligands in the Ni(P(OC/sub 2/H/sub 5/)/sub 3/)/sub 4// BF/sub 3/(OC/sub 2/H/sub 5/)/sub 2//C/sub 2/H/sub 5/OH system, and a UV spectroscopic study showed that the catalytic activity was proportional to the concentration of NHC in the system. Tables, spectra, and 16 references.

  18. The catalytic kinetic method for the determination of trace formaldehyde (FA) base on a bromate-eosin Y system

    Science.gov (United States)

    Tang, Yufang; Chen, Hao; Weng, Chao; Tang, Xiaohui; Zhang, Miaoling; Yang, Qiongqiong; Hu, Tao; Cai, Changqun

    A new simple and highly sensitive catalytic kinetic method for the determination of trace amount of FA in food sample has been established. The method was based on the catalytic effect of FA on the oxidation of eosin Y by potassium bromate in present of phosphoric acid. The reaction was monitored spectrophotometrically by measuring the decrease in absorbance of eosin Y at 518 nm. Under the optimized experimental conditions, the developed method allowed the determination of FA in the range of 0.03-0.6 μg mL-1 with a good precision, and the limit of detection was down to 0.00988 μg mL-1. The relative standard deviation of five replicate measurements for the determination of FA in concentration 0.12 μg mL-1 was 1.8%. The proposed method was successfully applied to the determination of FA in food directly and satisfactory results were obtained.

  19. Strip biosensor for amplified detection of nerve growth factor-beta based on a molecular translator and catalytic DNA circuit.

    Science.gov (United States)

    Liu, Jun; Lai, Ting; Mu, Kejie; Zhou, Zheng

    2014-10-07

    We have demonstrated a new visual detection approach based on a molecular translator and a catalytic DNA circuit for the detection of nerve growth factor-beta (NGF-β). In this assay, a molecular translator based on the binding-induced DNA strand-displacement reaction was employed to convert the input protein to an output DNA signal. The molecular translator is composed of a target recognition element and a signal output element. Target recognition is achieved by the binding of the anti-NGF-β antibody to the target protein. Polyclonal anti-NGF-β antibody is conjugated to DNA1 and DNA2. The antibody conjugated DNA1 is initially hybridized to DNA3 to form a stable DNA1/DNA3 duplex. In the presence of NGF-β, the binding of the same target protein brings DNA1 and DNA2 into close proximity, resulting in an increase in their local effective concentration. This process triggers the strand-displacement reaction between DNA2 and DNA3 and releases the output DNA3. The released DNA3 is further amplified by a catalytic DNA circuit. The product of the catalytic DNA circuit is detected by a strip biosensor. This proposed assay has high sensitivity and selectivity with a dynamic response ranging from 10 fM to 10 pM, and its detection limit is 10 fM of NGF-β. This work provides a sensitive, enzyme-free, and universal strategy for the detection of other proteins.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. In-situ XPS analysis of oxidized and reduced plasma deposited ruthenium-based thin catalytic films

    Science.gov (United States)

    Balcerzak, Jacek; Redzynia, Wiktor; Tyczkowski, Jacek

    2017-12-01

    A novel in-situ study of the surface molecular structure of catalytically active ruthenium-based films subjected to the oxidation (in oxygen) and reduction (in hydrogen) was performed in a Cat-Cell reactor combined with a XPS spectrometer. The films were produced by the plasma deposition method (PEMOCVD). It was found that the films contained ruthenium at different oxidation states: metallic (Ru0), RuO2 (Ru+4), and other RuOx (Ru+x), of which content could be changed by the oxidation or reduction, depending on the process temperature. These results allow to predict the behavior of the Ru-based catalysts in different redox environments.

  5. DNA-Catalytically Active Gold Nanoparticle Conjugates-Based Colorimetric Multidimensional Sensor Array for Protein Discrimination.

    Science.gov (United States)

    Wei, Xiangcong; Chen, Zhengbo; Tan, Lulu; Lou, Tianhong; Zhao, Yan

    2017-01-03

    A series of single-strand oligonucleotides functionalized catalytically active gold nanoparticle (AuNPs) as nonspecific receptors have been designed to build a protein sensing array. We take advantage of the correlation between the catalytic activity and the exposed surface area of AuNPs, i.e., DNA-proteins interactions mask the surface area of AuNPs, leading to poor catalytic performance of AuNPs. As the number of DNA-bound proteins increases, the surfaces of AuNPs become more masked; thus, the time of 4- nitrophenol/NaBH 4 reaction for color change (yellow → colorless) of the solution increases. Taking advantage of three nonspecific SH-labeled DNA sequences (A15, C15, and T15) as array sensing elements and the color-change time (CCT) of the solution as signal readout, colorimetric response patterns can be obtained on the array and identified via linear discriminant analysis (LDA). Eleven proteins have been completely distinguished with 100% accuracy with the naked eye at the 30 nM level. Remarkably, two similar proteins (bovine serum albumin and human serum albumin), two different proteins (bovine serum albumin and concanavalin) at the same concentration, and the mixtures of the two proteins with different molar ratios have been discriminated with 100%. The practicability of this sensor array is further validated by high accuracy (100%) identification of 11 proteins in human serum samples.

  6. 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.

  7. 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.)

  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. Heterogeneous catalytic ozonation of biologically pretreated Lurgi coal gasification wastewater using sewage sludge based activated carbon supported manganese and ferric oxides as catalysts.

    Science.gov (United States)

    Zhuang, Haifeng; Han, Hongjun; Hou, Baolin; Jia, Shengyong; Zhao, Qian

    2014-08-01

    Sewage sludge of biological wastewater treatment plant was converted into sewage sludge based activated carbon (SBAC) with ZnCl₂ as activation agent, which supported manganese and ferric oxides as catalysts (including SBAC) to improve the performance of ozonation of real biologically pretreated Lurgi coal gasification wastewater. The results indicated catalytic ozonation with the prepared catalysts significantly enhanced performance of pollutants removal and the treated wastewater was more biodegradable and less toxic than that in ozonation alone. On the basis of positive effect of higher pH and significant inhibition of radical scavengers in catalytic ozonation, it was deduced that the enhancement of catalytic activity was responsible for generating hydroxyl radicals and the possible reaction pathway was proposed. Moreover, the prepared catalysts showed superior stability and most of toxic and refractory compounds were eliminated at successive catalytic ozonation runs. Thus, the process with economical, efficient and sustainable advantages was beneficial to engineering application. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. 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

    Heterogeneous catalysis studies were conducted on two crushed solid oxide fuel cell (SOFC) anodes in fixed-bed reactors. The baseline anode was Ni/ScYSZ (Ni/scandia and yttria stabilized zirconia), the other was Ni/ScYSZ modified with Pd/doped ceria (Ni/ScYSZ/Pd-CGO). Three main types......-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...

  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. Catalytic treatment

    Energy Technology Data Exchange (ETDEWEB)

    Bindley, W T.R.

    1931-04-18

    An apparatus is described for the catalytic treatment of liquids, semi-liquids, and gases comprising a vessel into which the liquid, semi-liquid, or gas to be treated is introduced through a common inlet to a chamber within the vessel whence it passes to contact with a catalyst through radially arranged channels or passages to a common outlet chamber.

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

    Science.gov (United States)

    2015-01-01

    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. PMID:25941559

  14. Synthesis, Characterization, and Photoelectrochemical Catalytic Studies of a Water-Stable Zinc-Based Metal-Organic Framework.

    Science.gov (United States)

    Altaf, Muhammad; Sohail, Manzar; Mansha, Muhammad; Iqbal, Naseer; Sher, Muhammad; Fazal, Atif; Ullah, Nisar; Isab, Anvarhusein A

    2018-02-09

    Metal-organic frameworks (MOFs) are class of porous materials that can be assembled in a modular manner by using different metal ions and organic linkers. Owing to their tunable structural properties, these materials are found to be useful for gas storage and separation technologies, as well as for catalytic applications. A cost-effective zinc-based MOF ([Zn(bpcda)(bdc)] n ) is prepared by using N,N'-bis(pyridin-4-ylmethylene)cyclohexane-1,4-diamine [N,N'-bis(pyridin-4-ylmethylene)cyclohexane-1,4-diamine] and benzenedicarboxylic acid (bdc) linkers. This new material exhibits remarkable photoelectrochemical (PEC) catalytic activity in water splitting for the evolution of oxygen. Notably, this non-noble metal-based MOF, without requiring immobilization on other supports or containing metal particles, produced a highest photocurrent density of 31 μA cm -2 at 0.9 V, with appreciable stability and negligible photocorrosion. Advantageously for the oxygen evolution process, no external reagents or sacrificial agents are required in the aqueous electrolyte solution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 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.

  16. Producing carbon-based boundary films from catalytically active lubricant additives

    Science.gov (United States)

    Erdemir, Ali; Mane, Anil U.; Elam, Jeffrey W.; Ramirez, Giovanni; Eryilmaz, Osman

    2018-04-24

    A lubricant composition includes an oil including a plurality of long-chain hydrocarbon molecules. A quantity of a catalytically active metal-organic additive is mixed with the oil. The metal-organic additive is formulated to fragment the long-chain hydrocarbon molecules of the oil into at least one of dimers and trimers under the influence of at least one of a mechanical loading and a thermal loading. In some embodiments, the metal-organic additive includes a compound of formula II: ##STR00001## where: X is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg or Cn, and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are alkyl or alkyl halide.

  17. Synthesis, spectroscopic characterization and catalytic oxidation ...

    Indian Academy of Sciences (India)

    were characterized by infrared, electronic, electron paramagnetic resonance ... The catalytic oxidation property of ruthenium(III) complexes were also ... cies at room temperature. ..... aldehyde part of Schiff base ligands, catalytic activ- ity of new ...

  18. Spectrophotometric determination of nitrite based on its catalytic effect on the reaction of nuclear fast red and potassium bromate

    Directory of Open Access Journals (Sweden)

    HASSAN ZAVVAR MOUSAVI

    2009-08-01

    Full Text Available A highly selective and sensitive catalytic spectrophotometric method was developed for the determination of nitrite in water samples. The method is based on its catalytic effect on the nuclear fast red–potassium bromate redox reaction in acidic medium. The reaction was followed spectrophotometrically by measuring the change in the absorbance at 518 nm of nuclear fast red 5 min after initiation of the reaction. In this study, the experimental parameters were optimized and the effects of other cations and anions on the determination of nitrite were examined. The calibration graph was linear in the range 2.0–45 µg mL-1 of nitrite. The relative standard deviations for the determination of 15 and 30 µg mL-1 of nitrite were 3.1 and 1.75 %, respectively (n = 8. The detection limit calculated from three times the standard deviation of the blank 3Sb was 0.7 µg mL-1. The method was successfully applied to the determination of nitrite in spiked tap, natural and wastewater samples.

  19. Hydrogen storage evaluation based on investigations of the catalytic properties of metal/metal oxides in electrospun carbon fibers

    Energy Technology Data Exchange (ETDEWEB)

    Im, Ji Sun; Lee, Young-Seak [Department of Fine Chemical Engineering and Chemistry, Chungnam National University, Daejeon 305-764 (Korea); Park, Soo-Jin [Department of Chemistry, Inha University, Incheon 402-751 (Korea); Kim, Taejin [Core Technology Research Center for Fuel Cell, Jeollabuk-do 561-844 (Korea)

    2009-05-15

    In order to investigate the catalytic capacity of metals and metal oxides based on electrospun carbon fibers for improving hydrogen storage, electrospinning and heat treatments were carried out to obtain metal/metal oxide-embedded carbon fibers. Although the fibers were treated with the same activation procedure, they had different pore structures, due to the nature of the metal oxide. When comparing the catalytic capacity of metal and metal oxide, metal exhibits better performance as a catalyst for the improvement of hydrogen storage, when considering the hydrogen storage system. When a metal oxide with an m.p. lower than the temperature of heat treatment was used, the metal oxide was changed to metal during the heat treatment, developing a micropore structure. The activation process produced a high specific surface area of up to 2900 m{sup 2}/g and a pore volume of up to 2.5 cc/g. The amount of hydrogen adsorption reached approximately 3 wt% at 100 bar and room temperature. (author)

  20. Catalytic wet air oxidation of coke-plant wastewater on ruthenium-based eggshell catalysts in a bubbling bed reactor.

    Science.gov (United States)

    Yang, M; Sun, Y; Xu, A H; Lu, X Y; Du, H Z; Sun, C L; Li, C

    2007-07-01

    Catalytic wet air of coke-plant wastewater was studied in a bubbling bed reactor. Two types of supported Ru-based catalysts, eggshell and uniform catalysts, were employed. Compared with the results in the wet air oxidation of coke-plant wastewater, supported Ru uniform catalysts showed high activity for chemical oxygen demand (COD) and ammonia/ammonium compounds (NH3-N) removal at temperature of 250 degrees C and pressure of 4.8 MPa, and it has been demonstrated that the catalytic activity of uniform catalyst depended strongly on the distribution of active sites of Ru on catalyst. Compared to the corresponding uniform catalysts with the same Ru loading (0.25 wt.% and 0.1 wt.%, respectively), the eggshell catalysts showed higher activities for CODcr removal and much higher activities for NH3-N degradation. The high activity of eggshell catalyst for treatment of coke-plant wastewater can be attributed to the higher density of active Ru sites in the shell layer than that of the corresponding uniform catalyst with the same Ru loading. It has been also evidenced that the active Ru sites in the internal core of uniform catalyst have very little or no contribution to CODcr and NH3-N removal in the total oxidation of coke-plant wastewater.

  1. Acid–Base Bifunctional Hf Nanohybrids Enable High Selectivity in the Catalytic Conversion of Ethyl Levulinate to γ-Valerolactone

    Directory of Open Access Journals (Sweden)

    Weibo Wu

    2018-06-01

    Full Text Available The catalytic upgrading of bio-based platform molecules is a promising approach for biomass valorization. However, most solid catalysts are not thermally or chemically stable, and are difficult to prepare. In this study, a stable organic phosphonate–hafnium solid catalyst (PPOA–Hf was synthesized, and acid–base bifunctional sites were found to play a cooperative role in the cascade transfer hydrogenation and cyclization of ethyl levulinate (EL to γ-valerolactone (GVL. Under relatively mild reaction conditions of 160 °C for 6 h, EL was completely converted to GVL with a good yield of 85%. The apparent activation energy was calculated to be 53 kJ/mol, which was lower than other solid catalysts for the same reaction. In addition, the PPOA-Hf solid catalyst did not significantly decrease its activity after five recycles, and no evident leaching of Hf was observed, indicating its high stability and potential practical application.

  2. A comparison of cationic polymerization and esterification for end-point detection in the catalytic thermometric titration of organic bases.

    Science.gov (United States)

    J Greenhow, E; Viñas, P

    1984-08-01

    A systematic comparison has been made of two indicator systems for the non-aqueous catalytic thermometric titration of strong and weak organic bases. The indicator reagents, alpha-methylstyrene and mixtures of acetic anhydride and hydroxy compounds, are shown to give results (for 14 representative bases) which do not diner significantly in coefficient of variation or titration error. Calibration graphs for all the samples, in the range 0.01-0.1 meq, are linear, with correlation coefficients of 0.995 or better. Aniline, benzylamine, n-butylamine, morpholine, pyrrole, l-dopa, alpha-methyl-l-dopa, dl-alpha-alanine, dl-leucine and l-cysteine cannot be determined when acetic anhydride is present in the sample solution, but some primary and second amines can. This is explained in terms of rates of acetylation of the amino groups.

  3. 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 ...

  4. Theoretical study for pyridinium-based ionic liquid 1-ethylpyridinium trifluoroacetate: synthesis mechanism, electronic structure, and catalytic reactivity.

    Science.gov (United States)

    Zhu, Xueying; Cui, Peng; Zhang, Dongju; Liu, Chengbu

    2011-07-28

    By performing density functional theory calculations, we have studied the synthesis mechanism, electronic structure, and catalytic reactivity of a pyridinium-based ionic liquid, 1-ethylpyridinium trifluoroacetate ([epy](+)[CF(3)COO](-)). It is found that the synthesis of the pyridinium salt follows a S(N)2 mechanism. The electronic structural analyses show that multiple H bonds are generally involved in the pyridinium-based ionic liquid, which may play a decisive role for stabilizing the ionic liquid. The cation-anion interaction mainly involves electron transfer between the lone pair of the oxygen atom in the anion and the antibonding orbital of the C*-H bond (C* denotes the carbon atom at the ortho-position of nitrogen atom in the cation). This present work has also given clearly the catalytic mechanism of [epy](+)[CF(3)COO](-) toward to the Diels-Alder (D-A) reaction of acrylonitrile with 2-methyl-1,3-butadiene. Both the cation and anion are shown to play important roles in promoting the D-A reaction. The cation [epy](+), as a Lewis acid, associates the C≡N group by C≡N···H H bond to increase the polarity of the C═C double bond in acrylonitrile, while the anion CF(3)COO(-) links with the methyl group in 2-methyl-1,3-butadiene by C-H···O H bond, which weakens the electron-donating capability of methyl and thereby lowers the energy barrier of the D-A reaction. The present results are expected to provide valuable information for the design and application of pyridinium-based ionic liquids. © 2011 American Chemical Society

  5. A quartz-based micro catalytic methane sensor by high resolution screen printing

    Science.gov (United States)

    Lu, Wenshuai; Jing, Gaoshan; Bian, Xiaomeng; Yu, Hongyan; Cui, Tianhong

    2016-02-01

    A micro catalytic methane sensor was proposed and fabricated on a bulk fused quartz substrate using a high resolution screen printing technique for the first time, with reduced power consumption and optimized sensitivity. The sensor was designed by the finite element method and quartz was chosen as the substrate material and alumina support with optimized dimensions. Fabrication of the sensor consisted of two MEMS processes, lift-off and high resolution screen printing, with the advantages of high yield and uniformity. When the sensor’s regional working temperature changes from 250 °C to 470 °C, its sensitivity increases, as well as the power consumption. The highest sensitivity can reach 1.52 mV/% CH4. A temperature of 300 °C was chosen as the optimized working temperature, and the sensor’s sensitivity, power consumption, nonlinearity and response time are 0.77 mV/% CH4, 415 mW, 2.6%, and 35 s, respectively. This simple, but highly uniform fabrication process and the reliable performance of this sensor may lead to wide applications for methane detection.

  6. A quartz-based micro catalytic methane sensor by high resolution screen printing

    International Nuclear Information System (INIS)

    Lu, Wenshuai; Jing, Gaoshan; Bian, Xiaomeng; Yu, Hongyan; Cui, Tianhong

    2016-01-01

    A micro catalytic methane sensor was proposed and fabricated on a bulk fused quartz substrate using a high resolution screen printing technique for the first time, with reduced power consumption and optimized sensitivity. The sensor was designed by the finite element method and quartz was chosen as the substrate material and alumina support with optimized dimensions. Fabrication of the sensor consisted of two MEMS processes, lift-off and high resolution screen printing, with the advantages of high yield and uniformity. When the sensor’s regional working temperature changes from 250 °C to 470 °C, its sensitivity increases, as well as the power consumption. The highest sensitivity can reach 1.52 mV/% CH 4 . A temperature of 300 °C was chosen as the optimized working temperature, and the sensor’s sensitivity, power consumption, nonlinearity and response time are 0.77 mV/% CH 4 , 415 mW, 2.6%, and 35 s, respectively. This simple, but highly uniform fabrication process and the reliable performance of this sensor may lead to wide applications for methane detection. (paper)

  7. 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.

  8. Alumina- and titania-based monolithic catalysts for low temperature selective catalytic reduction of nitrogen oxides

    International Nuclear Information System (INIS)

    Blanco, J.; Avila, P.; Suarez, S.; Martin, J.A.; Knapp, C.

    2000-01-01

    The selective catalytic reduction of NO+NO 2 (NO x ) at low temperature (180-230C) with ammonia has been investigated with copper-nickel and vanadium oxides supported on titania and alumina monoliths. The influence of the operating temperature, as well as NH 3 /NO x and NO/NO 2 inlet ratios has been studied. High NO x conversions were obtained at operating conditions similar to those used in industrial scale units with all the catalysts. Reaction temperature, ammonia and nitrogen dioxide inlet concentration increased the N 2 O formation with the copper-nickel catalysts, while no increase was observed with the vanadium catalysts. The vanadium-titania catalyst exhibited the highest DeNO x activity, with no detectable ammonia slip and a low N 2 O formation when NH 3 /NO x inlet ratio was kept below 0.8. TPR results of this catalyst with NO/NH 3 /O 2 , NO 2 /NH 3 /O 2 and NO/NO 2 /NH 3 /O 2 feed mixtures indicated that the presence of NO 2 as the only nitrogen oxide increases the quantity of adsorbed species, which seem to be responsible for N 2 O formation. When NO was also present, N 2 O formation was not observed

  9. 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.

  10. High Selectively Catalytic Conversion of Lignin-Based Phenols into para-/m-Xylene over Pt/HZSM-5

    Directory of Open Access Journals (Sweden)

    Guozhu Liu

    2016-01-01

    Full Text Available High selectively catalytic conversion of lignin-based phenols (m-cresol, p-cresol, and guaiacol into para-/m-xylene was performed over Pt/HZSM-5 through hydrodeoxygenation and in situ methylation with methanol. It is found that the p-/m-xylene selectivity is uniformly higher than 21%, and even increase up to 33.5% for m-cresol (with phenols/methanol molar ratio of 1/8. The improved p-/m-xylene selectivity in presence of methanol is attributed to the combined reaction pathways: methylation of m-cresol into xylenols followed by HDO into p-/m-xylene, and HDO of m-cresol into toluene followed by methylation into p-/m-xylene. Comparison of the product distribution over a series of catalysts indicates that both metals and supporters have distinct effect on the p-/m-xylene selectivity.

  11. 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.

  12. 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.

  13. Gold nanocatalyst-based immunosensing strategy accompanying catalytic reduction of 4-nitrophenol for sensitive monitoring of chloramphenicol residue.

    Science.gov (United States)

    Que, Xiaohua; Tang, Dianyong; Xia, Biyun; Lu, Minghua; Tang, Dianping

    2014-06-09

    A new competitive-type immunosensing system based on gold nanoparticles toward catalytic reduction of 4-nitrophenol (4-NP) was developed for sensitive monitoring of antibiotic residue (chloramphenicol, CAP, used in this case) by using ultraviolet-visible (UV-vis) spectrometry. Gold nanoparticle (AuNP) with 16 nm in diameter was initially synthesized and functionalized with CAP-bovine serum albumin (CAP-BSA) conjugate, which were used as the competitor on monoclonal anti-CAP antibody-coated polystyrene microtiter plate (MTP). In the presence of target CAP, the labeled CAP-BSA on the AuNP competed with target CAP for the immobilized antibody on the MTP. The conjugated amount of CAP-BSA-AuNP on the MTP decreased with the increase of target CAP in the sample. Upon addition of 4-NP and NaBH4 into the MTP, the carried AuNP could catalytically reduce 4-NP to 4-aminophenol (4-AP), and the as-produced 4-AP could be monitored by using UV-vis absorption spectroscopy. Experimental results indicated that the absorbance at 403 nm increased with the increment of target CAP concentration in the sample, and exhibited a dynamic range from 0.1 to 100 ng mL(-1) with a detection limit (LOD) of 0.03 ng mL(-1) at the 3s(blank) level. Intra- and inter-assay coefficients of variation were lower than 5.5% and 8.0%, respectively. In addition, the methodology was evaluated for CAP spiked honey and milk samples, respectively. The recovery was 92-112%. Copyright © 2014. Published by Elsevier B.V.

  14. 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.

  15. 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.

  16. 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.

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

    Science.gov (United States)

    Dietrich, Markus; Hagen, Gunter; Reitmeier, Willibald; Burger, Katharina; Hien, Markus; Grass, Philippe; Kubinski, David; Visser, Jaco; Moos, Ralf

    2017-07-12

    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 NO x 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.

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

    Science.gov (United States)

    Dietrich, Markus; Hagen, Gunter; Reitmeier, Willibald; Burger, Katharina; Hien, Markus; Grass, Philippe; Kubinski, David; Visser, Jaco; Moos, Ralf

    2017-01-01

    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. PMID:28704929

  19. 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.

  20. Catalytic pyrolysis of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Vail' eva, N A; Buyanov, R A

    1979-01-01

    Catalytic pyrolysis of petroleum fractions (undecane) was performed with the object of clarifying such questions as the mechanism of action of the catalyst, the concepts of activity and selectivity of the catalyst, the role of transport processes, the temperature ranges and limitations of the catalytic process, the effect of the catalyst on secondary processes, and others. Catalysts such as quartz, MgO, Al/sub 2/O/sub 3/, were used. Analysis of the experimental findings and the fact that the distribution of products is independent of the nature of the surface, demonstrate that the pyrolysis of hydrocarbons in the presence of catalysts is based on the heterogeneous-homogeneous radical-chain mechanism of action, and that the role of the catalysts reduces to increasing the concentration of free radicals. The concept of selectivity cannot be applied to catalysts here, since they do not affect the mechanism of the unfolding of the process of pyrolysis and their role consists solely in initiating the process. In catalytic pyrolysis the concepts of kinetic and diffusive domains of unfolding of the catalytic reaction do not apply, and only the outer surface of the catalyst is engaged, whereas the inner surface merely promotes deletorious secondary processes reducing the selectivity of the process and the activity of the catalyst. 6 references, 2 figures.

  1. 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)

  2. 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

    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...

  3. CATALYTIC ENZYME-BASED METHODS FOR WATER TREATMENT AND WATER DISTRIBUTION SYSTEM DECONTAMINATION

    Science.gov (United States)

    Current chemistry-based decontaminants for chemical or biological warfare agents and related toxic materials are caustic and have the potential for causing material and environmental damage. In addition, most are bulk liquids that require significant logistics and storage capabil...

  4. 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.

  5. Deep catalytic oxidative desulfurization (ODS) of dibenzothiophene (DBT) with oxalate-based deep eutectic solvents (DESs).

    Science.gov (United States)

    Lü, Hongying; Li, Pengcheng; Deng, Changliang; Ren, Wanzhong; Wang, Shunan; Liu, Pan; Zhang, Han

    2015-07-07

    An oxalate-based DES with a tetrabutyl ammonium chloride and oxalate acid molar ratio of 1/2 (TBO1 : 2) exhibited high activity in oxidative desulfurization (ODS) of dibenzothiophene (DBT) under mild reaction conditions. It is potentially a promising and highly environmentally friendly approach for desulfurization of fuels.

  6. 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

  7. DNA-based catalytic enantioselective intermolecular oxa-Michael addition reactions

    NARCIS (Netherlands)

    Megens, Rik P.; Roelfes, Gerard

    2012-01-01

    Using the DNA-based catalysis concept, a novel Cu(II) catalyzed enantioselective oxa-Michael addition of alcohols to enones is reported. Enantioselectivities of up to 86% were obtained. The presence of water is important for the reactivity, possibly by reverting unwanted side reactions such as

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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+.

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

    Directory of Open Access Journals (Sweden)

    Lei Zhang

    2018-04-01

    Full Text Available 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: ① The denitration efficiency of Mn-based bimetallic catalysts mainly relates to the metal type, the metal load quantity and the catalyst adjuvant type. ② 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. ③ 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+.

  14. Synthesis, characterization and catalytic activity of acid-base bifunctional materials through protection of amino groups

    Energy Technology Data Exchange (ETDEWEB)

    Shao, Yanqiu [College of Chemistry, Jilin University, Changchun 130023 (China); College of Chemistry, Mudanjiang Normal University, Mudanjiang 157012 (China); Liu, Heng; Yu, Xiaofang [College of Chemistry, Jilin University, Changchun 130023 (China); Guan, Jingqi, E-mail: guanjq@jlu.edu.cn [College of Chemistry, Jilin University, Changchun 130023 (China); Kan, Qiubin, E-mail: qkan@mail.jlu.edu.cn [College of Chemistry, Jilin University, Changchun 130023 (China)

    2012-03-15

    Graphical abstract: Acid-base bifunctional mesoporous material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized under low acidic medium through protection of amino groups. Highlights: Black-Right-Pointing-Pointer The acid-base bifunctional material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized through protection of amino groups. Black-Right-Pointing-Pointer The obtained bifunctional material was tested for aldol condensation. Black-Right-Pointing-Pointer The SO{sub 3}H-SBA-15-NH{sub 2} catalyst containing amine and sulfonic acid groups exhibited excellent acid-basic properties. -- Abstract: Acid-base bifunctional mesoporous material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized under low acidic medium through protection of amino groups. X-ray diffraction (XRD), N{sub 2} adsorption-desorption, transmission electron micrographs (TEM), back titration, {sup 13}C magic-angle spinning (MAS) NMR and {sup 29}Si magic-angle spinning (MAS) NMR were employed to characterize the synthesized materials. The obtained bifunctional material was tested for aldol condensation reaction between acetone and 4-nitrobenzaldehyde. Compared with monofunctional catalysts of SO{sub 3}H-SBA-15 and SBA-15-NH{sub 2}, the bifunctional sample of SO{sub 3}H-SBA-15-NH{sub 2} containing amine and sulfonic acid groups exhibited excellent acid-basic properties, which make it possess high activity for the aldol condensation.

  15. 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.

  16. A Viscosity-Based Model for Bubble-Propelled Catalytic Micromotors

    Directory of Open Access Journals (Sweden)

    Zhen Wang

    2017-06-01

    Full Text Available Micromotors have shown significant potential for diverse future applications. However, a poor understanding of the propelling mechanism hampers its further applications. In this study, an accurate mechanical model of the micromotor has been proposed by considering the geometric asymmetry and fluid viscosity based on hydrodynamic principles. The results obtained from the proposed model are in a good agreement with the experimental results. The effects of the semi-cone angle on the micromotor are re-analyzed. Furthermore, other geometric parameters, like the length-radius aspect ratio, exert great impact on the velocity. It is also observed that micromotors travel much slower in highly viscous solutions and, hence, viscosity plays an important role.

  17. Synthesis, catalytic and biological activity of novel dinuclear copper complex with Schiff base

    Institute of Scientific and Technical Information of China (English)

    WEI Danyi; LI Ning; LU Gui; YAO Kemin

    2006-01-01

    A novel dinuclear copper complex with tetraglycol aldehyde-phenylalanine Schiff base has been synthesized. It was characterized and formulated as [Cu2L(NO3)]NO3 by elemental analysis,magnetic susceptibility, TG-DTA, IR, EPR and 1H NMR spectra. The obtained complex can be used as a good catalyst for the polymerization of methyl methacrylate (MMA). The optimum polymerization conditions are: MMNcatalyst = 500 (molar ratio); [catalyst] = 7.5×10-3 mol. L-1; dioxane as solvent;80℃; 6 h. Polymethyl methacrylate (PMMA) with 80% conversion, 7.2×105 viscosity-average molecular weight and 60.5% syndiotacticity was obtained. This complex has also been shown to play an important role in scavenging O-·2.

  18. 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%).

  19. 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.

  20. Local Environment and Nature of Cu Active Sites in Zeolite-Based Catalysts for the Selective Catalytic Reduction of NOx

    NARCIS (Netherlands)

    Deka, U.|info:eu-repo/dai/nl/325811202; Lezcano-Gonzalez, I.; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397; Beale, A.M.|info:eu-repo/dai/nl/325802068

    2013-01-01

    Cu-exchanged zeolites have demonstrated widespread use as catalyst materials in the abatement of NOx, especially from mobile sources. Recent studies focusing on Cu-exchanged zeolites with the CHA structure have demonstrated them to be excellent catalysts in the ammonia-assisted selective catalytic

  1. 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

  2. Structural analysis of CuO / CeO2-based catalytic materials intended for PROX reaction: Part I

    International Nuclear Information System (INIS)

    Neiva, L.S.; Simoes, A.N.; Bispo, A.; Ribeiro, M.A.; Gama, L.

    2011-01-01

    This work relates the synthesis process of CuO/CeO 2 catalytic materials by a combustion reaction method as well as it introduces a structural analysis of the developed material, this structural analysis had as main focus to evaluate the influence of the doping substance (CuO) when being incorporated in the hostess matrix structure that is CeO 2 . The CuO/CeO catalytic materials developed in this work are destined to preferential oxidation of CO reaction (PROX). The developed materials were characterized by XRD, SEM and textural complete analysis by the BET method. According to the results, the CuO incorporation changed crystallinity of the structure of the catalytic materials. On the other hand, the morphologic and textural characteristics did not showed significant differences regarding the presence of the doping substance (CuO) in the structure of the developed materials. The porosity of the structures of the developed catalytic materials belongs to the type macroporous. (author)

  3. Magnetic nickel ferrite nanoparticles as highly durable catalysts for catalytic transfer hydrogenation of bio-based aldehydes

    DEFF Research Database (Denmark)

    He, Jian; Yang, Song; Riisager, Anders

    2018-01-01

    Magnetic nickel ferrite (NiFe2O4) nanoparticles were exploited as stable and easily separable heterogeneous catalysts for catalytic transfer hydrogenation (CTH) of furfural to furfuryl alcohol with 2-propanol as both the hydrogen source and the solvent providing 94% product yield at 180 degrees C...

  4. Synthesis, characterizations and catalytic studies of a new two-dimensional metal-organic framework based on Co-carboxylate secondary building units

    Science.gov (United States)

    Bagherzadeh, Mojtaba; Ashouri, Fatemeh; Đaković, Marijana

    2015-03-01

    A metal-organic framework [Co3(BDC)3(DMF)2(H2O)2] was synthesized and structurally characterized. X-ray single crystal analysis revealed that the framework contains a 2D polymeric chain through coordination of 1,4-benzenedicarboxylic acid linker ligand to cobalt centers. The polymer crystallize in monoclinic P21/n space group with a=13.989(3) Å, b=9.6728(17) Å, c=16.707(3) Å, and Z=2. The polymer features a framework based on the perfect octahedral Co-O6 secondary building units. The catalytic activities of [Co3(BDC)3(DMF)2(H2O)2]n for olefins oxidation was conducted. The heterogeneous catalyst could be facilely separated from the reaction mixture, and reused three times without significant degradation in catalytic activity. Furthermore, no contribution from homogeneous catalysis of active species leaching into reaction solution was detected.

  5. Heterobimetallic transition metal/rare earth metal bifunctional catalysis: a Cu/Sm/Schiff base complex for syn-selective catalytic asymmetric nitro-Mannich reaction.

    Science.gov (United States)

    Handa, Shinya; Gnanadesikan, Vijay; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2010-04-07

    The full details of a catalytic asymmetric syn-selective nitro-Mannich reaction promoted by heterobimetallic Cu/Sm/dinucleating Schiff base complexes are described, demonstrating the effectiveness of the heterobimetallic transition metal/rare earth metal bifunctional catalysis. The first-generation system prepared from Cu(OAc)(2)/Sm(O-iPr)(3)/Schiff base 1a = 1:1:1 with an achiral phenol additive was partially successful for achieving the syn-selective catalytic asymmetric nitro-Mannich reaction. The substrate scope and limitations of the first-generation system remained problematic. After mechanistic studies on the catalyst prepared from Sm(O-iPr)(3), we reoptimized the catalyst preparation method, and a catalyst derived from Sm(5)O(O-iPr)(13) showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)(3). The optimal system with Sm(5)O(O-iPr)(13) was applicable to various aromatic, heteroaromatic, and isomerizable aliphatic N-Boc imines, giving products in 66-99% ee and syn/anti = >20:1-13:1. Catalytic asymmetric synthesis of nemonapride is also demonstrated using the catalyst derived from Sm(5)O(O-iPr)(13).

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

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

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Ling [College of Chemistry and Chemical Engineering, Inner Mongolia University for Nationalities, Tongliao 028000 (China); Wang, Chunhua [Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry, Jilin University, Changchun 130023 (China); Guan, Jingqi, E-mail: guanjq@jlu.edu.cn [Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry, Jilin University, Changchun 130023 (China)

    2014-05-01

    Acid-base bifunctional mesoporous catalysts Al-KIT-6-NH{sub 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{sub 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{sub 2} with different Si/Al ratios has been successfully prepared. • 79.4% Yield was obtained over 46-Al-KIT-6-NH{sub 2} within 20 min in Knoevenagel reaction. • Low Al-content Al-KIT-6-NH{sub 2} shows better catalytic stability than high Al-content catalysts. • There is acid-base synergistic effect in Knoevenagel reaction.

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

    International Nuclear Information System (INIS)

    Zhou, Fuyi; Yao, Yao; Luo, Jianjun; Zhang, Xing; Zhang, Yu; Yin, Dengyang; Gao, Fenglei; Wang, Po

    2017-01-01

    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 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 −15 to 10 −11  g mL −1 and a detection limit of 0.43 × 10 −15  g mL −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 −16  g mL −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 −16  g mL −1 level with a dynamic range spanning 5 orders of magnitude.

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

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Liuqing [Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081 (China); Liu, Xiaoying [College of Science, Science and Technological Innovation Platform, Hunan Agricultural University, Hunan, Changsha 410128 (China); Lu, Qiujun; Huang, Na [Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081 (China); Liu, Meiling, E-mail: liumeilingww@126.com [Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081 (China); Zhang, Youyu; Yao, Shouzhuo [Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081 (China)

    2016-08-03

    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{sub 2}O{sub 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{sub 2}O{sub 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.

  15. 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.

  16. 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)

  17. 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

  18. Reversible switching of fluorophore property based on intrinsic conformational transition of adenylate kinase during its catalytic cycle.

    Science.gov (United States)

    Fujii, Akira; Hirota, Shun; Matsuo, Takashi

    2013-07-17

    Adenylate kinase shows a conformational transition (OPEN and CLOSED forms) during substrate binding and product release to mediate the phosphoryl transfer between ADP and ATP/AMP. The protein motional characteristics will be useful to construct switching systems of fluorophore properties caused by the catalytic cycle of the enzyme. This paper demonstrates in situ reversible switching of a fluorophore property driven by the conformational transition of the enzyme. The pyrene-conjugated mutant adenylate kinase is able to switch the monomer/excimer emission property of pyrene on addition of ADP or P(1)P(5)-di(adenosine-5')pentaphosphate (Ap5A, a transition state analog). The observation under the dilute condition (~0.1 μM) indicates that the emission spectral change was caused by the motion of a protein molecule and not led by protein-protein interactions through π-π stacking of pyrene rings. The switching can be reversibly conducted by using hexokinase-coupling reaction. The fashion of the changes in emission intensities at various ligand concentrations is different between ADP, Mg(2+)-bound ADP, and Mg(2+)-bound Ap5A. The emission property switching is repeatable by a sequential addition of a substrate in a one-pot process. It is proposed that the property of a synthetic molecule on the enzyme surface is switchable in response to the catalytic cycle of adenylate kinase.

  19. 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.

  20. Endurance and failure of an alumina-based monopropellant microthruster with integrated heater, catalytic bed and temperature sensors

    Science.gov (United States)

    Khaji, Zahra; Klintberg, Lena; Barbade, Dhananjay; Palmer, Kristoffer; Thornell, Greger

    2017-05-01

    Monopropellant ceramic microthrusters with an integrated heater, catalytic bed and two temperature sensors, but of various designs, were manufactured by milling a fluidic channel and chamber, and a nozzle, and screen printing platinum patterns on green tapes of alumina that were stacked and laminated before sintering. In order to increase the surface area of the catalytic bed, the platinum paste was mixed with a sacrificial paste that disappeared during sintering, to leave behind a porous and rough layer. As an early development level in manufacturing robust and high-temperature tolerant microthrusters, the influence of design on the temperature gradients and dry temperature tolerance of the devices was studied. On average, the small reaction chambers showed a more than 1.5 times higher dry temperature tolerance (in centigrade) compared to devices with larger chambers, independent of the heater and device size. However, for a given temperature, big devices consumed on average 2.9 times more power than the small ones. It was also found that over the same area and under the same heating conditions, devices with small chambers were subjected to approximately 40% smaller temperature differences. A pressure test done on two small devices with small chambers revealed that pressures of at least 26.3 bar could be tolerated. Above this pressure, the interfaces failed but the devices were not damaged. To investigate the cooling effect of the micropropellant, the endurance of a full thruster was also studied under wet testing where it was fed with 31 wt.% hydrogen peroxide. The thruster demonstrated complete evaporation and/or full decomposition at a power above 3.7 W for a propellant flow of 50 µl min-1. At this power, the catalytic bed locally reached a temperature of 147 °C. The component was successfully heated to an operating temperature of 307 °C, where it cracked. Under these firing conditions, and assuming complete decomposition, calculations give a thrust and

  1. 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

  2. Enhancement of catalytic activity of platinum-based nanoparticles towards electrooxidation of ethanol through interfacial modification with heteropolymolybdates

    Science.gov (United States)

    Barczuk, Piotr J.; Lewera, Adam; Miecznikowski, Krzysztof; Zurowski, Artur; Kulesza, Pawel J.

    As evidenced from the increase of electrocatalytic currents measured under voltammetric and chronoamperometric conditions, the activity of bimetallic Pt-Ru and Pt-Sn nanoparticles towards oxidation of ethanol is increased by modification of their surfaces with ultra-thin films of phosphododecamolybdic acid (H 3PMo 12O 40). The enhancement effect has been most pronounced in a case of heteropolymolybdate-modified carbon-supported Pt-Sn catalysts. Independent high-resolution XPS measurements indicate the ability of heteropolymolybdates to stabilize tin (in bimetallic Pt-Sn particles) at higher oxidation states (presumably as tin oxo species). The overall activation effect may also be ascribed to changes in the morphology of catalytic films following modification with heteropolymolybdates. Presence of the polyoxometallate is also likely to increase of the interfacial population of reactive oxo groups in the vicinity of platinum centers.

  3. Enhancement of catalytic activity of platinum-based nanoparticles towards electrooxidation of ethanol through interfacial modification with heteropolymolybdates

    Energy Technology Data Exchange (ETDEWEB)

    Barczuk, Piotr J.; Lewera, Adam; Miecznikowski, Krzysztof; Zurowski, Artur; Kulesza, Pawel J. [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland)

    2010-05-01

    As evidenced from the increase of electrocatalytic currents measured under voltammetric and chronoamperometric conditions, the activity of bimetallic Pt-Ru and Pt-Sn nanoparticles towards oxidation of ethanol is increased by modification of their surfaces with ultra-thin films of phosphododecamolybdic acid (H{sub 3}PMo{sub 12}O{sub 40}). The enhancement effect has been most pronounced in a case of heteropolymolybdate-modified carbon-supported Pt-Sn catalysts. Independent high-resolution XPS measurements indicate the ability of heteropolymolybdates to stabilize tin (in bimetallic Pt-Sn particles) at higher oxidation states (presumably as tin oxo species). The overall activation effect may also be ascribed to changes in the morphology of catalytic films following modification with heteropolymolybdates. Presence of the polyoxometallate is also likely to increase of the interfacial population of reactive oxo groups in the vicinity of platinum centers. (author)

  4. Preparation, characterization and testing of SiC-based catalytic sponges as structured catalysts for Fischer-Tropsch synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Baudry, A.; Schaub, G. [Karlsruhe Institute of Technology (KIT), Karlsruhe (Germany). Engler-Bunte-Inst.

    2011-07-01

    Solid sponges (open-cell foams) may be used as catalyst support, due to favorable thermal properties and low pressure drop. As an example, they may lead to improved temperature control in Fischer-Tropsch applications, if compared to fixed beds of catalyst particles. The aim of this study was to develop and test a wet method for impregnating ceramic foam materials with a CoRe/{gamma}-Al{sub 2}O{sub 3} catalyst. Defined catalyst layers were generated on 20 ppi SiC-sponges. Resulting catalytic activities are nearly identical to those of the corresponding powder catalyst material. The difference observed can be explained by either mass transfer limitation or backmixing in the fixed bed configuration used. (orig.)

  5. 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.)

  6. Electrochemical sensor for catechol and dopamine based on a catalytic molecularly imprinted polymer-conducting polymer hybrid recognition element.

    Science.gov (United States)

    Lakshmi, Dhana; Bossi, Alessandra; Whitcombe, Michael J; Chianella, Iva; Fowler, Steven A; Subrahmanyam, Sreenath; Piletska, Elena V; Piletsky, Sergey A

    2009-05-01

    One of the difficulties with using molecularly imprinted polymers (MIPs) and other electrically insulating materials as the recognition element in electrochemical sensors is the lack of a direct path for the conduction of electrons from the active sites to the electrode. We have sought to address this problem through the preparation and characterization of novel hybrid materials combining a catalytic MIP, capable of oxidizing the template, catechol, with an electrically conducting polymer. In this way a network of "molecular wires" assists in the conduction of electrons from the active sites within the MIP to the electrode surface. This was made possible by the design of a new monomer that combines orthogonal polymerizable functionality; comprising an aniline group and a methacrylamide. Conducting films were prepared on the surface of electrodes (Au on glass) by electropolymerization of the aniline moiety. A layer of MIP was photochemically grafted over the polyaniline, via N,N'-diethyldithiocarbamic acid benzyl ester (iniferter) activation of the methacrylamide groups. Detection of catechol by the hybrid-MIP sensor was found to be specific, and catechol oxidation was detected by cyclic voltammetry at the optimized operating conditions: potential range -0.6 V to +0.8 V (vs Ag/AgCl), scan rate 50 mV/s, PBS pH 7.4. The calibration curve for catechol was found to be linear to 144 microM, with a limit of detection of 228 nM. Catechol and dopamine were detected by the sensor, whereas analogues and potentially interfering compounds, including phenol, resorcinol, hydroquinone, serotonin, and ascorbic acid, had minimal effect (< or = 3%) on the detection of either analyte. Non-imprinted hybrid electrodes and bare gold electrodes failed to give any response to catechol at concentrations below 0.5 mM. Finally, the catalytic properties of the sensor were characterized by chronoamperometry and were found to be consistent with Michaelis-Menten kinetics.

  7. 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

  8. Ethanolysis conversion of spent frying oils over aluminium, calcium-phosphate based bi-functional formulated catalysts. Catalytic activity assessment study

    Energy Technology Data Exchange (ETDEWEB)

    Al-Zaini, Essam O.; Chesterfield, Dean; Adesina, Adesoji A. [The Univ. of New South Wales, Sydney (Australia). Reactor Engineering and Technology Group; Olsen, John [The Univ. of New South Wales, Sydney (Australia). School of Mechanical and Manufacturing Engineering

    2013-06-01

    The current study compares the catalytic performance of two bi-functional solid catalysts for the transesterification of waste cooking vegetable oil in presence of bio-ethanol acyl-acceptor. The two catalysts were aluminum oxide and seashell-derived calcium oxide supported K{sub 3}PO{sub 4}. The catalytic activity of the produced catalyst samples were assessed and evaluated in terms of their textural and surface chemical properties. Evaluative runs showed that increased amounts of K{sub 3}PO{sub 4} have differently controlled the textural and surface chemical property of the finally synthesised catalyst samples. The behaviour revealed a strong correlation between the percentage yield of ethyl esters EEY% and acid-base site density and strength between the two types of catalysts. Possible leaching test of the catalysts was also used as a measure of performance and as a result, the optimum catalyst, on the basis of both ester yield and resistance to leaching was identified as the sample containing between 10 and 15wt% of K{sub 3}PO{sub 4} on AlO{sub 3} and CaO respectively. (orig.)

  9. Comparison of Elemental Mercury Oxidation Across Vanadium and Cerium Based Catalysts in Coal Combustion Flue Gas: Catalytic Performances and Particulate Matter Effects.

    Science.gov (United States)

    Wan, Qi; Yao, Qiang; Duan, Lei; Li, Xinghua; Zhang, Lei; Hao, Jiming

    2018-03-06

    This paper discussed the field test results of mercury oxidation activities over vanadium and cerium based catalysts in both coal-fired circulating fluidized bed boiler (CFBB) and chain grate boiler (CGB) flue gases. The characterizations of the catalysts and effects of flue gas components, specifically the particulate matter (PM) species, were also discussed. The catalytic performance results indicated that both catalysts exhibited mercury oxidation preference in CGB flue gas rather than in CFBB flue gas. Flue gas component studies before and after dust removal equipment implied that the mercury oxidation was well related to PM, together with gaseous components such as NO, SO 2 , and NH 3 . Further investigations demonstrated a negative PM concentration-induced effect on the mercury oxidation activity in the flue gases before the dust removal, which was attributed to the surface coverage by the large amount of PM. In addition, the PM concentrations in the flue gases after the dust removal failed in determining the mercury oxidation efficiency, wherein the presence of different chemical species in PM, such as elemental carbon (EC), organic carbon (OC) and alkali (earth) metals (Na, Mg, K, and Ca) in the flue gases dominated the catalytic oxidation of mercury.

  10. The Enhanced Catalytic Activities of Asymmetric Au-Ni Nanoparticle Decorated Halloysite-Based Nanocomposite for the Degradation of Organic Dyes

    Science.gov (United States)

    Jia, Lei; Zhou, Tao; Xu, Jun; Li, Xiaohui; Dong, Kun; Huang, Jiancui; Xu, Zhouqing

    2016-02-01

    Janus particles (JPs) are unique among the nano-/microobjects because they provide asymmetry and can thus impart drastically different chemical or physical properties. In this work, we have fabricated the magnetic halloysite nanotube (HNT)-based HNTs@Fe3O4 nanocomposite (NCs) and then anchored the Janus Au-Ni or isotropic Au nanoparticles (NPs) to the surface of external wall of sulfydryl modified magnetic nanotubes. The characterization by physical methods authenticates the successful fabrication of two different magnetic HNTs@Fe3O4@Au and HNTs@Fe3O4@Au-Ni NCs. The catalytic activity and recyclability of the two NCs have been evaluated considering the degradation of Congo red (CR) and 4-nitrophenol (4-NP) using sodium borohydride as a model reaction. The results reveal that the symmetric Au NPs participated NCs display low activity in the degradation of the above organic dyes. However, a detailed kinetic study demonstrates that the employ of bimetallic Janus Au-Ni NPs in the NCs indicates enhanced catalytic activity, owing to the structurally specific nature. Furthermore, the magnetic functional NCs reported here can be used as recyclable catalyst which can be recovered simply by magnet.

  11. 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.

  12. Highly selective and sensitive paper-based colorimetric sensor using thiosulfate catalytic etching of silver nanoplates for trace determination of copper ions.

    Science.gov (United States)

    Chaiyo, Sudkate; Siangproh, Weena; Apilux, Amara; Chailapakul, Orawon

    2015-03-25

    A novel, highly selective and sensitive paper-based colorimetric sensor for trace determination of copper (Cu(2+)) ions was developed. The measurement is based on the catalytic etching of silver nanoplates (AgNPls) by thiosulfate (S2O3(2-)). Upon the addition of Cu(2+) to the ammonium buffer at pH 11, the absorption peak intensity of AuNPls/S2O3(2-) at 522 nm decreased and the pinkish violet AuNPls became clear in color as visible to the naked eye. This assay provides highly sensitive and selective detection of Cu(2+) over other metal ions (K(+), Cr(3+), Cd(2+), Zn(2+), As(3+), Mn(2+), Co(2+), Pb(2+), Al(3+), Ni(2+), Fe(3+), Mg(2+), Hg(2+) and Bi(3+)). A paper-based colorimetric sensor was then developed for the simple and rapid determination of Cu(2+) using the catalytic etching of AgNPls. Under optimized conditions, the modified AgNPls coated at the test zone of the devices immediately changes in color in the presence of Cu(2+). The limit of detection (LOD) was found to be 1.0 ng mL(-1) by visual detection. For semi-quantitative measurement with image processing, the method detected Cu(2+) in the range of 0.5-200 ng mL(-1)(R(2)=0.9974) with an LOD of 0.3 ng mL(-1). The proposed method was successfully applied to detect Cu(2+) in the wide range of real samples including water, food, and blood. The results were in good agreement according to a paired t-test with results from inductively coupled plasma-optical emission spectrometry (ICP-OES). Copyright © 2015. Published by Elsevier B.V.

  13. Improvement of Toluene Selectivity via the Application of an Ethanol Oxidizing Catalytic Cell Upstream of a YSZ-Based Sensor for Air Monitoring Applications

    Science.gov (United States)

    Sato, Tomoaki; Breedon, Michael; Miura, Norio

    2012-01-01

    The sensing characteristics of a yttria-stabilized zirconia (YSZ)-based sensor utilizing a NiO sensing-electrode (SE) towards toluene (C7H8) and interfering gases (C3H6, H2, CO, NO2 and C2H5OH) were evaluated with a view to selective C7H8 monitoring in indoor atmospheres. The fabricated YSZ-based sensor showed preferential responses toward 480 ppb C2H5OH, rather than the target 50 ppb C7H8 at an operational temperature of 450 °C under humid conditions (RH ≃ 32%). To overcome this limitation, the catalytic activity of Cr2O3, SnO2, Fe2O3 and NiO powders were evaluated for their selective ethanol oxidation ability. Among these oxides, SnO2 was found to selectively oxidize C2H5OH, thus improving C7H8 selectivity. An inline pre-catalytic cell loaded with SnO2 powder was installed upstream of the YSZ-based sensor utilizing NiO-SE, which enabled the following excellent abilities by selectively catalyzing common interfering gases; sensitive ppb level detection of C7H8 lower than the established Japanese Guideline value; low interferences from 50 ppb C3H6, 500 ppb H2, 100 ppb CO, 40 ppb NO2, as well as 480 ppb C2H5OH. These operational characteristics are all indicative that the developed sensor may be suitable for real-time C7H8 concentration monitoring in indoor environments. PMID:22666053

  14. 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.

  15. Synthesis, Thermal, Electrical and Catalytic Studies of Some Transition Metal Polychelates of Bis-bidentate Schiff Base

    Institute of Scientific and Technical Information of China (English)

    BANSOD Ashish; ASWAR Anand

    2007-01-01

    Polychelates of Mn(Ⅱ),Fe(Ⅱ),Co(Ⅱ), Ni(Ⅱ),Cu(Ⅱ),Zn(Ⅱ) and Cd(Ⅱ) with the bis salen-type ligand derivedfrom 4,4'-bis[(salicylaldehyde-5)azo]biphenyl and 1,4-diaminobutane have been synthesized.All the polychelates have been characterized by elemental analysis,magnetic susceptibility measurements,IR,electronic spectra and thermogravimetric studies.All the complexes isolated in solid state are dark coloured and insoluble in water and common organic solvents.The ligand behaves as a bis-bidentate molecule coordinating through the phenolic oxygen and azomethine nitrogen atoms.The thermal decomposition of these metal complexes was investigated by thermogravimetric analysis and data have been analyzed for kinetic parameters using Broido equation.The solid-state electrical conductivity of the ligand and its polychelates in the form of compressed pellet was studied in the temperature range from 313 to 413 K.All the polychelates were found to show semiconducting nature.The Mn(Ⅱ),Fe(Ⅱ),Co(Ⅱ) and Ni(Ⅱ) polychelates have been assessed for the catalytic epoxidation of styrene.

  16. A molecularly imprinted electrochemiluminescence sensor based on the mimetic enzyme catalytic effect for ultra-trace Ni2+ determination.

    Science.gov (United States)

    Yang, Bin; Li, Jianping; Zhang, Lianming; Xu, Guobao

    2016-10-21

    A novel molecularly imprinted polymer (MIP) electrochemiluminescence (MIP-ECL) sensor was developed for the highly sensitive and selective determination of ultra-trace levels of Ni 2+ . The complex Ni 2+ -dimethylglyoxime (Ni-DMG) was chosen as the template molecule to construct the MIP and then acted as a mimetic enzyme to catalyse the oxidisation of luminol to enhance the ECL signal. When the imprinted cavities were occupied by Ni-DMG in the rebinding process, the ECL intensities produced by the luminol-H 2 O 2 ECL system on the MIP-modified electrode surface increased with increased concentration of the Ni-DMG complex. The highly sensitive determination of Ni 2+ was achieved through a catalytic reaction. This technique could be used for the quantitative analysis of Ni 2+ with concentrations from 3.0 × 10 -12 mol L -1 to 6.0 × 10 -9 mol L -1 . The detection limit was 1.01 × 10 -12 mol L -1 , which is much lower than that reported previously. In addition, the allowable amounts of interference ions in the MIP-ECL sensor were higher than that in other common molecularly imprinted sensors because of its excellent recognition of 3D cavity-to-complex molecules and ligand-to-metal ions. This method was successfully used to determine Ni 2+ in real samples, such as apples, carrots and grapes, and has been proven feasible for practical applications.

  17. 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.

  18. 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.

  19. 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

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

    Directory of Open Access Journals (Sweden)

    Yu-Tung Chien

    2013-01-01

    Full Text Available 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.

  1. Catalytic modification of cellulose and hemicellulose - Sugarefine

    Energy Technology Data Exchange (ETDEWEB)

    Repo, T. [Helsinki Univ. (Finland),Laboratory of Inorganic Chemistry], email: timo.repo@helsinki.fi

    2012-07-01

    The main goal of the project is to develop catalytic methods for the modification of lignocellulose-based saccharides in the biorefineries. The products of these reactions could be used for example as biofuel components, raw materials for the chemical industry, solvents and precursors for biopolymers. The catalyst development aims at creating efficient, selective and green catalytic methods for profitable use in biorefineries. The project is divided in three work packages: In WP1 (Catalytic dehydration of cellulose) the aim is at developing non-toxic, efficient methods for the catalytic dehydration of cellulose the target molecule being here 5-hydroxymethylfurfural (5-HMF). 5-HMF is an interesting platform chemical for the production of fuel additives, solvents and polymers. In WP2 (Catalytic reduction), the objective of the catalytic reduction studies is to produce commercially interesting monofunctional chemicals, such as 1-butanol or 2-methyltetrahydrofuran (2-MeTHF). In WP3 (Catalytic oxidation), the research focuses on developing a green and efficient oxidation method for producing acids. Whereas acetic and formic acids are bulk chemicals, diacids such as glucaric and xylaric acids are valuable specialty chemicals for detergent, polymer and food production.

  2. 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.

  3. SHORT COMMUNICATION CATALYTIC KINETIC ...

    African Journals Online (AJOL)

    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 ...

  4. 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.

  5. Catalytic Aminohalogenation of Alkenes and Alkynes.

    Science.gov (United States)

    Chemler, Sherry R; Bovino, Michael T

    2013-06-07

    Catalytic aminohalogenation methods enable the regio- and stereoselective vicinal difunctionalization of alkynes, allenes and alkenes with amine and halogen moieties. A range of protocols and reaction mechanisms including organometallic, Lewis base, Lewis acid and Brønsted acid catalysis have been disclosed, enabling the regio- and stereoselective synthesis of halogen-functionalized acyclic amines and nitrogen heterocycles. Recent advances including aminofluorination and catalytic enantioselective aminohalogenation reactions are summarized in this review.

  6. 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

  7. 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.

  8. Crystal structures and catalytic performance of three new methoxy substituted salen type nickel(II) Schiff base complexes derived from meso-1,2-diphenyl-1,2-ethylenediamine

    Science.gov (United States)

    Ghaffari, Abolfazl; Behzad, Mahdi; Pooyan, Mahsa; Amiri Rudbari, Hadi; Bruno, Giuseppe

    2014-04-01

    Three new nickel(II) complexes of a series of methoxy substituted salen type Schiff base ligands were synthesized and characterized by IR, UV-Vis and 1H NMR spectroscopy and elemental analysis. The ligands were synthesized from the condensation of meso-1,2-diphenyl-1,2-ethylenediamine with n-methoxysalicylaldehyde (n = 3, 4 and 5). Crystal structures of these complexes were determined. Electrochemical behavior of the complexes was studied by means of cyclic voltammetry in DMSO solutions. Catalytic performance of the complexes was studied in the epoxidation of cyclooctene using tert-butylhydroperoxide (TBHP) as oxidant under various conditions to find the optimum operating parameters. Low catalytic activity with moderate epoxide selectivity was observed in in-solvent conditions but in the solvent-free conditions, enhanced catalytic activity with high epoxide selectivity was achieved.

  9. 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

  10. 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.

  11. 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...

  12. 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.

  13. 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.

  14. Catalytic nanoporous membranes

    Science.gov (United States)

    Pellin, Michael J; Hryn, John N; Elam, Jeffrey W

    2013-08-27

    A nanoporous catalytic membrane which displays several unique features Including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity. Also provided is a method for producing a catalytic membrane having flow-through pores and discreet catalytic clusters adhering to the inside surfaces of the pores.

  15. 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.

  16. 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.

  17. Carbon-based catalytic briquettes for the reduction of NO: Effect of H{sub 2}SO{sub 4} and HNO{sub 3} carbon support treatment

    Energy Technology Data Exchange (ETDEWEB)

    A. Boyano; M.E. Galvez; R. Moliner; M.J. Lazaro [Instituto de Carboquimica CSIC, Zaragoza (Spain)

    2008-08-15

    The influence of treating carbon with sulphuric and nitric acids on the activity of a carbon-based briquette catalyst for NO reduction with NH{sub 3} was examined in a fixed-bed reactor at low temperature (150{sup o}C). The briquette catalysts were prepared from a low-rank coal and a commercial tar pitch. The active phase was impregnated from a suspension of ashes of petroleum coke by means of an equilibrium adsorption method. The catalytic behaviour of NO reduction over acid treated briquettes was found to vary with the surface characteristics of the carbon support. This suggests that the number of oxygen-containing sites as well as vanadium load and dispersion affect the reaction activity. In the presence of oxygen, the SCR activity is enhanced with a nitric acid treatment, activity is promoted by the presence of acidic surface groups such as carboxyl and lactone, which can help not only to create a reservoir of reactants on the catalysts surface but also to improve the dispersion or even increase the amount of vanadium loading. Therefore, the results of this study suggest that the formation of acidic sites on the surface is an important step for NO reduction with NH{sub 3} over carbon-based catalysts. Additional techniques such as XPS and TPD to characterize the oxygen surface and those such as N{sub 2} adsorption to characterize the textural properties were also used in this study. 46 refs., 6 figs., 5 tabs.

  18. 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

  19. 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.

  20. 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_3H@Fe/JHC) and base (Na_2SiO_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_3H@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_2SiO_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 force

  1. Catalytic cracking models developed for predictive control purposes

    Directory of Open Access Journals (Sweden)

    Dag Ljungqvist

    1993-04-01

    Full Text Available The paper deals with state-space modeling issues in the context of model-predictive control, with application to catalytic cracking. Emphasis is placed on model establishment, verification and online adjustment. Both the Fluid Catalytic Cracking (FCC and the Residual Catalytic Cracking (RCC units are discussed. Catalytic cracking units involve complex interactive processes which are difficult to operate and control in an economically optimal way. The strong nonlinearities of the FCC process mean that the control calculation should be based on a nonlinear model with the relevant constraints included. However, the model can be simple compared to the complexity of the catalytic cracking plant. Model validity is ensured by a robust online model adjustment strategy. Model-predictive control schemes based on linear convolution models have been successfully applied to the supervisory dynamic control of catalytic cracking units, and the control can be further improved by the SSPC scheme.

  2. 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

  3. 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.

  4. Colorimetric determination of copper ions based on the catalytic leaching of silver from the shell of silver-coated gold nanorods

    International Nuclear Information System (INIS)

    Wang, Xiaokun; Chen, Lingxin; Chen, Ling

    2014-01-01

    We have developed a method for the colorimetric determination of copper ions (Cu 2+ ) that is based on the use of silver-coated gold nanorods (Au–Ag NRs). Its outstanding selectivity and sensitivity result from the catalytic leaching process that occurs between Cu 2+ , thiosulfate (S 2 O 3 2− ), and the surface of the Au–Ag NRs. The intrinsic color of the Au–Ag NRs changes from bright red to bluish green with decreasing thickness of the silver coating. The addition of Cu 2+ accelerates the leaching of silver from the shell caused in the presence of S 2 O 3 2− . This result in a decrease in the thickness of the silver shell which is accompanied a change in color and absorption spectra of the colloidal solution. The shifts in the absorption maxima are linearly related to the concentrations of Cu 2+ over the 3–1,000 nM concentration range (R = 0.996). The method is cost effective and was applied to the determination of Cu 2+ in real water samples. (author)

  5. Fragment-Based Discovery of a Potent, Orally Bioavailable Inhibitor That Modulates the Phosphorylation and Catalytic Activity of ERK1/2.

    Science.gov (United States)

    Heightman, Tom D; Berdini, Valerio; Braithwaite, Hannah; Buck, Ildiko M; Cassidy, Megan; Castro, Juan; Courtin, Aurélie; Day, James E H; East, Charlotte; Fazal, Lynsey; Graham, Brent; Griffiths-Jones, Charlotte M; Lyons, John F; Martins, Vanessa; Muench, Sandra; Munck, Joanne M; Norton, David; O'Reilly, Marc; Palmer, Nick; Pathuri, Puja; Reader, Michael; Rees, David C; Rich, Sharna J; Richardson, Caroline; Saini, Harpreet; Thompson, Neil T; Wallis, Nicola G; Walton, Hugh; Wilsher, Nicola E; Woolford, Alison J-A; Cooke, Michael; Cousin, David; Onions, Stuart; Shannon, Jonathan; Watts, John; Murray, Christopher W

    2018-05-31

    Aberrant activation of the MAPK pathway drives cell proliferation in multiple cancers. Inhibitors of BRAF and MEK kinases are approved for the treatment of BRAF mutant melanoma, but resistance frequently emerges, often mediated by increased signaling through ERK1/2. Here, we describe the fragment-based generation of ERK1/2 inhibitors that block catalytic phosphorylation of downstream substrates such as RSK but also modulate phosphorylation of ERK1/2 by MEK without directly inhibiting MEK. X-ray crystallographic and biophysical fragment screening followed by structure-guided optimization and growth from the hinge into a pocket proximal to the C-α helix afforded highly potent ERK1/2 inhibitors with excellent kinome selectivity. In BRAF mutant cells, the lead compound suppresses pRSK and pERK levels and inhibits proliferation at low nanomolar concentrations. The lead exhibits tumor regression upon oral dosing in BRAF mutant xenograft models, providing a promising basis for further optimization toward clinical pERK1/2 modulating ERK1/2 inhibitors.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. Catalytic Conversion of Biofuels

    DEFF Research Database (Denmark)

    Jørgensen, Betina

    This thesis describes the catalytic conversion of bioethanol into higher value chemicals. The motivation has been the unavoidable coming depletion of the fossil resources. The thesis is focused on two ways of utilising ethanol; the steam reforming of ethanol to form hydrogen and the partial oxida...

  12. Catalytic methanol dissociation

    International Nuclear Information System (INIS)

    Alcinikov, Y.; Fainberg, V.; Garbar, A.; Gutman, M.; Hetsroni, G.; Shindler, Y.; Tatrtakovsky, L.; Zvirin, Y.

    1998-01-01

    Results of the methanol dissociation study on copper/potassium catalyst with alumina support at various temperatures are presented. The following gaseous and liquid products at. The catalytic methanol dissociation is obtained: hydrogen, carbon monoxide, carbon dioxide, methane, and dimethyl ether. Formation rates of these products are discussed. Activation energies of corresponding reactions are calculated

  13. 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.

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

    Directory of Open Access Journals (Sweden)

    Atikah Kadri

    2015-06-01

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

  15. 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

  16. Direct synthesis of acid-base bifunctionalized hexagonal mesoporous silica and its catalytic activity in cascade reactions.

    Science.gov (United States)

    Shang, Fanpeng; Sun, Jianrui; Wu, Shujie; Liu, Heng; Guan, Jingqi; Kan, Qiubin

    2011-03-01

    A series of efficient acid-base bifunctionalized hexagonal mesoporous silica (HMS) catalysts contained aminopropyl and propanesulfonic acid have been synthesized through a simple co-condensation by protection of amino group. The results of small-angle XRD, TEM, and N(2) adsorption-desorption measurements show that the resultant materials have mesoscopic structures. X-ray photoelectron spectroscopies, elemental analysis (EA), back titration, (29)Si NMR and (13)C NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The resultant catalysts exhibit excellent acid-basic properties, which make them possess high activity for one-pot deacetalization-Knoevenagel and deacetalization-nitroaldol (Henry) reactions. Copyright © 2010 Elsevier Inc. All rights reserved.

  17. The forming of coke by catalytic cracking of black mineral oil by catalysts on the base of activated aluminium alloys

    International Nuclear Information System (INIS)

    Mirzaeva, L.M.; Akhverdiev, R.B.; Aliev, Eh.T.; Gusejnova, A.D.; Gadzhi-Kasumov, V.S.; Akerson, V.I.; Sarmurzina, R.G.

    1995-01-01

    The paper deals with an investigation in coke formation under black mineral oil reactions on oxide catalysts which care based on activated aluminium alloys containing 2-20% of active components of In and Ga. The coke yield is of extreme nature and depends on the content of active components in the catalyst composition. The application of thermogravimetric method shows that the oxidation of coke depositions after black mineral oil cracking proceeds in the same temperature range while after the steam-water treatment of coked catalysts the oxidation of coke deposition proceeds at higher temperatures with different temperature maximums which points to the inhomogeneity of coke depositions. It is shown that the catalyst phase composition changes significantly during the reaction under the effect of reaction mixture. 4 refs., 3 figs

  18. Optical detection of organophosphorus compounds based on Mn-doped ZnSe d-dot enzymatic catalytic sensor.

    Science.gov (United States)

    Gao, Xue; Tang, Guangchao; Su, Xingguang

    2012-01-01

    In this paper, we report a sensitive and selective method for detection of organophosphorus compounds (OPs) based on Mn:ZnSe d-dots-enzyme-hydrogen peroxide (H(2)O(2)) fluorescence quenching system. Acetylcholine esterase (AChE) can hydrolyze acetylcholine (ACh) to choline. Subsequently, choline oxidase (ChOx) oxidizes choline to generate H(2)O(2). The enzyme-generated H(2)O(2) can quench the fluorescence of Mn:ZnSe d-dots. When paraoxon are introduced in solution, it can interact with the active centers of AChE and decrease the enzyme activity. This leads to the decrease of the H(2)O(2) production and then the fluorescence quenching rate of Mn:ZnSe d-dots. Experimental results showed that the enzyme inhibition percentage of Mn:ZnSe d-dots-ChOx-AChE-ACh system was proportional to the logarithm of paraoxon in the range 4.84×10(-11) to 4.84×10(-6) mol/L with the detection limit (S/N=3) of 1.31×10(-11) mol/L. The proposed biosensor has been employed for quick determination of paraoxon in tap water and milk samples with satisfactory reproducibility and accuracy. This nano-biosensor was proved to be sensitive, rapid, simple and tolerance of most interfering substances. Copyright © 2012 Elsevier B.V. All rights reserved.

  19. A novel electrochemical sensor based on metal-organic framework for electro-catalytic oxidation of L-cysteine.

    Science.gov (United States)

    Hosseini, Hadi; Ahmar, Hamid; Dehghani, Ali; Bagheri, Akbar; Tadjarodi, Azadeh; Fakhari, Ali Reza

    2013-04-15

    A novel electrochemical sensor based on Au-SH-SiO₂ nanoparticles supported on metal-organic framework (Au-SH-SiO₂@Cu-MOF) has been developed for electrocatalytic oxidation and determination of L-cysteine. The Au-SH-SiO₂@Cu-MOF was characterized by scanning electron microscopy, transmission electron microscopy, x-ray diffraction and cyclic voltammetry. The electrochemical behavior of L-cysteine at the Au-SH-SiO₂@Cu-MOF was investigated by cyclic voltammetry. The Au-SH-SiO₂@Cu-MOF showed a very efficient electrocatalytic activity for the oxidation of L-cysteine in 0.1 M phosphate buffer solution (pH 5.0). The oxidation overpotentials of L-cysteine decreased significantly and their oxidation peak currents increased dramatically at Au-SH-SiO₂@Cu-MOF. The potential utility of the sensor was demonstrated by applying it to the analytical determination of L-cysteine concentration. The results showed that the electrocatalytic current increased linearly with the L-cysteine concentration in the range of 0.02-300 μM and the detection limit was 0.008 μM. Finally, the sensor was applied to determine L-cysteine in water and biological samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Yu; Wang, Yan-Mei; Xu, Ji; Liu, Pan; Weththasinha, H.A.B.M.D.; Wu, Yun-Long; Lu, Xiao-Qing; Xie, Ji-Min, E-mail: xiejm391@sohu.com

    2014-11-15

    Two lanthanide coordination polymers, namely, ([La(TTTA)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (La-TTTA) and [Nd(TTTA)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (Nd-TTTA) have been hydrothermally synthesized through the reaction of lanthanide ions (La{sup 3+} and Nd{sup 3+}) with the flexible tripodal ligand 2,2′,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid (H{sub 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{sup 3+}, Cu{sup 2+}, Mg{sup 2+}, Cr{sup 3+} and Co{sup 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{sub 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{sup 3+}, Cu{sup 2+}, Mg{sup 2+}, Cr{sup 3+} and Co{sup 2+} ions via quenching the peak around 361 nm. • They act as efficient Lewis acid catalysts for the cyanosilylation reactions in high yields.

  2. 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.

  3. Concentric catalytic combustor

    Science.gov (United States)

    Bruck, Gerald J [Oviedo, FL; Laster, Walter R [Oviedo, FL

    2009-03-24

    A catalytic combustor (28) includes a tubular pressure boundary element (90) having a longitudinal flow axis (e.g., 56) separating a first portion (94) of a first fluid flow (e.g., 24) from a second portion (95) of the first fluid flow. The pressure boundary element includes a wall (96) having a plurality of separate longitudinally oriented flow paths (98) annularly disposed within the wall and conducting respective portions (100, 101) of a second fluid flow (e.g., 26) therethrough. A catalytic material (32) is disposed on a surface (e.g., 102, 103) of the pressure boundary element exposed to at least one of the first and second portions of the first fluid flow.

  4. Improving the temperature characteristics and catalytic efficiency of a mesophilic xylanase from Aspergillus oryzae, AoXyn11A, by iterative mutagenesis based on in silico design.

    Science.gov (United States)

    Li, Xue-Qing; Wu, Qin; Hu, Die; Wang, Rui; Liu, Yan; Wu, Min-Chen; Li, Jian-Fang

    2017-12-01

    To improve the temperature characteristics and catalytic efficiency of a glycoside hydrolase family (GHF) 11 xylanase from Aspergillus oryzae (AoXyn11A), its variants were predicted based on in silico design. Firstly, Gly 21 with the maximum B-factor value, which was confirmed by molecular dynamics (MD) simulation on the three-dimensional structure of AoXyn11A, was subjected to site-saturation mutagenesis. Thus, one variant with the highest thermostability, AoXyn11A G21I , was selected from the mutagenesis library, E. coli/Aoxyn11A G21X (X: any one of 20 amino acids). Secondly, based on the primary structure multiple alignment of AoXyn11A with seven thermophilic GHF11 xylanases, AoXyn11A Y13F or AoXyn11A G21I-Y13F , was designed by replacing Tyr 13 in AoXyn11A or AoXyn11A G21I with Phe. Finally, three variant-encoding genes, Aoxyn11A G21I , Aoxyn11A Y13F and Aoxyn11A G21I-Y13F , were constructed by two-stage whole-plasmid PCR method, and expressed in Pichia pastoris GS115, respectively. The temperature optimum (T opt ) of recombinant (re) AoXyn11A G21I-Y13F was 60 °C, being 5 °C higher than that of reAoXyn11A G21I or reAoXyn11A Y13F , and 10 °C higher than that of reAoXyn11A. The thermal inactivation half-life (t 1/2 ) of reAoXyn11A G21I-Y13F at 50 °C was 240 min, being 40-, 3.4- and 2.5-fold longer than those of reAoXyn11A, reAoXyn11A G21I and reAoXyn11A Y13F . The melting temperature (T m ) values of reAoXyn11A, reAoXyn11A G21I , reAoXyn11A Y13F and reAoXyn11A G21I-Y13F were 52.3, 56.5, 58.6 and 61.3 °C, respectively. These findings indicated that the iterative mutagenesis of both Gly21Ile and Tyr13Phe improved the temperature characteristics of AoXyn11A in a synergistic mode. Besides those, the catalytic efficiency (k cat /K m ) of reAoXyn11A G21I-Y13F was 473.1 mL mg -1 s -1 , which was 1.65-fold higher than that of reAoXyn11A.

  5. 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.

  6. Catalytic exhaust control

    Energy Technology Data Exchange (ETDEWEB)

    Heinemann, H

    1973-09-01

    Recent achievements and problems in the development of exhaust control devices in the USA are reviewed. To meet the 1976 emission standards, catalytic systems for the oxidation of carbon monoxide and hydrocarbons and for the reduction of nitrogen oxides to nitrogen and water are needed. While oxidizing catalysts using platinum, palladium, copper, vanadium, and chromium appplied on alumina or ceramic materials are more or less effective in emission control, there are no catalytic devices for the reduction of nitrogen oxides with the required useful life of 25,000 to 50,000 miles as yet available. In the case of platinum catalysts on monolithic supports, the operating temperature of 650 to 750/sup 0/C as required for the oxidation process may cause inactivation of the catalysts and fusion of the support material. The oxidation of CO and hydrocarbons is inhibited by high concentrations of CO, nitric oxide, and hydrocarbons. The use of catalytic converters requires the use of lead-free or low-lead gasoline. The nitrogen oxides conversion efficiency is considerably influenced by the oxygen-to-CO ratio of the exhaust gas, which makes limitation of this ratio necessary.

  7. 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.

  8. 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.

  9. 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.

  10. Petrochemical promoters in catalytic cracking

    International Nuclear Information System (INIS)

    Gomez, Maria; Vargas, Clemencia; Lizcano, Javier

    2010-01-01

    This study is based on the current scheme followed by a refinery with available Catalytic Cracking capacity to process new feedstocks such as Straight Run Naphtha and Naphthas from FCC. These feedstocks are of petrochemical interest to produce Ethane, Ethylene, Propylene, i-Butane, Toluene and Xylene. To evaluate the potential of these new streams versus the Cracking-charged Residues, it was performed a detailed chemical analysis on the structural groups in carbons [C1-C12] at the reactor product obtained in pilot plant. A catalyst with and without Propylene Promoter Additive was used. This study analyzes the differences in the chemical composition of the feedstocks, relating them to the yield of each petrochemical product. Straight Run Naphthas with a high content of Naphthenes, and Paraffines n[C5-C12] and i[C7-C12] are selective to the production of i-Butane and Propane, while Naphthas from FCC with a high content of n[C5-C12]Olefins, i-Olefins, and Aromatics are more selective to Propylene, Toluene, and Xylene. Concerning Catalytic Cracking of Naphthas, the Additive has similar selectivity for all the petrochemical products, their yields increase by about one point with 4%wt of Additive, while in cracking of Residues, the Additive increases in three points Propylene yield, corresponding to a selectivity of 50% (?C3= / ?LPG).

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

    African Journals Online (AJOL)

    Preferred Customer

    method is based on the catalytic effect of Mn(II) with the oxidation of Celestine blue .... water samples were filtered through a 0.45 μm pore size membrane filter to remove suspended .... slope of the calibration graph as the optimization criterion. ..... In presence of Phen as stability enhancement agent in indicator system. ( ) +.

  12. Catalytic biomass pyrolysis process

    Science.gov (United States)

    Dayton, David C.; Gupta, Raghubir P.; Turk, Brian S.; Kataria, Atish; Shen, Jian-Ping

    2018-04-17

    Described herein are processes for converting a biomass starting material (such as lignocellulosic materials) into a low oxygen containing, stable liquid intermediate that can be refined to make liquid hydrocarbon fuels. More specifically, the process can be a catalytic biomass pyrolysis process wherein an oxygen removing catalyst is employed in the reactor while the biomass is subjected to pyrolysis conditions. The stream exiting the pyrolysis reactor comprises bio-oil having a low oxygen content, and such stream may be subjected to further steps, such as separation and/or condensation to isolate the bio-oil.

  13. 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.

  14. 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.

  15. Catalytic hydrogenation of carbon monoxide

    International Nuclear Information System (INIS)

    Wayland, B.B.

    1993-12-01

    Focus of this project is on developing new approaches for hydrogenation of carbon monoxide to produce organic oxygenates at mild conditions. The strategies to accomplish CO reduction are based on favorable thermodynamics manifested by rhodium macrocycles for producing a series of intermediates implicated in the catalytic hydrogenation of CO. Metalloformyl complexes from reactions of H 2 and CO, and CO reductive coupling to form metallo α-diketone species provide alternate routes to organic oxygenates that utilize these species as intermediates. Thermodynamic and kinetic-mechanistic studies are used in guiding the design of new metallospecies to improve the thermodynamic and kinetic factors for individual steps in the overall process. Electronic and steric effects associated with the ligand arrays along with the influences of the reaction medium provide the chemical tools for tuning these factors. Non-macrocyclic ligand complexes that emulate the favorable thermodynamic features associated with rhodium macrocycles, but that also manifest improved reaction kinetics are promising candidates for future development

  16. The application of Cu/SiO2 catalytic system in chemical mechanical planarization based on the stability of SiO2 sol

    International Nuclear Information System (INIS)

    Li Yan; Liu Yuling; Wang Aochen; Yang Zhixin; Sun Mingbin; Cheng Chuan; Zhang Yufeng; Zhang Nannan

    2014-01-01

    There is a lot of hydroxyl on the surface of nano SiO 2 sol used as an abrasive in the chemical mechanical planarization (CMP) process, and the chemical reaction activity of the hydroxyl is very strong due to the nano effect. In addition to providing a mechanical polishing effect, SiO 2 sol is also directly involved in the chemical reaction. The stability of SiO 2 sol was characterized through particle size distribution, zeta potential, viscosity, surface charge and other parameters in order to ensure that the chemical reaction rate in the CMP process, and the surface state of the copper film after CMP was not affected by the SiO 2 sol. Polarization curves and corrosion potential of different concentrations of SiO 2 sol showed that trace SiO 2 sol can effectively weaken the passivation film thickness. In other words, SiO 2 sol accelerated the decomposition rate of passive film. It was confirmed that the SiO 2 sol as reactant had been involved in the CMP process of copper film as reactant by the effect of trace SiO 2 sol on the removal rate of copper film in the CMP process under different conditions. In the CMP process, a small amount of SiO 2 sol can drastically alter the chemical reaction rate of the copper film, therefore, the possibility that Cu/SiO 2 as a catalytic system catalytically accelerated the chemical reaction in the CMP process was proposed. According to the van't Hoff isotherm formula and the characteristics of a catalyst which only changes the chemical reaction rate with out changing the total reaction standard Gibbs free energy, factors affecting the Cu/SiO 2 catalytic reaction were derived from the decomposition rate of Cu (OH) 2 and the pH value of the system, and then it was concluded that the CuSiO 3 as intermediates of Cu/SiO 2 catalytic reaction accelerated the chemical reaction rate in the CMP process. It was confirmed that the Cu/SiO 2 catalytic system generated the intermediate of the catalytic reaction (CuSiO 3 ) in the CMP process

  17. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is ...

  18. 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

  19. 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.

  20. 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.

  1. A model of protocell based on the introduction of a semi-permeable membrane in a stochastic model of catalytic reaction networks

    Directory of Open Access Journals (Sweden)

    Marco Villani

    2013-09-01

    Full Text Available In this work we introduce some preliminary analyses on the role of a semi-permeable membrane in the dynamics of a stochastic model of catalytic reaction sets (CRSs of molecules. The results of the simulations performed on ensembles of randomly generated reaction schemes highlight remarkable differences between this very simple protocell description model and the classical case of the continuous stirred-tank reactor (CSTR. In particular, in the CSTR case, distinct simulations with the same reaction scheme reach the same dynamical equilibrium, whereas, in the protocell case, simulations with identical reaction schemes can reach very different dynamical states, despite starting from the same initial conditions.

  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. 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

  4. Small-angle scattering studies show distinct conformations of calmodulin in its complexes with two peptides based on the regulatory domain of the catalytic subunit of phosphorylase kinase

    International Nuclear Information System (INIS)

    Trewhella, J.; Blumenthal, D.K.; Rokop, S.E.; Seeger, P.A.

    1990-01-01

    Small-angle X-ray and neutron scattering have been used to study the solution structures of calmodulin complexed with synthetic peptides corresponding to residues 342-366 and 301-326, designated PhK5 and PhK13, respectively, in the regulatory domain of the catalytic subunit of skeletal muscle phosphorylase kinase. The scattering data show that binding of PhK5 to calmodulin induces a dramatic contraction of calmodulin, similar to that previously observed when calmodulin is complexed with the calmodulin-binding domain peptide from rabbit skeletal muscle myosin light chain kinase. In contrast, calmodulin remains extended upon binding PhK13. In the presence of both peptides, calmodulin also remains extended. Apparently, the presence of PhK13 inhibits calmodulin from undergoing the PhK5-induced contraction. These data indicate that there is a fundamentally different type of calmodulin-target enzyme interaction in the case of the catalytic subunit of phosphorylase kinase compared with that for myosin light chain kinase

  5. 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.

  6. 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.

  7. 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.)

  8. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    126, No. 2, March 2014, pp. 341–351. c Indian Academy of Sciences. ... enhancement was realized by catalyst design, appropriate choice of reactor, better injection and .... Gas–liquid and liquid–solid transport processes in catalytic reactors.5.

  9. Aerobic, catalytic oxidation of alcohols in ionic liquids

    Directory of Open Access Journals (Sweden)

    Souza Roberto F. de

    2006-01-01

    Full Text Available An efficient and simple catalytic system based on RuCl3 dissolved in ionic liquids has been developed for the oxidation of alcohols into aldehydes and ketones under mild conditions. A new fluorinated ionic liquid, 1-n-butyl-3-methylimidazolium pentadecafluorooctanoate, was synthesized and demonstrated better performance that the other ionic liquids employed. Moreover this catalytic system utilizes molecular oxygen as an oxidizing agent, producing water as the only by-product.

  10. 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.

  11. Catalytic activity of dual catalysts system based on nano-manganese oxide and cobalt octacyanophthalocyanine toward four-electron reduction of oxygen in alkaline media

    International Nuclear Information System (INIS)

    Zhang, Dun; Chi, Dahe; Okajima, Takeyoshi; Ohsaka, Takeo

    2007-01-01

    The electrocatalysis of the dual functional catalysts system composed of electrolytic nano-manganese oxide (nano-MnOx) and cobalt octacyanophthalocyanine (CoPcCN) toward 4-electron reduction of oxygen (O 2 ) in alkaline media was studied. Nano-MnOx electrodeposited on the CoPcCN monolayer-modified glassy carbon (GC) electrode was clarified as the nano-rods with ca. 10-20 nm diameter by scanning electron microscopy. The peak current for O 2 reduction at the dual catalysts-modified GC electrode increases largely and the peak potential shifts by ca. 160 mV to the positive direction in cyclic voltammograms compared with those obtained at the bare GC electrode. The Koutecky-Levich plots indicate that the O 2 reduction at the dual catalysts-modified GC electrode is an apparent 4-electron process. Collection efficiencies obtained at the dual catalysts-modified GC electrode are much lower than those at the GC electrode and are almost similar to those at the Pt nano-particles modified GC electrode. The obtained results demonstrate that the dual catalysts system possesses a bifuctional catalytic activity for redox-mediating 2-electron reduction of O 2 to HO 2 - by CoPcCN as well as catalyzing the disproportionation of HO 2 - to OH - and O 2 by nano-MnOx, and enables an apparent 4-electron reduction of O 2 at a relatively low overpotential in alkaline media. In addition, it has been found that the cleaning of the dual catalysts-modified electrode by soaking in 0.1 M sulfuric acid solution enhances its catalytic activity toward the reduction of O 2

  12. Hydrogénations catalytiques. De la recherche de base à l'application industrielle Catalytic Hydrogenation from Basic Research to Industrial Applications

    Directory of Open Access Journals (Sweden)

    Boitiaux J. P.

    2006-11-01

    Full Text Available Les premiers travaux concernant l'hydrogénation catalytique ont montré la spécificité des différents métaux pour les différents types d'hydrogénation (acétyléniques, oléfines, aromatiques, aldéhydes, nitriles. . . . Cette observation incluait de façon encore vague la notion de l'importance du couple métal-substrat. Une contradiction avec le caractère non sensible à la structure de ces réactions apparaissait alors. Des travaux récents effectués sur des catalyseurs au palladium de dispersions variées ont clairement démontré l'influence de la taille de particule sur la vitesse d'hydrogénation des acétyléniques et dioléfines en C4. Un tel comportement a été depuis confirmé par d'autres travaux sur palladium, platine et rhodium. Le phénomène est dû à une adsorption trop forte des réactifs sur les petites particules : celles-ci sont électrodéficientes et adsorbent très fortement les composés électrodonneurs comme les hydrocarbures insaturés. L'explication est confirmée par l'effet additif que produit la pipéridine. Sa coadsorption sur le catalyseur déstabilise la liaison métal-substrat et augmente l'activité. Une étude cinétique complète a permis d'affiner cette interprétation en démontrant la constance de l'activité intrinsèque et la relation entre la sensibilité à la dispersion métallique et une complexation du site métallique du type de celle que l'on rencontre sur les catalyseurs homogènes. Ces études fondamentales ont des conséquences très importantes pour la mise au point des catalyseurs industriels : pour chaque procédé, et donc pour chaque hydrogénation, il est nécessaire de déterminer la dispersion optimale du métal pour obtenir l'activité et la sélectivité les plus élevées, c'est-à-dire la meilleure rentabilité du procédé. Par ailleurs, les concepts établis grâce à ces recherches de base permettent d'unifier l'interprétation de l'influence des solvants, des

  13. 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.

  14. Non-thermal plasmas for non-catalytic and catalytic VOC abatement

    International Nuclear Information System (INIS)

    Vandenbroucke, Arne M.; Morent, Rino; De Geyter, Nathalie; Leys, Christophe

    2011-01-01

    Highlights: → We review the current status of catalytic and non-catalytic VOC abatement based on a vast number of research papers. → The underlying mechanisms of plasma-catalysis for VOC abatement are discussed. → Critical process parameters that determine the influent are discussed and compared. - Abstract: This paper reviews recent achievements and the current status of non-thermal plasma (NTP) technology for the abatement of volatile organic compounds (VOCs). Many reactor configurations have been developed to generate a NTP at atmospheric pressure. Therefore in this review article, the principles of generating NTPs are outlined. Further on, this paper is divided in two equally important parts: plasma-alone and plasma-catalytic systems. Combination of NTP with heterogeneous catalysis has attracted increased attention in order to overcome the weaknesses of plasma-alone systems. An overview is given of the present understanding of the mechanisms involved in plasma-catalytic processes. In both parts (plasma-alone systems and plasma-catalysis), literature on the abatement of VOCs is reviewed in close detail. Special attention is given to the influence of critical process parameters on the removal process.

  15. 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

  16. Catalytic applications of bio-inspired nanomaterials

    Science.gov (United States)

    Pacardo, Dennis Kien Balaong

    The biomimetic synthesis of Pd nanoparticles was presented using the Pd4 peptide, TSNAVHPTLRHL, isolated from combinatorial phage display library. Using this approach, nearly monodisperse and spherical Pd nanoparticles were generated with an average diameter of 1.9 +/- 0.4 nm. The peptide-based nanocatalyst were employed in the Stille coupling reaction under energy-efficient and environmentally friendly reaction conditions of aqueous solvent, room temperature and very low catalyst loading. To this end, the Pd nanocatalyst generated high turnover frequency (TOF) value and quantitative yields using ≥ 0.005 mol% Pd as well as catalytic activities with different aryl halides containing electron-withdrawing and electron-donating groups. The Pd4-capped Pd nanoparticles followed the atom-leaching mechanism and were found to be selective with respect to substrate identity. On the other hand, the naturally-occurring R5 peptide (SSKKSGSYSGSKGSKRRIL) was employed in the synthesis of biotemplated Pd nanomaterials which showed morphological changes as a function of Pd:peptide ratio. TOF analysis for hydrogenation of olefinic alcohols showed similar catalytic activity regardless of nanomorphology. Determination of catalytic properties of these bio-inspired nanomaterials are important as they serve as model system for alternative green catalyst with applications in industrially important transformations.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. Catalytic activity of Au nanoparticles

    DEFF Research Database (Denmark)

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

    2007-01-01

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

  2. 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.

  3. Immobilization of glucose oxidase onto a novel platform based on modified TiO{sub 2} and graphene oxide, direct electrochemistry, catalytic and photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Haghighi, Nasibeh, E-mail: Haghighi.nasibeh@yahoo.com [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Hallaj, Rahman, E-mail: Rhallaj@uok.ac.ir [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Nanotechnology Research Center, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Salimi, Abdollah [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Nanotechnology Research Center, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)

    2017-04-01

    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{sub 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{sub 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{sub 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{sup −1}. The GO/TiO{sub 2}-OISL can catalyze the electroreduction and electrooxidation of hydrogen peroxide. The GC/GO/TiO{sub 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.

  4. 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.

  5. Post-treatment of biologically treated wastewater containing organic contaminants using a sequence of H2O2 based advanced oxidation processes: photolysis and catalytic wet oxidation.

    Science.gov (United States)

    Rueda-Márquez, J J; Sillanpää, M; Pocostales, P; Acevedo, A; Manzano, M A

    2015-03-15

    In this paper the feasibility of a multi-barrier treatment (MBT) for the regeneration of synthetic industrial wastewater (SIWW) was evaluated. Industrial pollutants (orange II, phenol, 4-chlorophenol and phenanthrene) were added to the effluent of municipal wastewater treatment plant. The proposed MBT begins with a microfiltration membrane pretreatment (MF), followed by hydrogen peroxide photolysis (H2O2/UVC) and finishing, as a polishing step, with catalytic wet peroxide oxidation (CWPO) using granular activated carbon (GAC) at ambient conditions. During the microfiltration step (0.7 μm) the decrease of suspended solids concentration, turbidity and Escherichia coli in treated water were 88, 94 and 99%, respectively. Also, the effluent's transmittance (254 nm) was increased by 14.7%. Removal of more than 99.9% of all added pollutants, mineralization of 63% of organic compounds and complete disinfection of total coliforms were reached during the H2O2/UVC treatment step (H2O2:TOC w/w ratio = 5 and an UVC average dose accumulated by wastewater 8.80 WUVC s cm(-2)). The power and efficiency of the lamp, the water transmittance and photoreactor geometry are taken into account and a new equation to estimate the accumulated dose in water is suggested. Remaining organic pollutants with a higher oxidation state of carbon atoms (+0.47) and toxic concentration of residual H2O2 were present in the effluent of the H2O2/UVC process. After 2.3 min of contact time with GAC at CWPO step, 90 and 100% of total organic carbon and residual H2O2 were removed, respectively. Also, the wastewater toxicity was studied using Vibrio fischeri and Sparus aurata larvae. The MBT operational and maintenance costs (O&M) was estimated to be 0.59 € m(-3). Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Catalytic hydrogenation of carbon monoxide

    Energy Technology Data Exchange (ETDEWEB)

    Wayland, B.B.

    1992-12-01

    This project is focused on developing strategies to accomplish the reduction and hydrogenation of carbon monoxide to produce organic oxygenates at mild conditions. Our approaches to this issue are based on the recognition that rhodium macrocycles have unusually favorable thermodynamic values for producing a series of intermediate implicated in the catalytic hydrogenation of CO. Observations of metalloformyl complexes produced by reactions of H{sub 2} and CO, and reductive coupling of CO to form metallo {alpha}-diketone species have suggested a multiplicity of routes to organic oxygenates that utilize these species as intermediates. Thermodynamic and kinetic-mechanistic studies are used in constructing energy profiles for a variety of potential pathways, and these schemes are used in guiding the design of new metallospecies to improve the thermodynamic and kinetic factors for individual steps in the overall process. Variation of the electronic and steric effects associated with the ligand arrays along with the influences of the reaction medium provide the chemical tools for tuning these factors. Emerging knowledge of the factors that contribute to M-H, M-C and M-O bond enthalpies is directing the search for ligand arrays that will expand the range of metal species that have favorable thermodynamic parameters to produce the primary intermediates for CO hydrogenation. Studies of rhodium complexes are being extended to non-macrocyclic ligand complexes that emulate the favorable thermodynamic features associated with rhodium macrocycles, but that also manifest improved reaction kinetics. Multifunctional catalyst systems designed to couple the ability of rhodium complexes to produce formyl and diketone intermediates with a second catalyst that hydrogenates these imtermediates are promising approaches to accomplish CO hydrogenation at mild conditions.

  7. 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

  8. 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...... and quantum state merging, and leads to a resource theory of decoupling....

  9. 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

  10. 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.

  11. Catalytic Conversion of Carbohydrates

    DEFF Research Database (Denmark)

    Osmundsen, Christian Mårup

    a renewable route to aromatics. The conversion of biomass by high temperature processes is a desirable prospect due to the high volumetric production rates which can be achieved, and the ability of these types of processes to convert a wide range of substrates. Current processes however typically have rather...... 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...... to be an efficient initial conversion step in the utilization of biomass for chemicals production. The shift from an oil based chemical industry to one based on renewable resources is bound to happen sooner or later, however the environmental problems associated with the burning of fossil resources means...

  12. 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

  13. Catalytic pyrolysis of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    1937-04-07

    To convert the heavier and less valuable portions of crude petroleums and the like into lower boiling products, they are subjcted at elevated temperatures to the action of catalysts. The catalysts may be comprised of altered silicates, clays of the montomorillonite type in which a portion of the combined alumina has been removed by acid treatment, or feldspars, or natural or artificial zeolites, in which the alkali metals and/or alkaline earth metals have been partly or completely replaced by other bases.

  14. Catalytic process for tritium exchange reaction

    International Nuclear Information System (INIS)

    Hansoo Lee; Kang, H.S.; Paek, S.W.; Hongsuk Chung; Yang Geun Chung; Sook Kyung Lee

    2001-01-01

    The catalytic activities for a hydrogen isotope exchange were measured through the reaction of a vapor and gas mixture. The catalytic activity showed to be comparable with the published data. Since the gas velocity is relatively low, the deactivation was not found clearly during the 5-hour experiment. Hydrogen isotope transfer experiments were also conducted through the liquid phase catalytic exchange reaction column that consisted of a catalytic bed and a hydrophilic bed. The efficiencies of both the catalytic and hydrophilic beds were higher than 0.9, implying that the column performance was excellent. (author)

  15. Catalytic Fast Pyrolysis: A Review

    Directory of Open Access Journals (Sweden)

    Theodore Dickerson

    2013-01-01

    Full Text Available Catalytic pyrolysis is a promising thermochemical conversion route for lignocellulosic biomass that produces chemicals and fuels compatible with current, petrochemical infrastructure. Catalytic modifications to pyrolysis bio-oils are geared towards the elimination and substitution of oxygen and oxygen-containing functionalities in addition to increasing the hydrogen to carbon ratio of the final products. Recent progress has focused on both hydrodeoxygenation and hydrogenation of bio-oil using a variety of metal catalysts and the production of aromatics from bio-oil using cracking zeolites. Research is currently focused on developing multi-functional catalysts used in situ that benefit from the advantages of both hydrodeoxygenation and zeolite cracking. Development of robust, highly selective catalysts will help achieve the goal of producing drop-in fuels and petrochemical commodities from wood and other lignocellulosic biomass streams. The current paper will examine these developments by means of a review of existing literature.

  16. Catalytic processes for cleaner fuels

    International Nuclear Information System (INIS)

    Catani, R.; Marchionna, M.; Rossini, S.

    1999-01-01

    More stringent limitations on vehicle emissions require different measurement: fuel reformulation is one of the most important and is calling for a noticeable impact on refinery assets. Composition rangers of the future fuels have been defined on a time scale. In this scenario the evolution of catalytic technologies becomes a fundamental tool for allowing refinery to reach the fixed-by-law targets. In this paper, the refinery process options to meet each specific requirements of reformulated fuels are surveyed [it

  17. Dependence of crystal size on the catalytic performance of a porous coordination polymer.

    Science.gov (United States)

    Kiyonaga, Tomokazu; Higuchi, Masakazu; Kajiwara, Takashi; Takashima, Yohei; Duan, Jingui; Nagashima, Kazuro; Kitagawa, Susumu

    2015-02-14

    Submicrosized MOF-76(Yb) exhibits a higher catalytic performance for esterification than microsized MOF-76(Yb). Control of the crystal size of porous heterogeneous catalysts, such as PCP/MOFs, offers a promising approach to fabricating high-performance catalysts based on accessibility to the internal catalytic sites.

  18. A simple and sensitive flow injection method based on the catalytic activity of CdS quantum dots in an acidic permanganate chemiluminescence system for determination of formaldehyde in water and wastewater.

    Science.gov (United States)

    Khataee, Alireza; Lotfi, Roya; Hasanzadeh, Aliyeh; Iranifam, Mortaza

    2016-04-01

    A simple and sensitive flow injection chemiluminescence (CL) method in which CdS quantum dots (QDs) enhanced the CL intensity of a KMnO4-formaldehyde (HCHO) reaction was offered for the determination of HCHO. This CL system was based on the catalytic activity of CdS QDs and their participation in the CL resonance energy transfer (CRET) phenomenon. A possible mechanism for the supplied CL system was proposed using the kinetic curves of the CL systems and the spectra of CL, photoluminescence (PL) and ultraviolet-visible (UV-Vis). The emanated CL intensity of the KMnO4-CdS QDs system was amplified in the presence of a trace level of HCHO. Based on this enhancement effect, a simple and sensitive flow injection CL method was suggested for the determination of HCHO concentration in environmental water and wastewater samples. Under selected optimized experimental conditions, the increased CL intensity was proportional to the HCHO concentration in the range of 0.03-4.5 μg L(-1) and 4.5-10.0 μg L(-1). The detection limits (3σ) were 0.0003 μg L(-1) and 1.2 μg L(-1). The relative standard deviations (RSD%) for eleven replicate determinations of 4.0 μg L(-1) HCHO were 2.2%. Furthermore, the feasibility of the developed method was investigated via the determination of HCHO concentration in environmental water and wastewater samples.

  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. Catalytic aromatization of methane.

    Science.gov (United States)

    Spivey, James J; Hutchings, Graham

    2014-02-07

    Recent developments in natural gas production technology have led to lower prices for methane and renewed interest in converting methane to higher value products. Processes such as those based on syngas from methane reforming are being investigated. Another option is methane aromatization, which produces benzene and hydrogen: 6CH4(g) → C6H6(g) + 9H2(g) ΔG°(r) = +433 kJ mol(-1) ΔH°(r) = +531 kJ mol(-1). Thermodynamic calculations for this reaction show that benzene formation is insignificant below ∼600 °C, and that the formation of solid carbon [C(s)] is thermodynamically favored at temperatures above ∼300 °C. Benzene formation is insignificant at all temperatures up to 1000 °C when C(s) is included in the calculation of equilibrium composition. Interestingly, the thermodynamic limitation on benzene formation can be minimized by the addition of alkanes/alkenes to the methane feed. By far the most widely studied catalysts for this reaction are Mo/HZSM-5 and Mo/MCM-22. Benzene selectivities are generally between 60 and 80% at methane conversions of ∼10%, corresponding to net benzene yields of less than 10%. Major byproducts include lower molecular weight hydrocarbons and higher molecular weight substituted aromatics. However, carbon formation is inevitable, but the experimental findings show this can be kinetically limited by the use of H2 or oxidants in the feed, including CO2 or steam. A number of reactor configurations involving regeneration of the carbon-containing catalyst have been developed with the goal of minimizing the cost of regeneration of the catalyst once deactivated by carbon deposition. In this tutorial review we discuss the thermodynamics of this process, the catalysts used and the potential reactor configurations that can be applied.

  1. Enhanced catalytic activity through the tuning of micropore environment and supercritical CO2 processing: Al(porphyrin)-based porous organic polymers for the degradation of a nerve agent simulant.

    Science.gov (United States)

    Totten, Ryan K; Kim, Ye-Seong; Weston, Mitchell H; Farha, Omar K; Hupp, Joseph T; Nguyen, SonBinh T

    2013-08-14

    An Al(porphyrin) functionalized with a large axial ligand was incorporated into a porous organic polymer (POP) using a cobalt-catalyzed acetylene trimerization strategy. Removal of the axial ligand afforded a microporous POP that is catalytically active in the methanolysis of a nerve agent simulant. Supercritical CO2 processing of the POP dramatically increased the pore size and volume, allowing for significantly higher catalytic activities.

  2. 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.

  3. Chemically-modified cellulose paper as a microstructured catalytic reactor.

    Science.gov (United States)

    Koga, Hirotaka; Kitaoka, Takuya; Isogai, Akira

    2015-01-15

    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.

  4. 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.

  5. 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.

  6. 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

  7. Direct catalytic cross-coupling of organolithium compounds

    NARCIS (Netherlands)

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

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

  8. 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.

  9. Synthesis, characterization, spectroscopic and catalytic oxidation studies of Fe(III), Ni(II), Co(III), V(IV) and U(VI) Schiff base complexes with N, O donor ligands derived from 2,3-diaminopyridine

    Energy Technology Data Exchange (ETDEWEB)

    Zabardasti, Abedien; Shangaie, Sayed Asad [Lorestan Univ., Khorramabad (Iran, Islamic Republic of). Dept. of Chemistry

    2016-10-15

    Fifteen new complexes of transition metals were designed using three Schiff base ligands and aldol condensation of 2,3-diaminopyridine with 5-R-2-hydroxybenzaldehyde (R = F, Cl, Br) in the 1:2 molar ratio. The tetradentate ligands N,N{sup '}-bis(5-R-2-hydroxybenzaldehyde) pyridine were acquired with the common formula H{sub 2}[(5-R-sal){sub 2}py] and characterized by IR, UV-Vis spectra, {sup 1}H-NMR and elemental analysis. These ligands produce 1:1 complexes M[(5-R-sal){sub 2}py] with Fe(III), Ni(II), Co(III), V(IV) and U(VI) metal ions. The electronic property and nature of complexes were identified by IR, UV-Vis spectra, elemental analysis, X-ray crystallography and cyclic voltammetric methods. The catalytic activity of complexes for epoxidation of styrene with UHP as primary oxidant at minimal temperature (10 C) has been planned. The spectral data of the ligands and their complexes are deliberate in connection with the structural changes which happen due to complex preparation. The electrochemical outcome has good conformability with what suggested for electronic interaction among metal center and ligand by the UV-Vis and IR measurements.

  10. 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

  11. 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

  12. Catalytic cracking of hydrocarbon oils

    Energy Technology Data Exchange (ETDEWEB)

    1940-09-12

    A process is described for the vapor phase catalytic cracking of hydrocarbon oils boiling substantially in the gas oil range. The reaction takes place in the presence of a solid catalyst between 700 to 900/sup 0/F under pressure between atmospheric and 400 psi. A gas containing between 20 and 90 mol % of free hydrogen is used. The reaction is allowed to proceed until consumption of the free begins. The reaction is discontinued at that point and the catalyst is regenerated for further use.

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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).

  1. 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

  2. Ionic Liquids: The Synergistic Catalytic Effect in the Synthesis of Cyclic Carbonates

    Directory of Open Access Journals (Sweden)

    Flora T.T. Ng

    2013-10-01

    Full Text Available This review presents the synergistic effect in the catalytic system of ionic liquids (ILs for the synthesis of cyclic carbonate from carbon dioxide and epoxide. The emphasis of this review is on three aspects: the catalytic system of metal-based ionic liquids, the catalytic system of hydrogen bond-promoted ionic liquids and supported ionic liquids. Metal and ionic liquids show a synergistic effect on the cycloaddition reactions of epoxides. The cations and anions of ionic liquids show a synergistic effect on the cycloaddition reactions. The functional groups in cations or supports combined with the anions have a synergistic effect on the cycloaddition reactions. Synergistic catalytic effects of ILs play an important role of promoting the cycloaddition reactions of epoxides. The design of catalytic system of ionic liquids will be possible if the synergistic effect on a molecular level is understood.

  3. Experimental Investigation of Flow Resistance in a Coal Mine Ventilation Air Methane Preheated Catalytic Oxidation Reactor

    Directory of Open Access Journals (Sweden)

    Bin Zheng

    2015-01-01

    Full Text Available This paper reports the results of experimental investigation of flow resistance in a coal mine ventilation air methane preheated catalytic oxidation reactor. The experimental system was installed at the Energy Research Institute of Shandong University of Technology. The system has been used to investigate the effects of flow rate (200 Nm3/h to 1000 Nm3/h and catalytic oxidation bed average temperature (20°C to 560°C within the preheated catalytic oxidation reactor. The pressure drop and resistance proportion of catalytic oxidation bed, the heat exchanger preheating section, and the heat exchanger flue gas section were measured. In addition, based on a large number of experimental data, the empirical equations of flow resistance are obtained by the least square method. It can also be used in deriving much needed data for preheated catalytic oxidation designs when employed in industry.

  4. 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.

  5. Soluble organic nanotubes for catalytic systems

    Science.gov (United States)

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

    2016-03-01

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

  6. Soluble organic nanotubes for catalytic systems.

    Science.gov (United States)

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

    2016-03-18

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

  7. 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.

  8. 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)

  9. 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.

  10. 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- ...

  11. 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

  12. 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.

  13. Catalytic Flash Pyrolysis of Biomass Using Different Types of Zeolite and Online Vapor Fractionation

    KAUST Repository

    Imran, Ali; Bramer, Eddy; Seshan, Kulathuiyer; Brem, Gerrit

    2016-01-01

    -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

  14. 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...

  15. Method of fabricating a catalytic structure

    Science.gov (United States)

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

    2009-09-22

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

  16. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-12-31

    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.)

  17. 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.

  18. Studies of Catalytic Model Systems

    DEFF Research Database (Denmark)

    Holse, Christian

    The overall topic of this thesis is within the field of catalysis, were model systems of different complexity have been studied utilizing a multipurpose Ultra High Vacuum chamber (UHV). The thesis falls in two different parts. First a simple model system in the form of a ruthenium single crystal...... 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......-ray Photoelectron Electron Spectroscopy (XPS) and in situ Transmission Electron Microscopy (TEM). The surface composition of the nanoparticles changes reversibly as the nanoparticles exposed to cycles of high-pressure oxidation and reduction (200 mbar). Furthermore, the presence of metallic Zn is observed by XPS...

  19. 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.)

  20. 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.

  1. 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.

  2. 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

  3. Mechanisms of catalytic activity in heavily coated hydrocracking catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Millan, M.; Adell, C.; Hinojosa, C.; Herod, A.A.; Kandiyoti, R. [University of London Imperial College Science Technology & Medicine, London (United Kingdom). Dept. of Chemical Engineering

    2008-01-15

    Catalyst deactivation by coke deposition has a direct impact on the economic viability of heavy hydrocarbon upgrading processes, such as coal liquefaction and oil residue hydroprocessing. Coke deposition is responsible for rapid loss of catalytic activity and it mostly takes place in the early stages of hydrocracking. The effect of carbonaceous deposition on the catalytic activity of a chromium pillared montmorillonite has been studied in the present work. Its catalytic activity in hydrocracking a coal extract was evaluated based on the boiling point distributions of feed and products obtained by thermogravimetric analysis (TGA), and their characterisation by size exclusion chromatography (SEC) and UV-Fluorescence spectroscopy (UV-F). A large deposition on the catalyst was observed after two successive 2-hour long runs in which the catalyst recovered from the first run was reused in the second. The pillared clay retained its activity even though it showed high carbon loading, a large drop in surface area and complete apparent pore blockage. Some observations may contribute to explain this persistent catalytic activity. First, there is evidence suggesting the dynamic nature of the carbonaceous deposits, which continuously exchange material with the liquid, allowing catalytic activity to continue. Secondly, Scanning Electron Microscopy (SEM) on the used Cr montmorillonite has shown preferential deposition on some regions of the catalyst, which leaves a fraction of the surface relatively exposed. Finally, evidence from SEM coupled to X-ray microanalysis also suggest that deposits are thinner in areas where the active phase of the catalyst is present in higher concentrations. Hydrogenation on the active sites would make the deposits more soluble in the liquid cleaning of surrounding area from deposits.

  4. 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......The article develops the concept of catalytic processes in relation to social work with adolescents in an attempt to both reach a more nuanced understanding of social work and at the same time to develop the concept of catalytic processes in psychology. The social work is pedagogical treatment...

  5. Efficient catalytic combustion in integrated micropellistors

    International Nuclear Information System (INIS)

    Bársony, I; Ádám, M; Fürjes, P; Dücső, Cs; Lucklum, R; Hirschfelder, M; Kulinyi, S

    2009-01-01

    This paper analyses two of the key issues of the development of catalytic combustion-type sensors: the selection and production of active catalytic particles on the micropellistor surface as well as the realization of a reliable thermal conduction between heater element and catalytic surface, for the sensing of temperature increase produced by the combustion. The report also demonstrates that chemical sensor product development by a MEMS process is a continuous struggle for elimination of all uncertainties influencing reliability and sensitivity of the final product

  6. Preparation of Photo catalytic Materials Based on Bi{sub 4}Ti{sub 3}O{sub 1}2 Doped with Transition Metals; Preparacion de Materiales Fotocatalizadores Basados en Bi{sub 4}Ti{sub 3}O{sub 1}2 Dopados con Metales de Transicion

    Energy Technology Data Exchange (ETDEWEB)

    Calatalyud, D. G.; Rodriguez, M.; Gallego, B.; Fernandez-Hevia, D.; Jardiel, T.

    2012-07-01

    The production of hydrogen from water using ceramic semiconductors with photo catalytic properties has gained special relevance in the last years, due to their potential use for the generation of hydrogen in a direct and clean way. Doping with transition metals has demonstrated to be an effective method to obtain new active photo catalysts in the visible range of the solar spectrum by changing the band gap of the material. In this paper we study the effect of the addition of various dopants (Fe, Ni, Cr, Mn, Co, Cu) in the structure and band gap of Bi{sub 4}Ti{sub 3}O{sub 1}2, in order to improve its photo catalytic activity and make it visible light active. Accordingly, doped BIT based materials have been obtained by solid state processing and different amounts of an additional phase with sillenite structure, Bi{sub 1}2TiO{sub 2}0, have been detected. With the dopant a shift of the absorption spectra is produced towards higher wavelengths and consequently towards lower band gap values. The band gap values obtained for many of the prepared compositions are quite promising, promoting the study of their catalytic properties.. (Author)

  7. Catalytic synthesis of alcoholic fuels for transportation from syngas

    OpenAIRE

    Wu, Qiongxiao; Jensen, Anker Degn; Grunwaldt, Jan-Dierk; Temel, Burcin; Christensen, Jakob Munkholt

    2013-01-01

    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 composition have been identified as potential candidates for methanol synthesis. These Cu-Ni alloy catalysts have been synthesized and tested in a fixed-bed continuous-flow reactor for CO hydrogenatio...

  8. Vacuum-insulated catalytic converter

    Science.gov (United States)

    Benson, David K.

    2001-01-01

    A catalytic converter has an inner canister that contains catalyst-coated substrates and an outer canister that encloses an annular, variable vacuum insulation chamber surrounding the inner canister. An annular tank containing phase-change material for heat storage and release is positioned in the variable vacuum insulation chamber a distance spaced part from the inner canister. A reversible hydrogen getter in the variable vacuum insulation chamber, preferably on a surface of the heat storage tank, releases hydrogen into the variable vacuum insulation chamber to conduct heat when the phase-change material is hot and absorbs the hydrogen to limit heat transfer to radiation when the phase-change material is cool. A porous zeolite trap in the inner canister absorbs and retains hydrocarbons from the exhaust gases when the catalyst-coated substrates and zeolite trap are cold and releases the hydrocarbons for reaction on the catalyst-coated substrate when the zeolite trap and catalyst-coated substrate get hot.

  9. Catalytic hydrotreatment of refinery waste

    Energy Technology Data Exchange (ETDEWEB)

    1989-01-01

    The object of the project is to produce liquid hydrocarbons by the catalytic hydroprocessing of solid refinery wastes (hard pitches) in order to improve the profitability of deep conversion processes and reduce the excess production of heavy fuels. The project was mostly carried out on the ASVAHL demonstration platform site, at Solaize, and hard pitches were produced primarily by deasphalting of atmospheric or vacuum distillation residues. The project includes two experimental phases and an economic evaluation study phase. In phase 1, two granular catalysts were used to transform pitch into standard low sulphur fuel oil: a continuously moving bed, with demetallation and conversion catalyst; a fixed bed, with hydrorefining catalyst. In phase 2 of the project, it was proven that a hydrotreatment process using a finely dispersed catalyst in the feedstock, can, under realistic operating conditions, transform with goods yields hard pitch into distillates that can be refined through standard methods. In phase 3 of the project, it was shown that the economics of such processes are tightly linked to the price differential between white and black oil products, which is expected to increase in the future. Furthermore, the evolution of environmental constraints will impel the use of such methods, thus avoiding the coproduction of polluting solid residues.

  10. 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.

  11. 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.

  12. Chemistry and engineering of catalytic hydrodesulfurization

    NARCIS (Netherlands)

    Schuit, G.C.A.; Gates, B.C.

    1973-01-01

    A review with 74 refs. on catalytic hydrodesulfurization of pure compds. and petroleum feedstocks, with emphasis on reaction intermediates and structures of Al2O3-supported Ni-W and Co-Mo catalysts. [on SciFinder (R)

  13. Catalytic production of hydrogen from methanol for mobile, stationary and portable fuel-cell power plants

    International Nuclear Information System (INIS)

    Lukyanov, Boris N

    2008-01-01

    Main catalytic processes for hydrogen production from methanol are considered. Various schemes of fuel processors for hydrogen production in stationary, mobile and portable power plants based on fuel cells are analysed. The attention is focussed on the design of catalytic reactors of fuel processors and on the state-of-the-art in the design of catalysts for methanol conversion, carbon monoxide steam conversion and carbon monoxide selective oxidation. Prospects for the use of methanol in on-board fuel processors are discussed.

  14. Kinetic catalytic studies of scorpion's hemocyanin

    International Nuclear Information System (INIS)

    Queinnec, E.; Vuillaume, M.; Gardes-Albert, M.; Ferradini, C.; Ducancel, F.

    1991-01-01

    Hemocyanins are copper proteins which function as oxygen carriers in the haemolymph of Molluscs and Arthropods. They possess enzymatic properties: peroxidatic and catalatic activities, although they have neither iron nor porphyrin ring at the active site. The kinetics of the catalytic reaction is described. The reaction of superoxide anion with hemocyanin has been studied using pulse radiolysis at pH 9. The catalytic rate constant is 3.5 X 10 7 mol -1 .l.s -1 [fr

  15. 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.

  16. Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry.

    Science.gov (United States)

    Klankermayer, Jürgen; Wesselbaum, Sebastian; Beydoun, Kassem; Leitner, Walter

    2016-06-20

    The present Review highlights the challenges and opportunities when using the combination CO2 /H2 as a C1 synthon in catalytic reactions and processes. The transformations are classified according to the reduction level and the bond-forming processes, covering the value chain from high volume basic chemicals to complex molecules, including biologically active substances. Whereas some of these concepts can facilitate the transition of the energy system by harvesting renewable energy into chemical products, others provide options to reduce the environmental impact of chemical production already in today's petrochemical-based industry. Interdisciplinary fundamental research from chemists and chemical engineers can make important contributions to sustainable development at the interface of the energetic and chemical value chain. The present Review invites the reader to enjoy this exciting area of "catalytic chess" and maybe even to start playing some games in her or his laboratory. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Emerging catalytic technologies related to the denoxing of waste gases from thermal power stations

    International Nuclear Information System (INIS)

    Busca, G.

    2002-01-01

    The emerging catalytic technologies related to the DeNOxing of waste gases from thermal power stations are briefly discussed. In the case of the Selective Catalytic Reduction of NO x with hydrocarbons new zeolite-based or metal oxide catalytic systems are under development, whose stability and performances approach more and more those needed for a commercial process. The processes for the low temperature Selective Catalytic Reduction of NO x with ammonia are apparently promising allowing a possible application in a tail-end process configuration, at least after a total abatement of SO x . The processes of combined abatement of NO x and dioxins are already applied industrially. Also the Selective Oxidation of ammonia slip to nitrogen is already proposed as commercial process. In both last cases, however, few information is available in the open literature [it

  18. 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.

  19. 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

    2018-04-25

    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.

  20. Catalytic hydrolysis of ammonia borane via cobalt palladium nanoparticles.

    Science.gov (United States)

    Sun, Daohua; Mazumder, Vismadeb; Metin, Önder; Sun, Shouheng

    2011-08-23

    Monodisperse 8 nm CoPd nanoparticles (NPs) with controlled compositions were synthesized by the reduction of cobalt acetylacetonate and palladium bromide in the presence of oleylamine and trioctylphosphine. These NPs were active catalysts for hydrogen generation from the hydrolysis of ammonia borane (AB), and their activities were composition dependent. Among the 8 nm CoPd catalysts tested for the hydrolysis of AB, the Co(35)Pd(65) NPs exhibited the highest catalytic activity and durability. Their hydrolysis completion time and activation energy were 5.5 min and 27.5 kJ mol(-1), respectively, which were comparable to the best Pt-based catalyst reported. The catalytic performance of the CoPd/C could be further enhanced by a preannealing treatment at 300 °C under air for 15 h with the hydrolysis completion time reduced to 3.5 min. This high catalytic performance of Co(35)Pd(65) NP catalyst makes it an exciting alternative in pursuit of practical implementation of AB as a hydrogen storage material for fuel cell applications. © 2011 American Chemical Society

  1. 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)

  2. 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.

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

    Science.gov (United States)

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

    2007-06-18

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Suarez-Ojeda, Maria Eugenia [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain); Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Kim, Jungkwon [Chemical Engineering and Analytical Sciences Department, University of Manchester, Manchester (United Kingdom); Carrera, Julian [Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Metcalfe, Ian S. [Chemical Engineering and Advanced Materials Department, University of Newcastle upon Tyne, Newcastle upon Tyne (United Kingdom); Font, Josep [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain)]. E-mail: jose.font@urv.cat

    2007-06-18

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

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

    International Nuclear Information System (INIS)

    Suarez-Ojeda, Maria Eugenia; Kim, Jungkwon; Carrera, Julian; Metcalfe, Ian S.; Font, Josep

    2007-01-01

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

  6. 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

  7. 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

  8. A new approach to inertise the containments during catalytic removal of hydrogen

    International Nuclear Information System (INIS)

    Chakraborty, A.K.; Markandeya, S.G.

    1994-01-01

    Use of catalytic recombiners for the removal of hydrogen during a severe accident has been recommended by the German Reactor Safety Commission (RSK) due to numerous successful demonstrations of their performances. At the early stages of the accident, a huge quantity of hydrogen is expected to be released in some compartments requiring supplementary measures to ensure that the excess hydrogen concentration wouldn't pose a threat of deflagration /1/. In this presentation a new idea based on catalytic removal of hydrogen with simultaneous passive inertisation of the atmosphere is proposed for large dry containments particularly for those compartments where high H 2 -concentrations are expected. During the catalytic oxidation of hydrogen, the large exothermic heat of reaction causes strong heating of the catalytic plates as well as a continuous energy input in the containment. This can be limited if this large heat energy is efficiently used for heating some chemical compounds to release inert gases such as steam and/or CO 2 by dissociation at moderate temperatures. Such compounds can be arranged in the form of thin slabs in good thermal contact with the catalytic plates. Several such compounds have been identified which are capable of releasing steam and CO 2 equivalent to about 40 - 75% of their mass. Preliminary calculations have been carded out to demonstrate the effectiveness of the proposed concept for the case of two such selected chemicals placed adjacent to the catalytic plate type recombiners. The calculations performed show promising results. (author)

  9. Reactivity of organic compounds in catalytic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Minachev, Kh M; Bragin, O V

    1978-01-01

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

  10. 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.

  11. 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...

  12. Modeling and simulation of heterogeneous catalytic processes

    CERN Document Server

    Dixon, Anthony

    2014-01-01

    Heterogeneous catalysis and mathematical modeling are essential components of the continuing search for better utilization of raw materials and energy, with reduced impact on the environment. Numerical modeling of chemical systems has progressed rapidly due to increases in computer power, and is used extensively for analysis, design and development of catalytic reactors and processes. This book presents reviews of the state-of-the-art in modeling of heterogeneous catalytic reactors and processes. Reviews by leading authorities in the respective areas Up-to-date reviews of latest techniques in modeling of catalytic processes Mix of US and European authors, as well as academic/industrial/research institute perspectives Connections between computation and experimental methods in some of the chapters.

  13. 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.

  14. 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.

  15. Catalytic Kinetic Resolution of Biaryl Compounds.

    Science.gov (United States)

    Ma, Gaoyuan; Sibi, Mukund P

    2015-08-10

    Biaryl compounds with axial chirality are very common in synthetic chemistry, especially in catalysis. Axially chiral biaryls are important due to their biological activities and extensive applications in asymmetric catalysis. Thus the development of efficient enantioselective methods for their synthesis has attracted considerable attention. This Minireview discusses the progress made in catalytic kinetic resolution of biaryl compounds and chronicles significant advances made recently in catalytic kinetic resolution of biaryl scaffolds. © 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 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.

  17. Janus droplet as a catalytic micromotor

    Science.gov (United States)

    Shklyaev, Sergey

    2015-06-01

    Self-propulsion of a Janus droplet in a solution of surfactant, which reacts on a half of a drop surface, is studied theoretically. The droplet acts as a catalytic motor creating a concentration gradient, which generates its surface-tension-driven motion; the self-propulsion speed is rather high, 60 μ \\text{m/s} and more. This catalytic motor has several advantages over other micromotors: simple manufacturing, easily attained neutral buoyancy. In contrast to a single-fluid droplet, which demonstrates a self-propulsion as a result of symmetry breaking instability, for the Janus one no stability threshold exists; hence, the droplet radius can be scaled down to micrometers.

  18. Catalytic burners in larger boiler appliances

    Energy Technology Data Exchange (ETDEWEB)

    Silversand, Fredrik; Persson, Mikael (Catator AB, Lund (Sweden))

    2009-02-15

    This project focuses on the scale up of a Catator's catalytic burner technology to enable retrofit installation in existing boilers and the design of new innovative combinations of catalytic burners and boilers. Different design approaches are discussed and evaluated in the report and suggestions are made concerning scale-up. Preliminary test data, extracted from a large boiler installation are discussed together with an accurate analysis of technical possibilities following an optimization of the boiler design to benefit from the advantages of catalytic combustion. The experimental work was conducted in close collaboration with ICI Caldaie (ICI), located in Verona, Italy. ICI is a leading European boiler manufacturer in the effect segment ranging from about 20 kWt to several MWt. The study shows that it is possibly to scale up the burner technology and to maintain low emissions. The boilers used in the study were designed around conventional combustion and were consequently not optimized for implementation of catalytic burners. From previous experiences it stands clear that the furnace volume can be dramatically decreased when applying catalytic combustion. In flame combustion, this volume is normally dimensioned to avoid flame impingement on cold surfaces and to facilitate completion of the gas-phase reactions. The emissions of nitrogen oxides can be reduced by decreasing the residence time in the furnace. Even with the over-dimensioned furnace used in this study, we easily reached emission values close to 35 mg/kWh. The emissions of carbon monoxide and unburned hydrocarbons were negligible (less than 5 ppmv). It is possible to decrease the emissions of nitrogen oxides further by designing the furnace/boiler around the catalytic burner, as suggested in the report. Simultaneously, the size of the boiler installation can be reduced greatly, which also will result in material savings, i.e. the production cost can be reduced. It is suggested to optimize the

  19. 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.)

  20. Using electron beams to investigate catalytic materials

    International Nuclear Information System (INIS)

    Zhang, Bingsen; Su, Dang Sheng

    2014-01-01

    Transmission Electron microscopy (TEM) enables us, not only to reveal the morphology, but also to provide structural, chemical and electronic information about solid catalysts at the atomic level, providing a dramatic driving force for the development of heterogeneous catalysis. Almost all catalytic materials have been studied with TEM in order to obtain information about their structures, which can help us to establish the synthesis-structure-property relationships and to design catalysts with new structures and desired properties. Herein, several examples will be reviewed to illustrate the investigation of catalytic materials by using electron beams. (authors)

  1. 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.

  2. 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

  3. 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

  4. Kinetic equation of heterogeneous catalytic isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

    Trokhimets, A I [AN Belorusskoj SSR, Minsk. Inst. Fiziko-Organicheskoj Khimii

    1979-12-01

    A kinetic equation is derived for the bimolecular isotope exchange reaction between AXsub(n)sup(*) and BXsub(m)sup(o), all atoms of element X in each molecule being equivalent. The equation can be generalized for homogeneous and heterogeneous catalytic isotope exchange.

  5. Complementary structure sensitive and insensitive catalytic relationships

    NARCIS (Netherlands)

    Santen, van R.A.

    2009-01-01

    The burgeoning field of nanoscience has stimulated an intense interest in properties that depend on particle size. For transition metal particles, one important property that depends on size is catalytic reactivity, in which bonds are broken or formed on the surface of the particles. Decreased

  6. Toward Facilitative Mentoring and Catalytic Interventions

    Science.gov (United States)

    Smith, Melissa K.; Lewis, Marilyn

    2015-01-01

    In TESOL teacher mentoring, giving advice can be conceptualized as a continuum, ranging from directive to facilitative feedback. The goal, over time, is to lead toward the facilitative end of the continuum and specifically to catalytic interventions that encourage self-reflection and autonomous learning. This study begins by examining research on…

  7. Electrochemical Promotion of Catalytic Reactions Using

    DEFF Research Database (Denmark)

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

    2007-01-01

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

  8. 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.

  9. 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....

  10. Catalytic asymmetric synthesis of the alkaloid (+)-myrtine

    NARCIS (Netherlands)

    Pizzuti, Maria Gabriefla; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    A new protocol for the asymmetric synthesis of trans-2,6-disubstituted-4-piperidones has been developed using a catalytic enantioselective conjugate addition reaction in combination with a diastereoselective lithiation-substitution sequence; an efficient synthesis of (+)-myrtine has been achieved

  11. Catalytic oxidation of cyclohexane to cyclohexanone

    Indian Academy of Sciences (India)

    ... a precursor and characterized by chemical analysis using the ICP–AES method, XRD, TEM, FTIR and BET surface area determination. The oxidation reaction was carried out at 70°C under atmospheric pressure. The results showed the catalytic performance of Pt/Al2O3 as being very high in terms of turnover frequency.

  12. 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...

  13. Flame assisted synthesis of catalytic ceramic membranes

    DEFF Research Database (Denmark)

    Johansen, Johnny; Mosleh, Majid; Johannessen, Tue

    2004-01-01

    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...

  14. 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...

  15. Catalytic characterization of bi-functional catalysts derived from Pd ...

    Indian Academy of Sciences (India)

    Unknown

    1995; Lyubovsky and Pfefferle 1999; Sales et al 1999;. Hill et al 2000). ... For a catalytic system, whose activity ... catalytic systems containing Pd, supported on various acid- ..... Further studies are needed to optimize a balance between.

  16. Catalytically favorable surface patterns in Pt-Au nanoclusters

    KAUST Repository

    Mokkath, Junais Habeeb; Schwingenschlö gl, Udo

    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

  17. Catalytic control of automotive NO{sub x}: a review

    Energy Technology Data Exchange (ETDEWEB)

    Bhattacharyya, Souvik [Canterbury Univ., Mechanical Engineering Dept., Christchurch (New Zealand); Das, Randip K. [Mahindra and Mahindra Ltd., R and D Centre, Nashik (India)

    1999-07-01

    This article summarises several technical studies reported in the literature on catalytic conversion technology to control pollution due to automotive exhausts with specific focus on NO{sub x} reduction. While simple theoretical reactions are stated, the review concisely presents the various techniques available with their specifications and performances. Noble-metal converters, in spite of their proven-technology advantage, are considered expensive while zeolite-based catalysts are preferred today as increasingly more research findings have made this technology more mature. Conclusion and recommendations on specific applications have been presented as well. (Author)

  18. A review of liquid-phase catalytic hydrodechlorination

    Directory of Open Access Journals (Sweden)

    Alba Nelly Ardila Arias

    2007-09-01

    Full Text Available This survey was aimed at introducing the effect of light organochlorinated compound emissions on the envi-ronment, particularly on water, air, soil, biota and human beings. The characteristics and advantages of liquid phase catalytic hydrodechlorination as a technology for degrading these chlorinated compounds is also outlined and the main catalysts used in the hydrodechlorination process are described. Special emphasis is placed on palladium catalysts, their activity, the nature of active species and deactivation. The effect of several parameters is introduced, such as HCl, solvent, base addition and type of reducing agent used. The main results of kinetic studies, reactors used and the most important survey conclusions are presented.

  19. 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...... between errors in density functional theory calculations is shown to play an important role in reducing the predicted error on calculated rates. Uncertainties depend strongly on reaction conditions and catalyst material, and the relative rates between different catalysts are considerably better described...

  20. Investigations for the implementation of catalytic recombiners in large dry containments in Germany

    International Nuclear Information System (INIS)

    Rohde, J.; Tiltmann, M.; Froehmel, T.

    1997-01-01

    During the past few years, several concepts of mitigation have been developed and tested to limit the hydrogen concentrations in the containment atmosphere during the course of a severe accident. Extensive efforts have been given, especially in Germany and Canada, to investigate the use of catalytic recombiners. Based on the outcome of these research efforts in Germany it was recommended by the Reactor Safety Commission (RSK) in June 1994 to implement a hydrogen mitigation system, based on catalytic recombiners in large dry containments of PWR plants. Investigations are carried out at GRS, sponsored by the German Ministry of Environment, Nature Conservation and Nuclear Safety (BMU), to develop basic requirements for the implementation of a catalytic recombiner system in large dry containments. Severe accidents scenarios were calculated with the system code MELCOR to determine the mass- and energy release rates from the primary system into the containment, necessary to prepare the input data for the containment code calculations. A detailed nodalisation of the containment system of a German PWR plant (Konvoi-type) was developed for the code RA-LOC MOD4 to investigate the effectiveness of a catalytic recombiner system which consists of 53 of such devices, being distributed in the complex room arrangement. The effectiveness of such a system is demonstrated by comparing a representative severe accident sequence without and with the catalytic recombination of hydrogen. The results showed, that only in some limited areas in the containment combustible gas mixtures were formed for a limited time span and that at the end of the first day after the onset of the accident the catalytic reaction is limited due to oxygen depletion. The work is still in progress while additional severe accident sequences have to be analyzed to develop some generic guidelines for the implementation of a catalytic recombiner system in large dry containments. (author)

  1. Catalytic site identification—a web server to identify catalytic site structural matches throughout PDB

    Science.gov (United States)

    Kirshner, Daniel A.; Nilmeier, Jerome P.; Lightstone, Felice C.

    2013-01-01

    The catalytic site identification web server provides the innovative capability to find structural matches to a user-specified catalytic site among all Protein Data Bank proteins rapidly (in less than a minute). The server also can examine a user-specified protein structure or model to identify structural matches to a library of catalytic sites. Finally, the server provides a database of pre-calculated matches between all Protein Data Bank proteins and the library of catalytic sites. The database has been used to derive a set of hypothesized novel enzymatic function annotations. In all cases, matches and putative binding sites (protein structure and surfaces) can be visualized interactively online. The website can be accessed at http://catsid.llnl.gov. PMID:23680785

  2. 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.

  3. 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

  4. 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.

  5. Data Generated by Quantitative Liquid Chromatography-Mass Spectrometry Proteomics Are Only the Start and Not the Endpoint: Optimization of Quantitative Concatemer-Based Measurement of Hepatic Uridine-5'-Diphosphate-Glucuronosyltransferase Enzymes with Reference to Catalytic Activity.

    Science.gov (United States)

    Achour, Brahim; Dantonio, Alyssa; Niosi, Mark; Novak, Jonathan J; Al-Majdoub, Zubida M; Goosen, Theunis C; Rostami-Hodjegan, Amin; Barber, Jill

    2018-06-01

    Quantitative proteomic methods require optimization at several stages, including sample preparation, liquid chromatography-tandem mass spectrometry (LC-MS/MS), and data analysis, with the final analysis stage being less widely appreciated by end-users. Previously reported measurement of eight uridine-5'-diphospho-glucuronosyltransferases (UGT) generated by two laboratories [using stable isotope-labeled (SIL) peptides or quantitative concatemer (QconCAT)] reflected significant disparity between proteomic methods. Initial analysis of QconCAT data showed lack of correlation with catalytic activity for several UGTs (1A4, 1A6, 1A9, 2B15) and moderate correlations for UGTs 1A1, 1A3, and 2B7 ( R s = 0.40-0.79, P data analysis, starting from unprocessed LC-MS/MS data, was undertaken, with the aim of improving accuracy, defined by correlation against activity. Three main criteria were found to be important: choice of monitored peptides and fragments, correction for isotope-label incorporation, and abundance normalization using fractional protein mass. Upon optimization, abundance-activity correlations improved significantly for six UGTs ( R s = 0.53-0.87, P data analysis strategy and indicates, using examples, the significance of systematic data processing following acquisition. The proposed strategy offers significant improvement on existing guidelines applicable to clinically relevant proteins quantified using QconCAT. Copyright © 2018 by The American Society for Pharmacology and Experimental Therapeutics.

  6. 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

    2018-07-01

    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.

  7. Zeolitic catalytic conversion of alcohols to hydrocarbons

    Science.gov (United States)

    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.

  8. 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.

  9. 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.

  10. 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

  11. Catalytic extraction processing of contaminated scrap metal

    International Nuclear Information System (INIS)

    Griffin, T.P.; Johnston, J.E.; Payea, B.M.; Zeitoon, B.M.

    1995-01-01

    Molten Metal Technology was awarded a contract to demonstrate the applicability of the Catalytic Extraction Process, a proprietary process that could be applied to US DOE's inventory of low level mixed waste. This paper is a description of that technology, and included within this document are discussions of: (1) Program objectives, (2) Overall technology review, (3) Organic feed conversion to synthetic gas, (4) Metal, halogen, and transuranic recovery, (5) Demonstrations, (6) Design of the prototype facility, and (7) Results

  12. 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.

  13. Preparation, Characterization, and Catalytic Activity of MoCo/USY Catalyst on Hydrodeoxygenation Reaction of Anisole

    Science.gov (United States)

    Nugrahaningtyas, K. D.; Suharbiansah, R. S. R.; Rahmawati, F.

    2018-03-01

    This research aims to prepare, characterize, and study the catalytic activity of Molybdenum (Mo) and Cobalt (Co) metal with supporting material Ultra Stable Y-Zeolite (USY), to produce catalysts with activity in hydrotreatment reaction and in order to eliminate impurities compounds that containing unwanted groups heteroatoms. The bimetallic catalysts MoCo/USY were prepared by wet impregnation method with weight variation of Co metal 0%, 2%, 4%, 6%, 8%, and Mo metal 8% (w/w), respectively. Activation method of the catalyst included calcination, oxidation, reduction and the crystallinity was characterized using X-ray diffraction (XRD), the acidity of the catalyst was analyzed using Fourier Transform Infrared Spectroscopy (FT-IR) and gravimetry method, minerals present in the catalyst was analyzed using X-Ray Fluorescence (XRF), and surface of the catalyst was analyzed using Surface Area Analyzer (SAA). Catalytic activity test (benzene yield product) of MoCo/USY on hydrodeoxigenation reaction of anisole aimed to determine the effect of Mo-Co/USY for catalytic activity in the reaction hydrodeoxigenation (HDO) anisole. Based on characterization and test of catalytic activity, it is known that catalytic of MoCo/USY 2% (catalyst B) shows best activities with acidity of 10.209 mmol/g, specific area of catalyst of 426.295 m2/g, pore average of 14.135 Å, total pore volume 0.318 cc/g, and total yield of HDO products 6.06%.

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

    KAUST Repository

    Hong, Jongsup; Kirchen, Patrick; Ghoniem, Ahmed F.

    2013-01-01

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

  15. Exploration of alternate catalytic mechanisms and optimization strategies for retroaldolase design.

    Science.gov (United States)

    Bjelic, Sinisa; Kipnis, Yakov; Wang, Ling; Pianowski, Zbigniew; Vorobiev, Sergey; Su, Min; Seetharaman, Jayaraman; Xiao, Rong; Kornhaber, Gregory; Hunt, John F; Tong, Liang; Hilvert, Donald; Baker, David

    2014-01-09

    Designed retroaldolases have utilized a nucleophilic lysine to promote carbon-carbon bond cleavage of β-hydroxy-ketones via a covalent Schiff base intermediate. Previous computational designs have incorporated a water molecule to facilitate formation and breakdown of the carbinolamine intermediate to give the Schiff base and to function as a general acid/base. Here we investigate an alternative active-site design in which the catalytic water molecule was replaced by the side chain of a glutamic acid. Five out of seven designs expressed solubly and exhibited catalytic efficiencies similar to previously designed retroaldolases for the conversion of 4-hydroxy-4-(6-methoxy-2-naphthyl)-2-butanone to 6-methoxy-2-naphthaldehyde and acetone. After one round of site-directed saturation mutagenesis, improved variants of the two best designs, RA114 and RA117, exhibited among the highest kcat (>10(-3)s(-1)) and kcat/KM (11-25M(-1)s(-1)) values observed for retroaldolase designs prior to comprehensive directed evolution. In both cases, the >10(5)-fold rate accelerations that were achieved are within 1-3 orders of magnitude of the rate enhancements reported for the best catalysts for related reactions, including catalytic antibodies (kcat/kuncat=10(6) to 10(8)) and an extensively evolved computational design (kcat/kuncat>10(7)). The catalytic sites, revealed by X-ray structures of optimized versions of the two active designs, are in close agreement with the design models except for the catalytic lysine in RA114. We further improved the variants by computational remodeling of the loops and yeast display selection for reactivity of the catalytic lysine with a diketone probe, obtaining an additional order of magnitude enhancement in activity with both approaches. © 2013.

  16. 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.

  17. Vapor-Driven Propulsion of Catalytic Micromotors

    Science.gov (United States)

    Dong, Renfeng; Li, Jinxing; Rozen, Isaac; Ezhilan, Barath; Xu, Tailin; Christianson, Caleb; Gao, Wei; Saintillan, David; Ren, Biye; Wang, Joseph

    2015-08-01

    Chemically-powered micromotors offer exciting opportunities in diverse fields, including therapeutic delivery, environmental remediation, and nanoscale manufacturing. However, these nanovehicles require direct addition of high concentration of chemical fuel to the motor solution for their propulsion. We report the efficient vapor-powered propulsion of catalytic micromotors without direct addition of fuel to the micromotor solution. Diffusion of hydrazine vapor from the surrounding atmosphere into the sample solution is instead used to trigger rapid movement of iridium-gold Janus microsphere motors. Such operation creates a new type of remotely-triggered and powered catalytic micro/nanomotors that are responsive to their surrounding environment. This new propulsion mechanism is accompanied by unique phenomena, such as the distinct off-on response to the presence of fuel in the surrounding atmosphere, and spatio-temporal dependence of the motor speed borne out of the concentration gradient evolution within the motor solution. The relationship between the motor speed and the variables affecting the fuel concentration distribution is examined using a theoretical model for hydrazine transport, which is in turn used to explain the observed phenomena. The vapor-powered catalytic micro/nanomotors offer new opportunities in gas sensing, threat detection, and environmental monitoring, and open the door for a new class of environmentally-triggered micromotors.

  18. 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.

  19. 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.

  20. Electrochemical catalytic treatment of phenol wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Ma Hongzhu, E-mail: hzmachem@snnu.edu.cn [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China); Zhang Xinhai [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China); Ma Qingliang [Department of Applied Physics, College of Sciences, Taiyuan University of Technology, 030024 Taiyuan (China); Wang Bo [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China)

    2009-06-15

    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.

  1. 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.

  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. 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)

  4. 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....

  5. 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.

  6. Liquid-phase chemical hydrogen storage: catalytic hydrogen generation under ambient conditions.

    Science.gov (United States)

    Jiang, Hai-Long; Singh, Sanjay Kumar; Yan, Jun-Min; Zhang, Xin-Bo; Xu, Qiang

    2010-05-25

    There is a demand for a sufficient and sustainable energy supply. Hence, the search for applicable hydrogen storage materials is extremely important owing to the diversified merits of hydrogen energy. Lithium and sodium borohydride, ammonia borane, hydrazine, and formic acid have been extensively investigated as promising hydrogen storage materials based on their relatively high hydrogen content. Significant advances, such as hydrogen generation temperatures and reaction kinetics, have been made in the catalytic hydrolysis of aqueous lithium and sodium borohydride and ammonia borane as well as in the catalytic decomposition of hydrous hydrazine and formic acid. In this Minireview we briefly survey the research progresses in catalytic hydrogen generation from these liquid-phase chemical hydrogen storage materials.

  7. 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.

  8. 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

  9. 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

  10. 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.

  11. Removal of ammonia solutions used in catalytic wet oxidation processes.

    Science.gov (United States)

    Hung, Chang Mao; Lou, Jie Chung; Lin, Chia Hua

    2003-08-01

    Ammonia (NH(3)) is an important product used in the chemical industry, and is common place in industrial wastewater. Industrial wastewater containing ammonia is generally either toxic or has concentrations or temperatures such that direct biological treatment is unfeasible. This investigation used aqueous solutions containing more of ammonia for catalytic liquid-phase oxidation in a trickle-bed reactor (TBR) based on Cu/La/Ce composite catalysts, prepared by co-precipitation of Cu(NO(3))(2), La(NO(3))(2), and Ce(NO(3))(3) at 7:2:1 molar concentrations. The experimental results indicated that the ammonia conversion of the wet oxidation in the presence of the Cu/La/Ce composite catalysts was determined by the Cu/La/Ce catalyst. Minimal ammonia was removed from the solution by the wet oxidation in the absence of any catalyst, while approximately 91% ammonia removal was achieved by wet oxidation over the Cu/La/Ce catalyst at 230 degrees C with oxygen partial pressure of 2.0 MPa. Furthermore, the effluent streams were conducted at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes, and a reaction pathway was found linking the oxidizing ammonia to nitric oxide, nitrogen and water. The solution contained by-products, including nitrates and nitrites. Nitrite selectivity was minimized and ammonia removal maximized when the feed ammonia solution had a pH of around 12.0.

  12. 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.

  13. 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.

  14. Triblock copolymer-mediated synthesis of catalytically active gold nanostructures

    Science.gov (United States)

    Santos, Douglas C.; de Souza, Viviane C.; Vasconcelos, Diego A.; Andrade, George R. S.; Gimenez, Iara F.; Teixeira, Zaine

    2018-04-01

    The design of nanostructures based on poly(ethylene oxide)-poly(propylene)-poly(ethylene oxide) (PEO-PPO-PEO) and metal nanoparticles is becoming an important research topic due to their multiple functionalities in different fields, including nanomedicine and catalysis. In this work, water-soluble gold nanoparticles have been prepared through a green aqueous synthesis method using Pluronic F127 as both reducing and stabilizing agents. The size dependence (varying from 2 to 70 nm) and stability of gold nanoparticles were systematically studied by varying some parameters of synthesis, which were the polymer concentration, temperature, and exposure to UV-A light, being monitored by UV-Vis spectroscopy and TEM. Also, an elaborated study regarding to the kinetic of formation (nucleation and growth) was presented. Finally, the as-prepared Pluronic-capped gold nanoparticles have shown excellent catalytic activity towards the reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride, in which a higher catalytic performance was exhibited when compared with gold nanoparticles prepared by classical reduction method using sodium citrate. [Figure not available: see fulltext.

  15. 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.

  16. Catalytic fast pyrolysis of white oak wood in-situ using a bubbling fluidized bed reactor

    Science.gov (United States)

    Catalytic fast pyrolysis was performed on white oak wood using two zeolite-type catalysts as bed material in a bubbling fluidized bed reactor. The two catalysts chosen, based on a previous screening study, were Ca2+ exchanged Y54 (Ca-Y54) and a proprietary ß-zeolite type catalyst (catalyst M) both ...

  17. 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

  18. Molecular weight control in emulsion polymerization by catalytic chain transfer : a reaction engineering approach

    NARCIS (Netherlands)

    Smeets, N.M.B.; Meda, U.S.; Heuts, J.P.A.; Keurentjes, J.T.F.; Herk, van A.M.; Meuldijk, J.

    2007-01-01

    For the application of catalytic chain transfer in (mini)emulsion polymerization, catalyst partitioning and deactivation are key parameters that govern the actual catalyst concentration at the locus of polymerization and consequently the final molecular weight distribution. A global model, based on

  19. 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

  20. Turning goals into results: the power of catalytic mechanisms.

    Science.gov (United States)

    Collins, J

    1999-01-01

    Most executives have a big, hairy, audacious goal. They write vision statements, formalize procedures, and develop complicated incentive programs--all in pursuit of that goal. In other words, with the best of intentions, they install layers of stultifying bureaucracy. But it doesn't have to be that way. In this article, Jim Collins introduces the catalytic mechanism, a simple yet powerful managerial tool that helps translate lofty aspirations into concrete reality. Catalytic mechanisms are the crucial link between objectives and performance; they are a galvanizing, nonbureaucratic means to turn one into the other. What's the difference between catalytic mechanisms and most traditional managerial controls? Catalytic mechanisms share five characteristics. First, they produce desired results in unpredictable ways. Second, they distribute power for the benefit of the overall system, often to the discomfort of those who traditionally hold power. Third, catalytic mechanisms have teeth. Fourth, they eject "viruses"--those people who don't share the company's core values. Finally, they produce an ongoing effect. Catalytic mechanisms are just as effective for reaching individual goals as they are for corporate ones. To illustrate how catalytic mechanisms work, the author draws on examples of individuals and organizations that have relied on such mechanisms to achieve their goals. The same catalytic mechanism that works in one organization, however, will not necessarily work in another. Catalytic mechanisms must be tailored to specific goals and situations. To help readers get started, the author offers some general principles that support the process of building catalytic mechanisms effectively.

  1. 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.

  2. 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

  3. 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...... composition have been identified as potential candidates for methanol synthesis. These Cu-Ni alloy catalysts have been synthesized and tested in a fixed-bed continuous-flow reactor for CO hydrogenation. The metal area based activity for a Cu-Ni/SiO2 catalyst is at the same level as a Cu/ZnO/Al2O3 model...... catalyst. The high activity and selectivity of silica supported Cu-Ni alloy catalysts agrees with the fact that the DFT calculations identified Cu-Ni alloys as highly active and selective catalysts for the hydrogenation of CO to form methanol. This work has also provided a systematic study of Cu...

  4. 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.

  5. The impact of catalytic materials on fuel reformulation

    Energy Technology Data Exchange (ETDEWEB)

    Rossini, Stefano [Snamprogetti, S. Donato Milanese, Milan (Italy)

    2003-01-15

    Fuel reformulation has been seeded by the growing consciousness of the potential damages mankind was causing to the ecosystem and to itself. Fuel reformulation means that fuels are defined on a chemical composition base with additional engine-technology related standards rather than on pure performance bases. These standards, which are getting more and more stringent, can be met by different leverages, mainly catalysts and processes operating conditions.This survey reviews the contribution of catalytic materials to the production of cleaner fuel components through some significant examples selected from scientific and technical literature. Having described the trends in automotive fuels quality, production of gasoline and diesel pool components is discussed relating the required properties to the material active site configuration, i.e. acidity/basicity, structural parameters, physical constraints. While distinctions are made between pathways leading to gasoline and those leading to diesel, sulfur removal is faced on a more generalized approach.

  6. Highly Efficient Catalytic Cyclic Carbonate Formation by Pyridyl Salicylimines.

    Science.gov (United States)

    Subramanian, Saravanan; Park, Joonho; Byun, Jeehye; Jung, Yousung; Yavuz, Cafer T

    2018-03-21

    Cyclic carbonates as industrial commodities offer a viable nonredox carbon dioxide fixation, and suitable heterogeneous catalysts are vital for their widespread implementation. Here, we report a highly efficient heterogeneous catalyst for CO 2 addition to epoxides based on a newly identified active catalytic pocket consisting of pyridine, imine, and phenol moieties. The polymeric, metal-free catalyst derived from this active site converts less-reactive styrene oxide under atmospheric pressure in quantitative yield and selectivity to the corresponding carbonate. The catalyst does not need additives, solvents, metals, or co-catalysts, can be reused at least 10 cycles without the loss of activity, and scaled up easily to a kilogram scale. Density functional theory calculations reveal that the nucleophilicity of pyridine base gets stronger due to the conjugated imines and H-bonding from phenol accelerates the reaction forward by stabilizing the intermediate.

  7. 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.

  8. 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.

  9. Structural analysis of CuO / CeO{sub 2}-based catalytic materials intended for PROX reaction: Part I; Analise estrutural de materiais cataliticos a base de CuO/CeO{sub 2} destinados a reacao de PROX: parte I

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-01

    This work relates the synthesis process of CuO/CeO{sub 2} catalytic materials by a combustion reaction method as well as it introduces a structural analysis of the developed material, this structural analysis had as main focus to evaluate the influence of the doping substance (CuO) when being incorporated in the hostess matrix structure that is CeO{sub 2}. The CuO/CeO catalytic materials developed in this work are destined to preferential oxidation of CO reaction (PROX). The developed materials were characterized by XRD, SEM and textural complete analysis by the BET method. According to the results, the CuO incorporation changed crystallinity of the structure of the catalytic materials. On the other hand, the morphologic and textural characteristics did not showed significant differences regarding the presence of the doping substance (CuO) in the structure of the developed materials. The porosity of the structures of the developed catalytic materials belongs to the type macroporous. (author)

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

    Science.gov (United States)

    Collins, Gillian; Holmes, Justin D

    2016-07-01

    Recent developments in tailoring the structural and chemical properties of colloidal metal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal synthesis has also allowed tailor-made NPs to serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic and electrocatalytic applications. The engineering of future heterogenous catalysts is also moving beyond size, shape and composition considerations. Advancements in understanding structure-property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behavior of catalytic NPs. Exploiting plasmonic properties and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to the future design of catalytic NPs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Microwave-induced carbon nanotubes catalytic degradation of organic pollutants in aqueous solution

    International Nuclear Information System (INIS)

    Chen, Jing; Xue, Shuang; Song, Youtao; Shen, Manli; Zhang, Zhaohong; Yuan, Tianxin; Tian, Fangyuan; Dionysiou, Dionysios D.

    2016-01-01

    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"−"1, respectively. Therefore, this technology may have potential application for the treatment of targeted organic pollutants in wastewaters.

  12. 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.

  13. 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)

  14. 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.

  15. 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

  16. 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

  17. 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.

  18. Including lateral interactions into microkinetic models of catalytic reactions

    DEFF Research Database (Denmark)

    Hellman, Anders; Honkala, Johanna Karoliina

    2007-01-01

    In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three differ...... different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis....

  19. Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion.

    Science.gov (United States)

    Pozan, Gulin Selda

    2012-06-30

    The aim of this work was to study combustion of toluene (1000ppm) 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. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Catalytic membrane in reduction of aqueous nitrates: operational principles and catalytic performance

    NARCIS (Netherlands)

    Ilinitch, O.M.; Cuperus, F.P.; Nosova, L.V.; Gribov, E.N.

    2000-01-01

    The catalytic membrane with palladium-copper active component supported over the macroporous ceramic membrane, and a series of γ-Al 2O 3 supported Pd-Cu catalysts were prepared and investigated. In reduction of nitrate ions by hydrogen in water at ambient temperature, pronounced internal diffusion

  1. 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...

  2. 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.

  3. Computational and Physical Analysis of Catalytic Compounds

    Science.gov (United States)

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

    2015-03-01

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

  4. New separation technique. Catalytically functionated separation membrane

    Energy Technology Data Exchange (ETDEWEB)

    Urgami, Tadashi [Kansai Univ., Osaka (Japan)

    1989-02-01

    This report introduces research examples, showing the fundamental principle of the membrane by separating the catalytically functionated separation membrane into enzyme fixing separation membrane, polymerized metal complex separation membrane and polymer catalyst separation membrane. This membrane can achieve both functions of separation and catalytic reaction simultaneously and has sufficient possibility to combine powerful functions. Enzyme fixing separation membrane is prepared by carrier combination method, bridging method or covering method and the enzyme fixing method with polymerized complex in which enzyme is controlled to prevent the activity lowering as much as possible and enzyme is fixed from an aqueous solution into polymer membrane. This membrane is applied to the continuous manufacturing of invert sugar from cane sugar and adsorption and removing of harmful substances from blood by utilizing both micro-capsuled urease and active carbon. Alginic acid-copper (II) complex membrane is used for the polymerized metal complex membrane and polystyrene sulfonate membrane is used for the polymer catalyst separation membrane. 28 refs., 4 figs., 1 tabs.

  5. 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

  6. Catalytic hydroprocessing of heavy oil feedstocks

    International Nuclear Information System (INIS)

    Okunev, A G; Parkhomchuk, E V; Lysikov, A I; Parunin, P D; Semeikina, V S; Parmon, V N

    2015-01-01

    A grave problem of modern oil refining industry is continuous deterioration of the produced oil quality, on the one hand, and increase in the demand for motor fuels, on the other hand. This necessitates processing of heavy oil feedstock with high contents of sulfur, nitrogen and metals and the atmospheric residue. This feedstock is converted to light oil products via hydrogenation processes catalyzed by transition metal compounds, first of all, cobalt- or nickel-promoted molybdenum and tungsten compounds. The processing involves desulfurization, denitrogenation and demetallization reactions as well as reactions converting heavy hydrocarbons to lighter fuel components. The review discusses the mechanisms of reactions involved in the heavy feedstock hydroprocessing, the presumed structure and state of the catalytically active components and methods for the formation of supports with the desired texture. Practically used and prospective approaches to catalytic upgrading of heavy oil feedstock as well as examples of industrial processing of bitumen and vacuum residues in the presence of catalysts are briefly discussed. The bibliography includes 140 references

  7. Catalytic hydroprocessing of heavy oil feedstocks

    Science.gov (United States)

    Okunev, A. G.; Parkhomchuk, E. V.; Lysikov, A. I.; Parunin, P. D.; Semeikina, V. S.; Parmon, V. N.

    2015-09-01

    A grave problem of modern oil refining industry is continuous deterioration of the produced oil quality, on the one hand, and increase in the demand for motor fuels, on the other hand. This necessitates processing of heavy oil feedstock with high contents of sulfur, nitrogen and metals and the atmospheric residue. This feedstock is converted to light oil products via hydrogenation processes catalyzed by transition metal compounds, first of all, cobalt- or nickel-promoted molybdenum and tungsten compounds. The processing involves desulfurization, denitrogenation and demetallization reactions as well as reactions converting heavy hydrocarbons to lighter fuel components. The review discusses the mechanisms of reactions involved in the heavy feedstock hydroprocessing, the presumed structure and state of the catalytically active components and methods for the formation of supports with the desired texture. Practically used and prospective approaches to catalytic upgrading of heavy oil feedstock as well as examples of industrial processing of bitumen and vacuum residues in the presence of catalysts are briefly discussed. The bibliography includes 140 references.

  8. 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.

  9. A Hybrid Catalytic Route to Fuels from Biomass Syngas

    Energy Technology Data Exchange (ETDEWEB)

    Harmon, Laurel [LanzaTech, Inc., Skokie, IL (United States); 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., Skokie, IL (United States); Palou-Rivera, Ignasi [LanzaTech, Inc., Skokie, IL (United States); 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

  10. 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.

  11. Catalytic hydrotreating of waste cooking oil for renewable diesel production

    Energy Technology Data Exchange (ETDEWEB)

    Bezergianni, Stella; Dimitriadis, Athanasios [Centre for Research and Technology Hellas (CERTH), Thessaloniki (Greece)

    2013-06-01

    A new technology based on catalytic hydrotreating of Waste Cooking Oil (WCO) for biodiesel production has been developed in the Centre for Research and Technology Hellas (CERTH). The main premise of this process is the conversion of the WCO fatty acids into normal- and iso-paraffins. The technology was evaluated in hydroprocessing pilot plants of CERTH where feedstock origin as well as optimal catalysts and operating parameters where identified. The fractionated diesel product, called ''white'' diesel exhibits excellent fuel properties including higher heating value (over 49 MJ/kg), negligible acidity, higher oxidation stability and higher cetane number ({proportional_to}77) than conventional biodiesel. The overall product yield is {proportional_to}92% v/v. This new suggested technology is extremely appealing as it employs existing refinery infrastructure and expertise, offers feedstock flexibility, leaves no by-product and above all is economically attractive. (orig.)

  12. Catalytic production of sugar alcohols (polyols) and their application

    Energy Technology Data Exchange (ETDEWEB)

    Albert, R; Straetz, A; Vollheim, G

    1980-07-01

    The article surveys the numerous applications of the principal sugar alcohols sorbitol and xylitol and their world production in 1978. Nowadays, the industrial production of sugar alcohols is almost exclusively by catalytic hydrogenation of the corresponding sugars; thus sorbitol is manufactured by hydrogenation of D-glucose, xylitol by hydrogenation of xylose, and mannitol by hydrogenation of invert sugar or fructose. Some 80% of the world production of sugar alcohols are manufactured in batch suspension processes using Raney nickel catalysts. Apart from the Atlas Powder continuous suspension process employing nickel-carrier catalysts, continuous processes have recently been developed which use Raney nickel and prove more economical owing to the lower catalyst costs. Trickling processes with fixed catalyst continue to play a minor role. Available production capacity based on batch suspension processes can be expanded by process optimization and new catalyst developments. A newly developed special Raney nickel catalyst reduces the specific catalyst consumption by about 50%.

  13. 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.

  14. 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

  15. 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.)

  16. Structural/surface characterization and catalytic evaluation of rare-earth (Y, Sm and La) doped ceria composite oxides for CH{sub 3}SH catalytic decomposition

    Energy Technology Data Exchange (ETDEWEB)

    He, Dedong; Chen, Dingkai; Hao, Husheng; Yu, Jie; Liu, Jiangping; Lu, Jichang; Liu, Feng [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500 (China); Wan, Gengping [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500 (China); Research Center for Analysis and Measurement, Hainan University, Haikou, 570228 (China); He, Sufang [Research Center for Analysis and Measurement, Kunming University of Science and Technology, Kunming, 650093 (China); Luo, Yongming, E-mail: environcatalysis222@yahoo.com [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500 (China)

    2016-12-30

    Highlights: • Ce{sub 0.75}RE{sub 0.25}O{sub 2-δ} (RE = Y, Sm and La) were synthesized by citrate complexation method. • Ce{sub 0.75}Y{sub 0.25}O{sub 2-δ} exhibited the best stability for the decomposition of CH{sub 3}SH. • Cation radius played a key role in determining structure and surface characteristics. • Catalytic behavior depended on synergistic role of oxygen vacancies and basic sites. • Ce{sub 2}S{sub 3} accumulation on the surface was responsible for the deactivation of catalyst. - Abstract: A series of rare earth (Y, Sm and La) doped ceria composite oxides and pure CeO{sub 2} were synthesized and evaluated by conducting CH{sub 3}SH catalytic decomposition test. Several characterization studies, including XRD, BET, Raman, H{sub 2}-TPR, XPS, FT-IR, CO{sub 2}-TPD and CH{sub 3}SH-TPD, were undertaken to correlate structural and surface properties of the obtained ceria-based catalysts with their catalytic performance for CH{sub 3}SH decomposition. More oxygen vacancies and increased basic sites exhibited in the rare earth doped ceria catalysts. Y doped ceria sample (Ce{sub 0.75}Y{sub 0.25}O{sub 2-δ}), with a moderate increase in basic sites, contained more oxygen vacancies. More structural defects and active sites could be provided, and a relatively small amount of sulfur would accumulate, which resulted in better catalytic performance. The developed catalyst presented good catalytic behavior with stability very similar to that of typical zeolite-based catalysts reported previously. However, La doped ceria catalyst (Ce{sub 0.75}La{sub 0.25}O{sub 2-δ}) with the highest alkalinity was not the most active one. More sulfur species would be adsorbed and a large amount of cerium sulfide species (Ce{sub 2}S{sub 3}) would accumulate, which caused deactivation of the catalysts. The combined effect of increased oxygen vacancies and alkalinity led to the catalytic stability of Ce{sub 0.75}Sm{sub 0.25}O{sub 2-δ} sample was comparable to that of pure Ce

  17. Hydrogen Production From catalytic reforming of greenhouse gases ...

    African Journals Online (AJOL)

    ADOWIE PERE

    a fixed bed stainless steel reactor. The 20wt%. ... catalytic activity for hydrogen production with the highest yield and selectivity of 32.5% and 17.6% respectively. © JASEM ... CO2 reforming of methane is however not fully developed ..... Design and preparation of .... catalytic nickel membrane for gas to liquid (GTL) process.

  18. 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...

  19. synthesis, characterization, electrical and catalytic studies of some

    African Journals Online (AJOL)

    B. S. Chandravanshi

    catalytic activity of the VO(IV) and Mn(III) complexes have been tested in the epoxidation reaction of styrene ... Vanadyl sulfate pentahydrate, chromium chloride hexahydrate, anhydrous ferric ..... The catalytic oxidation of styrene gives the products styrene oxide, benzaldehyde, benzoic acid, ... bond via a radical mechanism.

  20. Catalytic combustion of methane over mixed oxides derived from Co-Mg/Al ternary hydrotalcites

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Zheng [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, OX1 3QR (United Kingdom); Research Centre of Eco-Environmental Sciences, CAS, Beijing 100085 (China); Jesus College, University of Oxford, OX1 3DW (United Kingdom); Yu, Junjie; Cheng, Jie; Hao, Zhengping [Research Centre of Eco-Environmental Sciences, CAS, Beijing 100085 (China); Xiao, Tiancun; Edwards, Peter P. [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, OX1 3QR (United Kingdom); Jones, Martin O. [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, OX1 3QR (United Kingdom); Rutherford Appleton Laboratory, Didcot, OX11 0QX (United Kingdom)

    2010-01-15

    Co{sub x}Mg{sub 3-x} /Al composite oxides (xCoMAO-800) were prepared by calcination of Co{sub x}Mg{sub 3-x}/Al hydrotalcites (x=0.0,0.5,1.0,1.5,2.0,2.5,3.0, respectively) at 800 C. The materials were characterized using XRD, TG-DSC, N{sub 2} adsorption-desorption and TPR. The methane catalytic combustion over the xCoMAO-800 was assessed in a fixed bed micro-reactor. The results revealed that cobalt can be homogenously dispersed into the matrices of the hydrotalcites and determines the structure, specific surface areas and porosity of the derived xCoMAO-800 oxide catalysts. The thermal stability and homogeneity of the hydrotalcites markedly depends on the cobalt concentration in the hydrotalcites. The Co-based hydrotalcite-derived oxides exhibit good activity in the catalytic combustion of methane. The catalytic activity over the xCoMAO-800 oxides enhances with increasing x up to 1.5, but subsequently decreases dramatically as cobalt loadings are further increased. The 1.5CoMAO-800 catalyst shows the best methane combustion activity, igniting methane at 450 C and completing methane combustion around 600 C. The catalytic combustion activity over the xCoMAO-800 oxides are closely related to the strong Co-Mg/Al interaction within the mixed oxides according to the TG-DSC, TPR and activity characteristics. (author)

  1. Catalytic fast pyrolysis of durian rind using silica-alumina catalyst: Effects of pyrolysis parameters.

    Science.gov (United States)

    Tan, Y L; Abdullah, A Z; Hameed, B H

    2018-05-18

    Silica-alumina catalyst was prepared and used in the catalytic fast pyrolysis of durian rind in a drop-type two-stage reactor. The effects of catalytic temperature (400 °C-600 °C) and catalyst-to-durian rind ratio (1:30-3:30) were evaluated. Bio-oil yield was increased with increased catalytic temperature due to considerable dehydration process, but it was reduced with high catalyst loading due to the overcracking of organics into light gases. Silica-alumina catalyst possessed good selectivity and the products changed according to the temperature. The major components in bio-oil were hydrocarbons, furan derivatives, and aromatic compounds at 400 °C, 500 °C, and 600 °C, respectively. The hydrogen and carbon contents of bio-oil were reduced with high catalyst loading due to the overcracking of organics, and the deoxygenation process became unfavorable. The silica-alumina catalyst worked well in catalytic fast pyrolysis of durian rind, and the condition may be adjusted based on the desired products. Copyright © 2018 Elsevier Ltd. All rights reserved.

  2. 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)

  3. 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.

  4. Catalytic dehydrogenation of alcohol over solid-state molybdenum sulfide clusters with an octahedral metal framework

    Energy Technology Data Exchange (ETDEWEB)

    Kamiguchi, Satoshi, E-mail: kamigu@riken.jp [Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako City, Saitama 351-0198 (Japan); Organometallic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako City, Saitama 351-0198 (Japan); Okumura, Kazu [School of Advanced Engineering, Kogakuin University, Nakano-machi, Hachioji City, Tokyo 192-0015 (Japan); Nagashima, Sayoko; Chihara, Teiji [Graduate School of Science and Engineering, Saitama University, Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan)

    2015-12-15

    Graphical abstract: - Highlights: • Solid-state molybdenum sulfide clusters catalyzed the dehydrogenation of alcohol. • The dehydrogenation proceeded without the addition of any oxidants. • The catalytic activity developed when the cluster was activated at 300–500 °C in H{sub 2}. • The Lewis-acidic molybdenum atom and basic sulfur ligand were catalytically active. • The clusters function as bifunctional acid–base catalysts. - Abstract: Solid-state molybdenum sulfide clusters with an octahedral metal framework, the superconducting Chevrel phases, are applied to catalysis. A copper salt of a nonstoichiometric sulfur-deficient cluster, Cu{sub x}Mo{sub 6}S{sub 8–δ} (x = 2.94 and δ ≈ 0.3), is stored in air for more than 90 days. When the oxygenated cluster is thermally activated in a hydrogen stream above 300 °C, catalytic activity for the dehydrogenation of primary alcohols to aldehydes and secondary alcohols to ketones develops. The addition of pyridine or benzoic acid decreases the dehydrogenation activity, indicating that both a Lewis-acidic coordinatively unsaturated molybdenum atom and a basic sulfur ligand synergistically act as the catalytic active sites.

  5. Hydrogen removal from LWR containments by catalytic-coated thermal insulation elements (THINCAT)

    International Nuclear Information System (INIS)

    Fischer, K.; Broeckerhoff, P.; Ahlers, G.; Gustavsson, V.; Herranz, L.; Polo, J.; Dominguez, T.; Royl, P.

    2003-01-01

    In the THINCAT project, an alternative concept for hydrogen mitigation in a light water reactor (LWR) containment is being developed. Based on catalytic coated thermal insulation elements of the main coolant loop components, it could be considered either as an alternative to backfitting passive autocatalytic recombiner devices, or as a reinforcement of their preventive effect. The present paper summarises the results achieved at about project mid-term. Potential advantages of catalytic thermal insulation studied in the project are:-reduced risk of unintended ignition,;-no work space obstruction in the containment,;-no need for seismic qualification of additional equipment,;-improved start-up behaviour of recombination reaction. Efforts to develop a suitable catalytic layer resulted in the identification of a coating procedure that ensures high chemical reactivity and mechanical stability. Test samples for use in forthcoming experiments with this coating were produced. Models to predict the catalytic rates were developed, validated and applied in a safety analysis study. Results show that an overall hydrogen concentration reduction can be achieved which is comparable to the reduction obtained using conventional recombiners. Existing experimental information supports the argument of a reduced ignition risk

  6. 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

  7. 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.

  8. IN SITU DESTRUCTION OF CHLORINATED HYDROCARBON COMPOUNDS IN GROUNDWATER USING CATALYTIC REDUCTIVE REDUCTIVE DEHALOGENATION IN A REACTIVE WELL: TESTING AND OPERATIONAL EXPERIENCES. (R825421)

    Science.gov (United States)

    A groundwater treatment technology based on catalytic reductive dehalogenation has been developed to efficiently destroy chlorinated hydrocarbons in situ using a reactive well approach. The treatment process utilizes dissolved H2 as an electron donor, in...

  9. 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.

  10. Chemical and catalytic effects of ion implantation

    International Nuclear Information System (INIS)

    Wolf, G.K.

    1982-01-01

    Energetic particles are used for inducing chemical reactions as well as for modifying the properties of materials with regard to their bulk and surface chemical behavior. The effects are partly caused by radiation damage or phase intermixing, partly by the chemical properties of the individual bombarding particles. In this contribution a survey of relevant applications of these techniques is presented: (1) Chemical reactions of implanted and recoil atoms and their use for syntheses, doping and labeling of compounds. (2) The formation of thin films by decomposing chemical compounds with ion beams. 3) Catalytic effects on substrates treated by sputtering or ion implantation. Recent results with nonmetallic substrates are reviewed. Mainly hydrogenation reactions at a solid/gas interface or redox reactions at an electrified solid/liquid interface are mentioned. The present status and future prospects of these kinds of investigations will be discussed. (author)

  11. Contact structure for use in catalytic distillation

    Science.gov (United States)

    Jones, E.M. Jr.

    1984-03-27

    A method is described 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 catalyst 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. 7 figs.

  12. Direct catalytic asymmetric aldol-Tishchenko reaction.

    Science.gov (United States)

    Gnanadesikan, Vijay; Horiuchi, Yoshihiro; Ohshima, Takashi; Shibasaki, Masakatsu

    2004-06-30

    A direct catalytic asymmetric aldol reaction of propionate equivalent was achieved via the aldol-Tishchenko reaction. Coupling an irreversible Tishchenko reaction to a reversible aldol reaction overcame the retro-aldol reaction problem and thereby afforded the products in high enantio and diastereoselectivity using 10 mol % of the asymmetric catalyst. A variety of ketones and aldehydes, including propyl and butyl ketones, were coupled efficiently, yielding the corresponding aldol-Tishchenko products in up to 96% yield and 95% ee. Diastereoselectivity was generally below the detection limit of 1H NMR (>98:2). Preliminary studies performed to clarify the mechanism revealed that the aldol products were racemic with no diastereoselectivity. On the other hand, the Tishchenko products were obtained in a highly enantiocontrolled manner.

  13. 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)

  14. Propulsion Mechanism of Catalytic Microjet Engines.

    Science.gov (United States)

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

    2014-02-01

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

  15. Catalytic Synthesis of Nitriles in Continuous Flow

    DEFF Research Database (Denmark)

    Nordvang, Emily Catherine

    The objective of this thesis is to report the development of a new, alternative process for the flexible production of nitrile compounds in continuous flow. Nitriles are an important class of compounds that find applications as solvents, chemical intermediates and pharmaceutical compounds......, 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...

  16. 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.

  17. Performance simulations of catalytic converters during the Federal Test Procedure

    Energy Technology Data Exchange (ETDEWEB)

    Shen, H.; Shamim, T.; Sengupta, S.; Son, S.; Adamczyk, A.A.

    1999-07-01

    A numerical study is carried out to predict the tailpipe emissions and emission conversion efficiencies of unburned hydrocarbon, nitrogen oxide and carbon monoxide flowing through a catalytic converter during the Federal Test Procedure (FTP). The model considers the effect of heat transfer in the catalytic converter, coupled with catalyst chemical kinetics, including an oxygen storage mechanism. The resulting governing equations based on the conservation of mass and energy are solved by a tridiagonal matrix algorithm (TDMA) with a successive line under relaxation method. The numerical scheme for this non-linear problem is found to have good convergence efficiency. The simulation for the complete FTP cycle is accomplished in less than fifteen minutes on a desktop personal computer. A 13-step reaction mechanism plus a nine-step O{sub 2} storage mechanism is used to simulate the chemical kinetics. The energy equations include the heat loss due to conduction and convection plus the energy liberated by chemical reactions. The effect of radiation is assumed to be negligible and is not considered. The results of the numerical model for both the instantaneous and accumulated emissions are found to be in good agreement with experimental measurements. The conversion efficiencies of HC, CO and NO as predicted by the model are found to be within 5% of those dynamic measurements, and calculated results of accumulated HC, CO and NO{sub x} are in fair agreement with experimental measurements. The transient measurements are also used to check the robustness of the numerical model. The model is found to be robust and hence can simulate various operating conditions of engine output to the converter.

  18. 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.

  19. 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.)

  20. Catalytic combustion in small wood burning appliances

    Energy Technology Data Exchange (ETDEWEB)

    Oravainen, H [VTT Energy, Jyvaeskylae (Finland)

    1997-12-31

    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.)

  1. 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

  2. Experimental investigation on emission reduction in neem oil biodiesel using selective catalytic reduction and catalytic converter techniques.

    Science.gov (United States)

    Viswanathan, Karthickeyan

    2018-05-01

    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.

  3. 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.

  4. Catalytic molecularly imprinted polymer membranes: development of the biomimetic sensor for phenols detection.

    Science.gov (United States)

    Sergeyeva, T A; Slinchenko, O A; Gorbach, L A; Matyushov, V F; Brovko, O O; Piletsky, S A; Sergeeva, L M; Elska, G V

    2010-02-05

    Portable biomimetic sensor devices for the express control of phenols content in water were developed. The synthetic binding sites mimicking active site of the enzyme tyrosinase were formed in the structure of free-standing molecularly imprinted polymer membranes. Molecularly imprinted polymer membranes with the catalytic activity were obtained by co-polymerization of the complex Cu(II)-catechol-urocanic acid ethyl ester with (tri)ethyleneglycoldimethacrylate, and oligourethaneacrylate. Addition of the elastic component oligourethaneacrylate provided formation of the highly cross-linked polymer with the catalytic activity in a form of thin, flexible, and mechanically stable membrane. High accessibility of the artificial catalytic sites for the interaction with the analyzed phenol molecules was achieved due to addition of linear polymer (polyethyleneglycol Mw 20,000) to the initial monomer mixture before the polymerization. As a result, typical semi-interpenetrating polymer networks (semi-IPNs) were formed. The cross-linked component of the semi-IPN was represented by the highly cross-linked catalytic molecularly imprinted polymer, while the linear one was represented by polyethyleneglycol Mw 20,000. Extraction of the linear polymer from the fully formed semi-IPN resulted in formation of large pores in the membranes' structure. Concentration of phenols in the analyzed samples was detected using universal portable device oxymeter with the oxygen electrode in a close contact with the catalytic molecularly imprinted polymer membrane as a transducer. The detection limit of phenols detection using the developed sensor system based on polymers-biomimics with the optimized composition comprised 0.063 mM, while the linear range of the sensor comprised 0.063-1 mM. The working characteristics of the portable sensor devices were investigated. Storage stability of sensor systems at room temperature comprised 12 months (87%). As compared to traditional methods of phenols

  5. Catalytic-Dielectric Barrier Discharge Plasma Reactor For Methane and Carbon Dioxide Conversion

    Directory of Open Access Journals (Sweden)

    Istadi Istadi

    2007-10-01

    Full Text Available A catalytic - DBD plasma reactor was designed and developed for co-generation of synthesis gas and C2+ hydrocarbons from methane. A hybrid Artificial Neural Network - Genetic Algorithm (ANN-GA was developed to model, simulate and optimize the reactor. Effects of CH4/CO2 feed ratio, total feed flow rate, discharge voltage and reactor wall temperature on the performance of catalytic DBD plasma reactor was explored. The Pareto optimal solutions and corresponding optimal operating parameters ranges based on multi-objectives can be suggested for catalytic DBD plasma reactor owing to two cases, i.e. simultaneous maximization of CH4 conversion and C2+ selectivity, and H2 selectivity and H2/CO ratio. It can be concluded that the hybrid catalytic DBD plasma reactor is potential for co-generation of synthesis gas and higher hydrocarbons from methane and carbon dioxide and showed better than the conventional fixed bed reactor with respect to CH4 conversion, C2+ yield and H2 selectivity for CO2 OCM process. © 2007 BCREC UNDIP. All rights reserved.[Presented at Symposium and Congress of MKICS 2007, 18-19 April 2007, Semarang, Indonesia][How to Cite: I. Istadi, N.A.S. Amin. (2007. Catalytic-Dielectric Barrier Discharge Plasma Reactor For Methane and Carbon Dioxide Conversion. Bulletin of Chemical Reaction Engineering and Catalysis, 2 (2-3: 37-44.  doi:10.9767/bcrec.2.2-3.8.37-44][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.2.2-3.8.37-44 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/8][Cited by: Scopus 1 |

  6. On the study of catalytic membrane reactor for water detritiation: Modeling approach

    International Nuclear Information System (INIS)

    Liger, Karine; Mascarade, Jérémy; Joulia, Xavier; Meyer, Xuan-Mi; Troulay, Michèle; Perrais, Christophe

    2016-01-01

    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_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.

  7. 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.

  8. 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

  9. Enhanced catalytic activity over MIL-100(Fe) loaded ceria catalysts for the selective catalytic reduction of NOx with NH₃ at low temperature.

    Science.gov (United States)

    Wang, Peng; Sun, Hong; Quan, Xie; Chen, Shuo

    2016-01-15

    The development of catalysts for selective catalytic reduction (SCR) reactions that are highly active at low temperatures and show good resistance to SO2 and H2O 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-CeO2/MIL-100(Fe) catalyst shows improved catalytic activity both at low temperatures and throughout a wide temperature window. The temperature window for 90% NOx 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 NO2 species responsible for fast SCR reactions. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. 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.

  11. A Review on Catalytic Membranes Production and Applications

    Directory of Open Access Journals (Sweden)

    Heba Abdallah

    2017-05-01

    Full Text Available The development of the chemical industry regarding reducing the production cost and obtaining a high-quality product with low environmental impact became the essential requirements of the world in these days. The catalytic membrane is considered as one of the new alternative solutions of catalysts problems in the industries, where the reaction and separation can be amalgamated in one unit. The catalytic membrane has numerous advantages such as breaking the thermodynamic equilibrium limitation, increasing conversion rate, reducing the recycle and separation costs. But the limitation or most disadvantages of catalytic membranes related to the high capital costs for fabrication or the fact that manufacturing process is still under development. This review article summarizes the most recent advances and research activities related to preparation, characterization, and applications of catalytic membranes. In this article, various types of catalytic membranes are displayed with different applications and explained the positive impacts of using catalytic membranes in various reactions. Copyright © 2017 BCREC Group. All rights reserved. Received: 1st April 2016; Revised: 14th February 2017; Accepted: 22nd February 2017 How to Cite: Abdallah, H. (2017. A Review on Catalytic Membranes Production and Applications. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (2: 136-156 (doi:10.9767/bcrec.12.2.462.136-156 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.2.462.136-156

  12. 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)

    1997-12-31

    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.)

  13. 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.)

  14. 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

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

    Energy Technology Data Exchange (ETDEWEB)

    Cantatore, Valentina, E-mail: valcan@chalmers.se; Panas, Itai [Department of Chemistry and Chemical Engineering, Energy & Materials, Chalmers University of Technology, Gothenburg (Sweden)

    2016-04-21

    We use density functional theory to describe a novel way for metal free catalytic reduction of nitric oxide NO utilizing boron doped graphene. The present study is based on the observation that boron doped graphene and O—N=N—O{sup −} act as Lewis acid-base pair allowing the graphene surface to act as a catalyst. The process implies electron assisted N=N bond formation prior to N—O dissociation. Two N{sub 2} + O{sub 2} product channels, one of which favoring N{sub 2}O formation, are envisaged as outcome of the catalytic process. Besides, we show also that the N{sub 2} + O{sub 2} formation pathways are contrasted by a side reaction that brings to N{sub 3}O{sub 3}{sup −} formation and decomposition into N{sub 2}O + NO{sub 2}{sup −}.

  16. 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.

  17. Catalytic amino acid production from biomass-derived intermediates

    KAUST Repository

    Deng, Weiping

    2018-04-30

    Amino acids are the building blocks for protein biosynthesis and find use in myriad industrial applications including in food for humans, in animal feed, and as precursors for bio-based plastics, among others. However, the development of efficient chemical methods to convert abundant and renewable feedstocks into amino acids has been largely unsuccessful to date. To that end, here we report a heterogeneous catalyst that directly transforms lignocellulosic biomass-derived α-hydroxyl acids into α-amino acids, including alanine, leucine, valine, aspartic acid, and phenylalanine in high yields. The reaction follows a dehydrogenation-reductive amination pathway, with dehydrogenation as the rate-determining step. Ruthenium nanoparticles supported on carbon nanotubes (Ru/CNT) exhibit exceptional efficiency compared with catalysts based on other metals, due to the unique, reversible enhancement effect of NH3 on Ru in dehydrogenation. Based on the catalytic system, a two-step chemical process was designed to convert glucose into alanine in 43% yield, comparable with the well-established microbial cultivation process, and therefore, the present strategy enables a route for the production of amino acids from renewable feedstocks. Moreover, a conceptual process design employing membrane distillation to facilitate product purification is proposed and validated. Overall, this study offers a rapid and potentially more efficient chemical method to produce amino acids from woody biomass components.

  18. 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)

  19. 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

  20. 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.)

  1. Combined hydrothermal liquefaction and catalytic hydrothermal gasification system and process for conversion of biomass feedstocks

    Science.gov (United States)

    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.

  2. 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.

  3. 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.

  4. Catalytic hydrotreatment of refinery waste: Demonstration project

    Energy Technology Data Exchange (ETDEWEB)

    1989-01-01

    The object of this project and report is to produce liquid hydrocarbons by the catalytic hydroprocessing of solid refinery wastes (hard pitches) in order to improve the profitability of deep conversion processes and reduce the excess production of heavy fuels. The project was mostly carried out on the ASVAHL demonstration platform site, at Solaize, and hard pitches were produced primarily by deasphalting of atmospheric or vacuum distillation residues. The project includes two experimental phases and an economic evaluation study phase. In Phase 1, two granular catalysts were used to transform pitch into standard low sulfur fuel oil: a continuously moving bed, with demetallation and conversion catalyst; a fixed bed, with hydrorefining catalyst. In Phase 2 of the project, it was proven that a hydrotreatment process using a finely dispersed catalyst in the feedstock, can, under realistic operating conditions, transform with good yields hard pitch into distillates that can be refined through standard methods. In Phase 3 of the project, it was shown that the economics of such processes are tightly linked to the price differential between white'' and black'' oil products, which is expected to increase in the future. Furthermore, the evolution of environmental constraints will impel the use of such methods, thus avoiding the coproduction of polluting solid residues. 11 figs., 1 tab.

  5. Electrochemical promotion of sulfur dioxide catalytic oxidation

    DEFF Research Database (Denmark)

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

    2000-01-01

    investigation was to study a possible non-Faradaic electrochemical promotion of the liquid-phase catalytic reaction. It has been shown that there are two negative potential promotion areas with maximum effects at approximately -0.1 and -0.2 V, and one positive potential promotion area with the maximum effect...... between 0.1 and 0.3 V. There were no Faradaic reactions in the negative polarization region, and there was an anodic current which was less than 16% of the theoretical value for an exclusively Faradaic SO2 oxidation. Therefore the promotion effects at negative polarization are completely non-Faradaic. All...... the promotion effects have been explained as mainly due to charging of the electric double layer at the gold electrode. The effect at -0.2 V also depends on the V2O5 concentration and is more pronounced at higher V2O5 concentrations. This has been ascribed to a destruction of the vanadium polymeric chains...

  6. 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.

  7. 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%

  8. Catalytic extraction processing of contaminated scrap metal

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-10-01

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

  9. 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

  10. Catalytic extraction processing of contaminated scrap metal

    International Nuclear Information System (INIS)

    Griffin, T.P.; Johnston, J.E.; Payea, B.M.

    1995-01-01

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

  11. Substrate-Directed Catalytic Selective Chemical Reactions.

    Science.gov (United States)

    Sawano, Takahiro; Yamamoto, Hisashi

    2018-05-04

    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.

  12. Catalytic glycerol steam reforming for hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-23

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

  13. 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

  14. 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

  15. 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.

  16. Novel catalytic micromotor of porous zeolitic imidazolate framework-67 for precise drug delivery.

    Science.gov (United States)

    Wang, Linlin; Zhu, Hongli; Shi, Ying; Ge, You; Feng, Xiaomiao; Liu, Ruiqing; Li, Yi; Ma, Yanwen; Wang, Lianhui

    2018-06-07

    Micromotors hold promise as drug carriers for targeted drug delivery owing to the characteristics of self-propulsion and directional navigation. However, several defects still exist, including high cost, short movement life, low drug loading and slow release rate. Herein, a novel catalytic micromotor based on porous zeolitic imidazolate framework-67 (ZIF-67) synthesized by a greatly simplified wet chemical method assisted with ultrasonication is described as an efficient anticancer drug carrier. These porous micromotors display effective autonomous motion in hydrogen peroxide and long durable movement life of up to 90 min. Moreover, the multifunctional micromotor ZIF-67/Fe3O4/DOX exhibits excellent performance in precise drug delivery under external magnetic field with high drug loading capacity of fluorescent anticancer drug DOX up to 682 μg mg-1 owing to its porous nature, high surface area and rapid drug release based on dual stimulus of catalytic reaction and solvent effects. Therefore, these porous ZIF-67-based catalytic micromotors combine the domains of metal-organic frameworks (MOFs) and micomotors, thus developing potential resources for micromotors and holding great potential as label-free and precisely controlled high-quality candidates of drug delivery systems for biomedical applications.

  17. Amperometric glucose sensor based on enhanced catalytic reduction of oxygen using glucose oxidase adsorbed onto core-shell Fe{sub 3}O{sub 4}-silica-Au magnetic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Wang Aijun [College of Geography and Environmental Science, College of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004 (China); Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007 (China); Li Yongfang [College of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Xinxiang 453003 (China); Li Zhonghua [Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007 (China); Feng Jiuju, E-mail: jjfengnju@gmail.com [College of Geography and Environmental Science, College of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004 (China); Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007 (China); Sun Yanli [Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007 (China); Chen Jianrong [College of Geography and Environmental Science, College of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004 (China)

    2012-08-01

    Monodisperse Fe{sub 3}O{sub 4} magnetic nanoparticles (NPs) were prepared under facile solvothermal conditions and successively functionalized with silica and Au to form core/shell Fe{sub 3}O{sub 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 Multiplication-Sign 10{sup -9} mol{center_dot}cm{sup -2}, and exhibited a surface-controlled quasi-reversible redox reaction, with a fast heterogeneous electron transfer rate of 7.98 {+-} 0.6 s{sup -1}. The glucose biosensor showed a broad linear range up to 3.97 mM with high sensitivity of 62.45 {mu}A{center_dot}mM{sup -1} cm{sup -2} and fast response (less than 5 s). - Graphical abstract: Core-shell structured Fe{sub 3}O{sub 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: Black-Right-Pointing-Pointer Synthesis of monodispersed Fe{sub 3}O{sub 4} nanoparticles. Black-Right-Pointing-Pointer Fabrication of core/shell Fe{sub 3}O{sub 4}-silica-Au nanoparticles. Black-Right-Pointing-Pointer Construction of a novel glucose sensor with wide linear range, high sensitivity and fast response.

  18. Simultaneous catalytic degradation of 2,4-D and MCPA herbicides using sulfate radical-based heterogeneous oxidation over persulfate activated by natural hematite (α-Fe2O3/PS)

    Science.gov (United States)

    Kermani, Majid; Mohammadi, Farzad; Kakavandi, Babak; Esrafili, Ali; Rostamifasih, Zeinab

    2018-06-01

    Herein, a sulfate radical (SO4rad -)-based oxidation process was utilized for simultaneous degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA) herbicides using mesoporous hematite-based natural semi-conductor minerals (HM-NSMs) as efficient activators of persulfate (PS). The features of the catalyst were characterized using field emission scanning electron microscopy (FESEM); Brunauer, Emmett and Teller (BET) analysis; X-ray diffraction (XRD); and energy-dispersive X-ray spectroscopy (EDS). The effect of some operational parameters, including solution pH, catalyst loading, PS dosage and temperature, on the performance system of PS/HM-NSMs was examined. A plausible oxidation mechanism for degradation of both pollutants was also proposed. Increasing the removal efficiency of herbicides follows the order of PS/HM-NSM > HM-NSM > PS. In all experiments, the 2,4-D removal rates were slightly lower than those for MCPA, indicating that 2,4-D has a more recalcitrant nature than MCPA. Under optimized conditions, degradation rates of 68.1% and 74.5% were achieved for 2,4-D and MCPA, respectively, during a 120-min reaction. HM-NSM displays a highly synergistic effect on the degradation of herbicides in the presence of PS. The trapping experiments demonstrated that both OHrad and SO4rad - radicals contribute significantly during the degradation of 2,4-D and MCPA and that sulfate radicals were the dominant species. A mineralization degree of 36% was obtained under optimum conditions. In conclusion, the coupling of PS and HM-NSM is a promising and effective technique to degrade organic matter for the treatment of herbicide-contaminated waters and wastewaters under real conditions.

  19. Patterned self-assembled monolayers for nanoscale lithography and the control of catalytically produced electroosmosis

    Science.gov (United States)

    Subramanian, Shyamala

    This thesis explores two applications of self-assembled monolayers (SAMs) (a) for developing novel molecular assembly based nanolithography techniques and (b) for tailoring zeta-potential of surfaces towards achieving directional control of catalytically induced fluid flow. The first half of the thesis develops the process of molecular ruler lithography using sacrificial host structures. This is a novel hybrid nanolithography technique which combines chemical self-assembly with conventional fabrication methods for improving the resolution of existing lithography tools to sub-50 nm. Previous work related to molecular ruler lithography have shown the use of thiol-SAMs, placed one on top of the other like a molecular resist, for scaling down feature sizes. In this thesis various engineering solutions for improving the reproducibility, yield, nanoscale roughness and overall manufacturability of the process are introduced. This is achieved by introducing a sacrificial inert layer underneath the gold parent structure. This bilayer sacrificial host allows for preferential, easy and quick removal of the parent structures, isolates the parent metal from the underlying substrate and improves reproducibility of the lift-off process. Also it opens avenues for fabrication of high aspect ratio features. Also molecular layer vapor deposition method is developed for building the multilayer molecular resist via vapor phase to reduce contaminations and yield issues associated with solution phase deposition. The smallest isolated metal features produced using this process were 40 nm in width. The second half of the thesis describes application of thiol-SAMs to tailor surface properties of gold, specifically the surface charge or zeta potential. Previous work has demonstrated that the direction of movement of fluid in the vicinity of a catalytically active bimetallic junction placed in a solution of dilute hydrogen peroxide depends on the charge of the gold surface. SAMs with

  20. Catalytic cleavage activities of 10–23 DNAzyme analogs functionalized with an amino group in its catalytic core

    Directory of Open Access Journals (Sweden)

    Qi Wang

    2012-02-01

    Full Text Available Functionalization of the catalytic loop of 10–23 DNAzyme with an amino group was performed by incorporation of 7-(3-aminopropyl-8-aza-7-deaza-2′-deoxyadenosine in different single positions. Among the nine modified positions in the catalytic loop, A9 is the unique position with positive contribution by such modification. These results indicated that more efficient deoxyribozymes remain to be explored by introduction of exogenous functional groups in an appropriate position in the catalytic loop of 10–23 DNAzyme, such as the combination of 7-functional group substituted 8-aza-7-deaza-2′-deoxyadenosine analogs and A9 position.