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Sample records for catalytic enantioselective reductions

  1. 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.

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

    DEFF Research Database (Denmark)

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

    2011-01-01

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

  3. The Catalytic Enantioselective Total Synthesis of (+)-Liphagal

    KAUST Repository

    Day, Joshua J.

    2011-06-10

    Ring a ding: The meroterpenoid natural product (+)-liphagal has been synthesized enantioselectively in 19 steps from commercially available materials. The trans-homodecalin system was achieved by ring expansion followed by stereoselective hydrogenation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. The Catalytic Enantioselective Total Synthesis of (+)-Liphagal

    KAUST Repository

    Day, Joshua J.; McFadden, Ryan M.; Virgil, Scott C.; Kolding, Helene; Alleva, Jennifer L.; Stoltz, Brian M.

    2011-01-01

    Ring a ding: The meroterpenoid natural product (+)-liphagal has been synthesized enantioselectively in 19 steps from commercially available materials. The trans-homodecalin system was achieved by ring expansion followed by stereoselective hydrogenation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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.

  6. Catalytic Enantioselective Alkylation of β-Keto Esters with Xanthydrol in the Presence of Chiral Palladium Complex

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kyu Yeon; Kim, Dae Young [Soonchunhyang Univ., Asan (Korea, Republic of)

    2016-01-15

    Our research interest has been directed toward the development of synthetic methods for the enantioselective construction of stereogenic carbon centers. Recently, we explored the catalytic enantioselective functionalization of active methines in the presence of chiral palladium(II) complexes. In conclusion, we have accomplished the efficient catalytic enantioselective alkylation of β-keto esters 1 with xanthydrol 2 with high yields and excellent enantioselectivity (up to 98% ee). It should be noted that this alkyaltion reaction proceeds well using air- and moisture-stable chiral palladium com- plexes with low loading (1 mol%)

  7. Combining silver- and organocatalysis: an enantioselective sequential catalytic approach towards pyrano-annulated pyrazoles.

    Science.gov (United States)

    Hack, Daniel; Chauhan, Pankaj; Deckers, Kristina; Mizutani, Yusuke; Raabe, Gerhard; Enders, Dieter

    2015-02-11

    A one-pot asymmetric Michael addition/hydroalkoxylation sequence, catalyzed by a sequential catalytic system consisting of a squaramide and a silver salt, provides a new series of chiral pyrano-annulated pyrazole derivatives in excellent yields (up to 95%) and high enantioselectivities (up to 97% ee).

  8. Catalytic enantioselective alkene aminohalogenation/cyclization involving atom transfer.

    Science.gov (United States)

    Bovino, Michael T; Chemler, Sherry R

    2012-04-16

    Problem solved: the title reaction was used for the synthesis of chiral 2-bromo, chloro, and iodomethyl indolines and 2-iodomethyl pyrrolidines. Stereocenter formation is believed to occur by enantioselective cis aminocupration and C-X bond formation is believed to occur by atom transfer. The ultility of the products as versatile synthetic intermediates was demonstrated, as was a radical cascade cyclization sequence. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Diastereoselective and enantioselective reduction of tetralin-1,4-dione

    Directory of Open Access Journals (Sweden)

    2008-10-01

    Full Text Available BackgroundThe chemistry of tetralin-1,4-dione, the stable tautomer of 1,4-dihydroxynaphthalene, has not been explored previously. It is readily accessible and offers interesting opportunities for synthesis.ResultsThe title reactions were explored. L-Selectride reduced the diketone to give preferentially the cis-diol (d.r. 84 : 16. Red-Al gave preferentially the trans-diol (d.r. 13 : 87. NaBH4, LiAlH4, and BH3 gave lower diastereoselectivities (yields: 76–98%. Fractional crystallization allowed isolation of the cis-diol and the trans-diol (55% and 66% yield, respectively. Borane was used to cleanly give the mono-reduction product. Highly enantioselective CBS reductions afforded the trans-diol (72% yield, 99% ee and the mono-reduction product (81%, 95% ee.ConclusionDiastereoselective and enantioselective reductions of the unexplored tetralin-1,4-dione provides a very convenient entry into a number of synthetically highly attractive 1,4-tetralindiols and 4-hydroxy-1-tetralone.

  10. Diastereoselective and enantioselective reduction of tetralin-1,4-dione.

    Science.gov (United States)

    Kündig, E Peter; Enriquez-Garcia, Alvaro

    2008-01-01

    The chemistry of tetralin-1,4-dione, the stable tautomer of 1,4-dihydroxynaphthalene, has not been explored previously. It is readily accessible and offers interesting opportunities for synthesis. The title reactions were explored. L-Selectride reduced the diketone to give preferentially the cis-diol (d.r. 84 : 16). Red-Al gave preferentially the trans-diol (d.r. 13 : 87). NaBH(4), LiAlH(4), and BH(3) gave lower diastereoselectivities (yields: 76-98%). Fractional crystallization allowed isolation of the cis-diol and the trans-diol (55% and 66% yield, respectively). Borane was used to cleanly give the mono-reduction product. Highly enantioselective CBS reductions afforded the trans-diol (72% yield, 99% ee) and the mono-reduction product (81%, 95% ee). Diastereoselective and enantioselective reductions of the unexplored tetralin-1,4-dione provides a very convenient entry into a number of synthetically highly attractive 1,4-tetralindiols and 4-hydroxy-1-tetralone.

  11. Preparative and mechanistic studies toward the rational development of catalytic, enantioselective selenoetherification reactions.

    Science.gov (United States)

    Denmark, Scott E; Kalyani, Dipannita; Collins, William R

    2010-11-10

    A systematic investigation into the Lewis base catalyzed, asymmetric, intramolecular selenoetherification of olefins is described. A critical challenge for the development of this process was the identification and suppression of racemization pathways available to arylseleniranium ion intermediates. This report details a thorough study of the influences of the steric and electronic modulation of the arylselenenyl group on the configurational stability of enantioenriched seleniranium ions. These studies show that the 2-nitrophenyl group attached to the selenium atom significantly attenuates the racemization of seleniranium ions. A variety of achiral Lewis bases catalyze the intramolecular selenoetherification of alkenes using N-(2-nitrophenylselenenyl)succinimide as the electrophile along with a Brønsted acid. Preliminary mechanistic studies suggest the intermediacy of ionic Lewis base-selenium(II) adducts. Most importantly, a broad survey of chiral Lewis bases revealed that 1,1'-binaphthalene-2,2'-diamine (BINAM)-derived thiophosphoramides catalyze the cyclization of unsaturated alcohols in the presence of N-(2-nitrophenylselenenyl)succinimide and methanesulfonic acid. A variety of cyclic seleno ethers were produced in good chemical yields and in moderate to good enantioselectivities, which constitutes the first catalytic, enantioselective selenofunctionalization of unactivated olefins.

  12. A catalytic reactor for the organocatalyzed enantioselective continuous flow alkylation of aldehydes.

    Science.gov (United States)

    Porta, Riccardo; Benaglia, Maurizio; Puglisi, Alessandra; Mandoli, Alessandro; Gualandi, Andrea; Cozzi, Pier Giorgio

    2014-12-01

    The use of immobilized metal-free catalysts offers the unique possibility to develop sustainable processes in flow mode. The challenging intermolecular organocatalyzed enantioselective alkylation of aldehydes was performed for the first time under continuous flow conditions. By using a packed-bed reactor filled with readily available supported enantiopure imidazolidinone, different aldehydes were treated with three distinct cationic electrophiles. In the organocatalyzed α-alkylation of aldehydes with 1,3-benzodithiolylium tetrafluoroborate, excellent enantioselectivities, in some cases even better than those obtained in the flask process (up to 95% ee at 25 °C), and high productivity (more than 3800 h(-1) ) were obtained, which thus shows that a catalytic reactor may continuously produce enantiomerically enriched compounds. Treatment of the alkylated products with Raney-nickel furnished enantiomerically enriched α-methyl derivatives, key intermediates for active pharmaceutical ingredients and natural products. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Predicting CYP2C19 Catalytic Parameters for Enantioselective Oxidations Using Artificial Neural Networks and a Chirality Code

    Science.gov (United States)

    Hartman, Jessica H.; Cothren, Steven D.; Park, Sun-Ha; Yun, Chul-Ho; Darsey, Jerry A.; Miller, Grover P.

    2013-01-01

    Cytochromes P450 (CYP for isoforms) play a central role in biological processes especially metabolism of chiral molecules; thus, development of computational methods to predict parameters for chiral reactions is important for advancing this field. In this study, we identified the most optimal artificial neural networks using conformation-independent chirality codes to predict CYP2C19 catalytic parameters for enantioselective reactions. Optimization of the neural networks required identifying the most suitable representation of structure among a diverse array of training substrates, normalizing distribution of the corresponding catalytic parameters (kcat, Km, and kcat/Km), and determining the best topology for networks to make predictions. Among different structural descriptors, the use of partial atomic charges according to the CHelpG scheme and inclusion of hydrogens yielded the most optimal artificial neural networks. Their training also required resolution of poorly distributed output catalytic parameters using a Box-Cox transformation. End point leave-one-out cross correlations of the best neural networks revealed that predictions for individual catalytic parameters (kcat and Km) were more consistent with experimental values than those for catalytic efficiency (kcat/Km). Lastly, neural networks predicted correctly enantioselectivity and comparable catalytic parameters measured in this study for previously uncharacterized CYP2C19 substrates, R- and S-propranolol. Taken together, these seminal computational studies for CYP2C19 are the first to predict all catalytic parameters for enantioselective reactions using artificial neural networks and thus provide a foundation for expanding the prediction of cytochrome P450 reactions to chiral drugs, pollutants, and other biologically active compounds. PMID:23673224

  14. Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system.

    Science.gov (United States)

    Huang, Xiaoqiang; Luo, Shipeng; Burghaus, Olaf; Webster, Richard D; Harms, Klaus; Meggers, Eric

    2017-10-01

    We report an unusual reaction design in which a chiral bis-cyclometalated rhodium(iii) complex enables the stereocontrolled chemistry of photo-generated carbon-centered radicals and at the same time catalyzes an enantioselective sulfonyl radical addition to an alkene. Specifically, employing inexpensive and readily available Hantzsch esters as the photoredox mediator, Rh-coordinated prochiral radicals generated by a selective photoinduced single electron reduction are trapped by allyl sulfones in a highly stereocontrolled fashion, providing radical allylation products with up to 97% ee. The hereby formed fragmented sulfonyl radicals are utilized via an enantioselective radical addition to form chiral sulfones, which minimizes waste generation.

  15. Enantioselective Evans-Tishchenko Reduction of b-Hydroxyketone Catalyzed by Lithium Binaphtholate

    Directory of Open Access Journals (Sweden)

    Makoto Nakajima

    2011-06-01

    Full Text Available Lithium diphenylbinaphtholate catalyzed the enantioselective Evans-Tishchenko reduction of achiral b-hydroxyketones to afford monoacyl-protected 1,3-diols with high stereoselectivities. In the reaction of racemic b-hydroxyketones, kinetic optical resolution occurred in a highly stereoselective manner.

  16. 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

  17. Catalytic reduction of ruthenium tetroxide

    International Nuclear Information System (INIS)

    Nakhutin, I.E.; Polyakov, A.S.; Ananyan, O.S.; Blinnikov, S.A.; Kulakov, A.I.; Takmazyan, A.S.

    1978-01-01

    RuO 4 removal from the gaseous phase by reduction to solid RuO 2 with carbon oxide has been investigated. The reaction has been shown to be autocatalytic. A catalyst (RuO 2 on Al 2 O 3 ) for the reduction has been developed. There have been determined the region of reaction RuO 4 +CO on the catalyst containing RuO 2 , the temperature dependence of the decontamination factor and the reaction order in RuO 4 . The feasibility of RuO 4 thermal decomposition on the catalyst has been shown. A number of other metal oxides that can catalyze the process is listed

  18. Boosting Chemical Stability, Catalytic Activity, and Enantioselectivity of Metal-Organic Frameworks for Batch and Flow Reactions.

    Science.gov (United States)

    Chen, Xu; Jiang, Hong; Hou, Bang; Gong, Wei; Liu, Yan; Cui, Yong

    2017-09-27

    A key challenge in heterogeneous catalysis is the design and synthesis of heterogeneous catalysts featuring high catalytic activity, selectivity, and recyclability. Here we demonstrate that high-performance heterogeneous asymmetric catalysts can be engineered from a metal-organic framework (MOF) platform by using a ligand design strategy. Three porous chiral MOFs with the framework formula [Mn 2 L(H 2 O) 2 ] are prepared from enantiopure phosphono-carboxylate ligands of 1,1'-biphenol that are functionalized with 3,5-bis(trifluoromethyl)-, bismethyl-, and bisfluoro-phenyl substituents at the 3,3'-position. For the first time, we show that not only chemical stability but also catalytic activity and stereoselectivity of the MOFs can be tuned by modifying the ligand structures. Particularly, the MOF incorporated with -CF 3 groups on the pore walls exhibits enhanced tolerance to water, weak acid, and base compared with the MOFs with -F and -Me groups. Under both batch and flow reaction systems, the CF 3 -containing MOF demonstrated excellent reactivity, selectivity, and recyclability, affording high yields and enantioselectivities for alkylations of indoles and pyrrole with a range of ketoesters or nitroalkenes. In contrast, the corresponding homogeneous catalysts gave low enantioselectivity in catalyzing the tested reactions.

  19. 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.

  20. 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

  1. Highly enantioselective catalytic cross-dehydrogenative coupling of N-carbamoyl tetrahydroisoquinolines and terminal alkynes.

    Science.gov (United States)

    Sun, Shutao; Li, Chengkun; Floreancig, Paul E; Lou, Hongxiang; Liu, Lei

    2015-04-03

    The first catalytic asymmetric cross-dehydrogenative coupling of cyclic carbamates and terminal alkynes has been established. The reaction features high enantiocontrol and excellent functional group tolerance and displays a wide range of structurally and electronically diverse carbamates as well as terminal alkynes. N-Acyl hemiaminals were identified as the reactive intermediates through preliminary control experiments. Employing readily removable carbamates as substrates rather than traditionally adopted N-aryl amines allows applications in complex molecule synthesis and therefore advances the C-H functionalization strategy to a synthetically useful level.

  2. Asymmetric Synthesis of Optically Active Spirocyclic Indoline Scaffolds through an Enantioselective Reduction of Indoles

    KAUST Repository

    Borrmann, Ruediger; Knop, Nils; Rueping, Magnus

    2016-01-01

    An enantioselective synthesis of spirocyclic indoline scaffolds was achieved by applying an asymmetric iridium-catalyzed hydrogenation of 3H-indoles. Low catalyst loadings and mild reaction conditions provide a broad range of differently substituted

  3. Catalytic Enantioselective Synthesis of 3,4-Unsubstituted Thiochromenes through Sulfa-Michael/Julia-Kocienski Olefination Cascade Reaction.

    Science.gov (United States)

    Simlandy, Amit Kumar; Mukherjee, Santanu

    2017-05-05

    A highly enantioselective cascade sulfa-Michael/Julia-Kocienski olefination reaction between 2-mercaptobenzaldehydes and β-substituted vinyl PT-sulfones has been realized for the synthesis of 3,4-unsubstituted 2H-thiochromenes. This reaction, catalyzed by diphenylprolinol TMS ether, proceeds through an aromatic iminium intermediate and furnishes a wide range of 2-substiuted 2H-thiochromenes with excellent enantioselectivities (up to 99:1 er).

  4. Asymmetric Synthesis of Optically Active Spirocyclic Indoline Scaffolds through an Enantioselective Reduction of Indoles

    KAUST Repository

    Borrmann, Ruediger

    2016-11-30

    An enantioselective synthesis of spirocyclic indoline scaffolds was achieved by applying an asymmetric iridium-catalyzed hydrogenation of 3H-indoles. Low catalyst loadings and mild reaction conditions provide a broad range of differently substituted products with excellent yields and enantioselectivities. The developed methodology allows an efficient synthesis of this important spirocyclic structural motif, which is present in numerous biologically active molecules and privileged structures in medicinal chemistry.

  5. Reductive Catalytic Fractionation of Corn Stover Lignin

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-12-05

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

  6. Catalytic/non-catalytic combination process for nitrogen oxides reduction

    International Nuclear Information System (INIS)

    Luftglass, B.K.; Sun, W.H.; Hofmann, J.E.

    1992-01-01

    This patent describes a process for the reduction of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel. It comprises introducing a nitrogenous treatment agent comprising urea, one or more of the hydrolysis products of urea, ammonia, compounds which produce ammonia as a by-product, ammonium salts of organic acids, 5- or 6-membered heterocyclic hydrocarbons having at least one cyclic nitrogen, hydroxy amino hydrocarbons, or mixtures thereof into the effluent at an effluent temperature between about 1200 degrees F and about 2100 degrees F; and contacting the treated effluent under conditions effective to reduce the nitrogen oxides in the effluent with a catalyst effective for the reduction of nitrogen oxides in the presence of ammonia

  7. Highly efficient catalytic reductive degradation of various organic ...

    Indian Academy of Sciences (India)

    aDepartment of Applied Sciences (Chemical Science Division), GUIST, Gauhati University, ... Highly improved catalytic reductive degradation of different organic dyes, in the ... was prepared by a facile co-precipitation method using ultra-high dilute aqueous solutions. ...... face chemical-modification for engineering the intrin-.

  8. 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

  9. INDUSTRIAL BOILER RETROFIT FOR NOX CONTROL: COMBINED SELECTIVE NONCATALYTIC REDUCTION AND SELECTIVE CATALYTIC REDUCTION

    Science.gov (United States)

    The paper describes retrofitting and testing a 590 kW (2 MBtu/hr), oil-fired, three-pass, fire-tube package boiler with a combined selective noncatalytic reduction (SNCR) and selective catalytic reduction (SCR) system. The system demonstrated 85% nitrogen oxides (NOx) reduction w...

  10. Catalytic and inhibitory effects of thechnetium on reduction processes

    International Nuclear Information System (INIS)

    Grases, F.; Genestar, C.; March, J.G.; March, P.

    1986-01-01

    Interactions between technetium and some anthraquinones and tartrazin in the presence of tin(II) are described. It was found that whereas the reductive process between Sn(II) and 1-amino-4-hydroxyanthraquinone is catalyzed by technetium, the reduction of tartrazin is inhibited by this element. Study of such process seems to indicate that the catalytic effect of technetium on the reduction processes is due to Tc(V) action whereas the inhibitory effect is due to the Tc(IV) species. (author)

  11. Development of a chronocoulometric method for uranium traces determination with basis on nitrate catalytic reduction

    International Nuclear Information System (INIS)

    Cantagallo, M.I.C.; Gutz, I.G.R.

    1990-01-01

    The application of chronocoulometric technique with catalytic reduction of uranium/nitrate with catalytic reduction of uranium/nitrate system is described to give a detection limits on the sub-nanomolar region of uranium. (author)

  12. Catalytic activity of lanthanum oxide for the reduction of cyclohexanone

    International Nuclear Information System (INIS)

    Sugunan, S.; Sherly, K.B.

    1994-01-01

    Lanthanum oxides, La 2 O 3 has been found to be an effective catalyst for the liquid phase reduction of cyclohexanone. The catalytic activities of La 2 O 3 activated at 300, 500 and 800 degC and its mixed oxides with alumina for the reduction of cylcohexanone with 2-propanol have been determined and the data parallel that of the electron donating properties of the catalysts. The electron donating properties of the catalysts have been determined from the adsorption of electron acceptors of different electron affinities on the surface of these oxides. (author). 15 refs., 2 figs., 1 tab

  13. Catalytic briquettes from low-rank coal for NO reduction

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-07-01

    The briquetting is one of the most ancient and widespread techniques of coal agglomeration which is nowadays becoming useless for combustion home applications. However, the social increasing interest in environmental protection opens new applications to this technique, especially in developed countries. In this work, a series of catalytic briquettes were prepared from low-rank Spanish coal and commercial pitch by means of a pressure agglomeration method. After that, they were cured in air and doped by equilibrium impregnation with vanadium compounds. Preparation conditions (especially those of activation and oxidizing process) were changed to study their effects on catalytic behaviour. Catalytic briquettes showed a relative high NO conversion at low temperatures in all cases, however, a strong relation between the preparation process and the reached NO conversion was observed. Preparation procedure has an effect not only on the NO reduction efficiency but also on the mechanical strength of the briquettes as a consequence of the structural and chemical changes carried out during the activation and oxidation procedures. Generally speaking mechanical resistance is enhanced by an optimal porous volume and the creation of new carboxyl groups on surface. Just on the contrary, NO reduction is promoted by high microporous structures and higher amounts of surface oxygen groups. Both facts force to find an optimum point in the preparation produce which will depend on the application. 24 refs., 4 figs., 3 tabs.

  14. Enantioselective syntheses and biological studies of aeruginosin 298-A and its analogs: application of catalytic asymmetric phase-transfer reaction.

    Science.gov (United States)

    Fukuta, Yuhei; Ohshima, Takashi; Gnanadesikan, Vijay; Shibuguchi, Tomoyuki; Nemoto, Tetsuhiro; Kisugi, Takaya; Okino, Tatsufumi; Shibasaki, Masakatsu

    2004-04-13

    Aeruginosin 298-A was isolated from the freshwater cyanobacterium Microcystis aeruginosa (NIES-298) and is an equipotent thrombin and trypsin inhibitor. A variety of analogs were synthesized to gain insight into the structure-activity relations. We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogs, in which all stereocenters were controlled by catalytic asymmetric phase-transfer reaction promoted by two-center asymmetric catalysts and catalytic asymmetric epoxidation promoted by a lanthanide-BINOL complex. Furthermore, serine protease inhibitory activities of aeruginosin 298-A and its analogs were examined.

  15. Bicyclic Guanidine Catalyzed Asymmetric Tandem Isomerization Intramolecular-Diels-Alder Reaction: The First Catalytic Enantioselective Total Synthesis of (+)-alpha-Yohimbine.

    Science.gov (United States)

    Feng, Wei; Jiang, Danfeng; Kee, Choon-Wee; Liu, Hongjun; Tan, Choon-Hong

    2016-02-04

    Hydroisoquinoline derivatives were prepared in moderate to good enantioselectivities via a bicyclic guanidine-catalyzed tandem isomerization intramolecular-Diels-Alder (IMDA) reaction of alkynes. With this synthetic method, the first enantioselective synthesis of (+)-alpha-yohimbine was completed in 9 steps from the IMDA products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. SNCR technology for NO sub x reduction in the cement industry. [Selective non-catalytic reduction

    Energy Technology Data Exchange (ETDEWEB)

    Kupper, D; Brentrup, L [Krupp Polysius AG, Beckum (Germany)

    1992-03-01

    This article discusses the selective non-catalytic (SNCR) process for reducing nitrogen oxides in exhaust gases from cement plants. Topics covered include operating experience, injection of additives, selection of the additive, operating costs, reduction efficiency of SNCR, capital expenditure, secondary emissions and cycles of ammonium. (UK).

  17. Enantioselective syntheses of aeruginosin 298-A and its analogues using a catalytic asymmetric phase-transfer reaction and epoxidation.

    Science.gov (United States)

    Ohshima, Takashi; Gnanadesikan, Vijay; Shibuguchi, Tomoyuki; Fukuta, Yuhei; Nemoto, Tetsuhiro; Shibasaki, Masakatsu

    2003-09-17

    We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogues, in which all stereocenters were controlled by a catalytic asymmetric phase-transfer reaction and epoxidation. Furthermore, drastic counteranion effects in phase-transfer catalysis were observed for the first time, making it possible to three-dimensionally fine-tune the catalyst (ketal part, aromatic part, and counteranion).

  18. Selective catalytic reduction of NO{sub x} by olefins

    Energy Technology Data Exchange (ETDEWEB)

    Radtke, F

    1997-12-31

    The removal of nitrogen oxides from the exhaust of lean-burn gasoline fuelled and diesel-fuelled engines, operating under net oxidizing conditions, has recently attracted considerable attention. In this work, three different catalytic systems (Al{sub 2}O{sub 3}, Cu/Al{sub 2}O{sub 3} and Cu/ZSM-5) are investigated for their suitability as catalysts for the selective reduction of nitrogen oxides by hydrocarbons in excess oxygen. Special emphasis is given to the formation of potentially harmful byproducts such as hydrogen cyanide (HCN), cyanic acid (HNCO), ammonia (NH{sub 3}) and nitrous oxide (N{sub 2}O). The effect of reaction temperature, nitrogen oxide (NO, NO{sub 2}), hydrocarbon (ethene, propene) and water on activity and the formation of byproducts is investigated. In situ FTIR spectroscopy and temperature-programmed surface reactions (TPSR) of absorbed species in different atmospheres were used to investigate the nature and reactivity of adsorbates formed under reaction conditions. The catalytic activity was strongly influenced by the presence of water in the feed. The effects of the other parameters were suppressed and the performance generally decreased, except when propene was used for the reduction of NO{sub x} over Cu/ZSM-5. Over Cu/ZSM-5 clearly higher conversion was obtained, when ethene was used as reducing agent, while there was no significant difference when starting from NO or NO{sub 2}. In contrast, with {gamma}-Al{sub 2}O{sub 3} NO{sub 2} was reduced more efficiently than NO with both reductants. The impregnation of {gamma}-Al{sub 2}O{sub 3} with copper led to an extensive loss of this performance. For dry feeds and with increasing CuO loading, the catalysts reached maximum activity at lower temperature and the maximum yield of nitrogen slightly decreased. (author) figs., tabs., refs.

  19. 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.

  20. 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.

  1. 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.

  2. Multi-Stage Selective Catalytic Reduction of NOx in Lean-Burn Engine Exhaust

    National Research Council Canada - National Science Library

    Penetrante, B

    1997-01-01

    .... A plasma can also be used to oxidize NO to NO2. This paper compares the multi-stage catalytic scheme with the plasma-assisted catalytic scheme for reduction of NOx in lean-burn engine exhausts. The advantages of plasma oxidation over catalytic oxidation are presented.

  3. COST OF SELECTIVE CATALYTIC REDUCTION (SCR) APPLICATION FOR NOX CONTROL ON COAL-FIRED BOILERS

    Science.gov (United States)

    The report provides a methodology for estimating budgetary costs associated with retrofit applications of selective catalytic reduction (SCR) technology on coal-fired boilers. SCR is a postcombustion nitrogen oxides (NOx) control technology capable of providing NOx reductions >90...

  4. A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines

    Directory of Open Access Journals (Sweden)

    Erli Sugiono

    2013-11-01

    Full Text Available A continuous-flow asymmetric organocatalytic photocyclization–transfer hydrogenation cascade reaction has been developed. The new protocol allows the synthesis of tetrahydroquinolines from readily available 2-aminochalcones using a combination of photochemistry and asymmetric Brønsted acid catalysis. The photocylization and subsequent reduction was performed with catalytic amount of chiral BINOL derived phosphoric acid diester and Hantzsch dihydropyridine as hydrogen source providing the desired products in good yields and with excellent enantioselectivities.

  5. Reaction Engineering of Biocatalytic Enantioselective Reduction: A Case Study for Aliphatic Ketones

    DEFF Research Database (Denmark)

    Leuchs, Susanne; Lima-Ramos, Joana; Greiner, Lasse

    2013-01-01

    , 15, 167–176.). In the present work, the process metrics of the ketone reduction were calculated. A cost analysis revealed that the enzyme costs are negligible, but the cost for nicotinamide cofactor NADP+ is dominating the overall cost of the chemical raw material followed by the ionic liquid (TEGO...... IL K5) used as solubiliser and the buffer. The overall cost of chemicals was €148/kgproduct. To assess the environmental impact of the process, the E-factor (kgwaste/kgproduct) 132 and the process mass intensity 133 (PMI, kgsubstrate/kgproduct) were calculated. A process model based on initial rate...

  6. Regioselectivity and Enantioselectivity in Nickel-Catalysed Reductive Coupling Reactions of Alkynes

    Science.gov (United States)

    Moslin, Ryan M.; Miller-Moslin, Karen; Jamison, Timothy F.

    2011-01-01

    Nickel-catalysed reductive coupling reactions of alkynes have emerged as powerful synthetic tools for the selective preparation of functionalized alkenes. One of the greatest challenges associated with these transformations is control of regioselectivity. Recent work from our laboratory has provided an improved understanding of several of the factors governing regioselectivity in these reactions, and related studies have revealed that the reaction mechanism can differ substantially depending on the ligand employed. A discussion of stereoselective transformations and novel applications of nickel catalysis in coupling reactions of alkynes is also included. PMID:17971951

  7. Diesel Engine Emission Reduction Using Catalytic Nanoparticles: An Experimental Investigation

    Directory of Open Access Journals (Sweden)

    Ajin C. Sajeevan

    2013-01-01

    Full Text Available Cerium oxide being a rare earth metal with dual valance state existence has exceptional catalytic activity due to its oxygen buffering capability, especially in the nanosized form. Hence when used as an additive in the diesel fuel it leads to simultaneous reduction and oxidation of nitrogen dioxide and hydrocarbon emissions, respectively, from diesel engine. The present work investigates the effect of cerium oxide nanoparticles on performance and emissions of diesel engine. Cerium oxide nanoparticles were synthesized by chemical method and techniques such as TEM, EDS, and XRD have been used for the characterization. Cerium oxide was mixed in diesel by means of standard ultrasonic shaker to obtain stable suspension, in a two-step process. The influence of nanoparticles on various physicochemical properties of diesel fuel has also been investigated through extensive experimentation by means of ASTM standard testing methods. Load test was done in the diesel engine to investigate the effect of nanoparticles on the efficiency and the emissions from the engine. Comparisons of fuel properties with and without additives are also presented.

  8. 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...

  9. Reaction mechanisms of CO2 activation and catalytic reduction

    International Nuclear Information System (INIS)

    Wolff, Niklas von

    2016-01-01

    The use of CO 2 as a C1 chemical feedstock for the fine chemical industry is interesting both economically and ecologically, as CO 2 is non-toxic, abundant and cheap. Nevertheless, transformations of CO 2 into value-added products is hampered by its high thermodynamic stability and its inertness toward reduction. In order to design new catalysts able to overcome this kinetic challenge, a profound understanding of the reaction mechanisms at play in CO 2 reduction is needed. Using novel N/Si+ frustrated Lewis pairs (FLPs), the influence of CO 2 adducts and different hydro-borane reducing agents on the reaction mechanism in the catalytic hydroboration of CO 2 were investigated, both by DFT calculations and experiments. In a second step, the reaction mechanism of a novel reaction for the creation of C-C bonds from CO 2 and pyridyl-silanes (C 5 H 4 N-SiMe 3 ) was analyzed by DFT calculations. It was shown that CO 2 plays a double role in this transformation, acting both as a catalyst and a C1-building block. The fine understanding of this transformation then led to the development of a novel approach for the synthesis of sulfones and sulfonamides. Starting from SO 2 and aromatic silanes/amine silanes, these products were obtained in a single step under metal-free conditions. Noteworthy, sulfones and sulfonamides are common motifs in organic chemistry and found in a variety of highly important drugs. Finally, this concept was extended to aromatic halides as coupling partners, and it was thus shown for the first time that a sulfonylative Hiyama reaction is a possible approach to the synthesis of sulfones. (author) [fr

  10. Physical chemistry of catalytic reduction of nitroarenes using various nanocatalytic systems: past, present, and future

    International Nuclear Information System (INIS)

    Begum, Robina; Rehan, Rida; Farooqi, Zahoor H.; Butt, Zonarah; Ashraf, Sania

    2016-01-01

    The catalytic reduction of nitroarenes under various catalytic systems has been widely reported in the flood of publications during last twenty years. This reaction has become a benchmark for testing catalytic activity of inorganic nanoparticles stabilized in various systems. This tutorial review presents design and classification of inorganic nanocatalysts along with their stabilizing agents used for catalytic reduction of nitroarenes. The techniques used for characterization of catalysts have been highlighted in this review. The mechanism of catalytic reduction has been described in a tutorial way. Factors affecting the rate of reduction of nitroarenes in the presence of metal nanoparticles stabilized in polyelectrolyte brushes, polyionic liquids, micelles, dendrimers, and microgels have been discussed for further development in this area.Graphical abstract

  11. Physical chemistry of catalytic reduction of nitroarenes using various nanocatalytic systems: past, present, and future

    Energy Technology Data Exchange (ETDEWEB)

    Begum, Robina [University of the Punjab, Centre for Undergraduate Studies (Pakistan); Rehan, Rida; Farooqi, Zahoor H., E-mail: zhfarooqi@gmail.com; Butt, Zonarah; Ashraf, Sania [University of the Punjab, Institute of Chemistry (Pakistan)

    2016-08-15

    The catalytic reduction of nitroarenes under various catalytic systems has been widely reported in the flood of publications during last twenty years. This reaction has become a benchmark for testing catalytic activity of inorganic nanoparticles stabilized in various systems. This tutorial review presents design and classification of inorganic nanocatalysts along with their stabilizing agents used for catalytic reduction of nitroarenes. The techniques used for characterization of catalysts have been highlighted in this review. The mechanism of catalytic reduction has been described in a tutorial way. Factors affecting the rate of reduction of nitroarenes in the presence of metal nanoparticles stabilized in polyelectrolyte brushes, polyionic liquids, micelles, dendrimers, and microgels have been discussed for further development in this area.Graphical abstract.

  12. Two-stage Catalytic Reduction of NOx with Hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Umit S. Ozkan; Erik M. Holmgreen; Matthew M. Yung; Jonathan Halter; Joel Hiltner

    2005-12-21

    A two-stage system for the catalytic reduction of NO from lean-burn natural gas reciprocating engine exhaust is investigated. Each of the two stages uses a distinct catalyst. The first stage is oxidation of NO to NO{sub 2} and the second stage is reduction of NO{sub 2} to N{sub 2} with a hydrocarbon. The central idea is that since NO{sub 2} is a more easily reduced species than NO, it should be better able to compete with oxygen for the combustion reaction of hydrocarbon, which is a challenge in lean conditions. Early work focused on demonstrating that the N{sub 2} yield obtained when NO{sub 2} was reduced was greater than when NO was reduced. NO{sub 2} reduction catalysts were designed and silver supported on alumina (Ag/Al{sub 2}O{sub 3}) was found to be quite active, able to achieve 95% N{sub 2} yield in 10% O{sub 2} using propane as the reducing agent. The design of a catalyst for NO oxidation was also investigated, and a Co/TiO{sub 2} catalyst prepared by sol-gel was shown to have high activity for the reaction, able to reach equilibrium conversion of 80% at 300 C at GHSV of 50,000h{sup -1}. After it was shown that NO{sub 2} could be more easily reduced to N{sub 2} than NO, the focus shifted on developing a catalyst that could use methane as the reducing agent. The Ag/Al{sub 2}O{sub 3} catalyst was tested and found to be inactive for NOx reduction with methane. Through iterative catalyst design, a palladium-based catalyst on a sulfated-zirconia support (Pd/SZ) was synthesized and shown to be able to selectively reduce NO{sub 2} in lean conditions using methane. Development of catalysts for the oxidation reaction also continued and higher activity, as well as stability in 10% water, was observed on a Co/ZrO{sub 2} catalyst, which reached equilibrium conversion of 94% at 250 C at the same GHSV. The Co/ZrO{sub 2} catalyst was also found to be extremely active for oxidation of CO, ethane, and propane, which could potential eliminate the need for any separate

  13. Development of tartaric acid derived chiral guanidines and their application to catalytic enantioselective α-hydroxylation of β-dicarbonyl compounds.

    Science.gov (United States)

    Zou, Liwei; Wang, Baomin; Mu, Hongfang; Zhang, Huanrui; Song, Yuming; Qu, Jingping

    2013-06-21

    A novel library of chiral guanidines featuring a tartaric acid skeleton was developed from diethyl l-tartrate. These guanidines are easily accessed with tunable steric and electronic properties. The utilities of the guanidines were highlighted by their ability to catalyze the α-hydroxylation of β-ketoesters and β-diketones with remarkable efficiency and excellent enantioselectivity.

  14. Catalytic reduction of NO by methane using a Pt/C/polybenzimidazole/Pt/C fuel cell

    DEFF Research Database (Denmark)

    Petrushina, Irina; Cleemann, Lars Nilausen; Refshauge, Rasmus

    2007-01-01

    with participation of H+ or electrochemically produced hydrogen. When added, methane partially suppresses the electrochemical reduction of NO. Methane outlet concentration monitoring has shown the CH4 participation in the chemical catalytic reduction, i.e., methane co-adsorption with NO inhibited the electrochemical...... NO reduction and introduced a dominant chemical path of the NO reduction. The products of the NO reduction with methane were N2, C2H4, and water. The catalytic NO reduction by methane was promoted when the catalyst was negatively polarized (−0.2 V). Repeated negative polarization of the catalyst increased...

  15. Metal-Free Catalytic Enantioselective C–B Bond Formation: (Pinacolato)boron Conjugate Additions to α,β-Unsaturated Ketones, Esters, Weinreb Amides and Aldehydes Promoted by Chiral N-Heterocyclic Carbenes

    Science.gov (United States)

    Wu, Hao; Radomkit, Suttipol; O’Brien, Jeannette M.; Hoveyda, Amir H.

    2012-01-01

    The first broadly applicable metal-free enantioselective method for boron conjugate addition (BCA) to α,β-unsaturated carbonyls is presented. The C–B bond forming reactions are promoted in the presence of 2.5–7.5 mol % of a readily accessible C1-symmetric chiral imidazolinium salt, which is converted, in situ, to the catalytically active diastereo- and enantiomerically pure N-heterocyclic carbene (NHC) by the common organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu). In addition to the commercially available bis(pinacolato)diboron [B2(pin)2], and in contrast to reactions with the less sterically demanding achiral NHCs, the presence of MeOH is required for high efficiency. Acyclic and cyclic α,β-unsaturated ketones, as well as acyclic esters, Weinreb amides and aldehydes can serve as suitable substrates; the desired β-boryl carbonyls are isolated in up to 94% yield and >98:2 enantiomer ratio (er). Transformations are often carried out at ambient temperature. In certain cases, such as when the relatively less reactive unsaturated amides are used, elevated temperatures are required (50–66 °C); nonetheless, reactions remain highly enantioselective. The utility of the NHC-catalyzed method is demonstrated through comparison with the alternative Cu-catalyzed protocols; in cases involving a polyfunctional substrate, unique profiles in chemoselectivity are exhibited by the metal-free approach (e.g., conjugate addition vs reaction with an alkyne, allene or aldehyde). PMID:22559866

  16. Novel, Regenerable Microlith Catalytic Reactor for CO2 Reduction via Bosch Process, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Precision Combustion, Inc. (PCI) proposes to develop an extremely compact, lightweight and regenerable MicrolithREG catalytic CO2 reduction reactor, capable of...

  17. Asymmetric NHC-catalyzed aza-Diels-Alder reactions: Highly enantioselective route to α-amino acid derivatives and DFT calculations

    KAUST Repository

    Yang, Limin; Wang, Fei; Lee, Richmond; Lv, Yunbo; Huang, Kuo-Wei; Zhong, Guofu

    2014-01-01

    A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study

  18. Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement

    OpenAIRE

    Liu, Wen-Bo; Okamoto, Noriko; Alexy, Eric J.; Hong, Allen Y.; Tran, Kristy; Stoltz, Brian M.

    2016-01-01

    A catalytic, enantioselective ? -alkylation of ?,?-unsaturated malonates and ketoesters is reported. This strategy entails a highly regio- and enantioselective iridium-catalyzed ?-alkylation of an extended enolate, and a subsequent translocation of chirality to the ?-position via a Cope rearrangement.

  19. Uniformity index measurement technology using thermocouples to improve performance in urea-selective catalytic reduction systems

    Science.gov (United States)

    Park, Sangki; Oh, Jungmo

    2018-05-01

    The current commonly used nitrogen oxides (NOx) emission reduction techniques employ hydrocarbons (HCs), urea solutions, and exhaust gas emissions as the reductants. Two of the primary denitrification NOx (DeNOx) catalyst systems are the HC-lean NOx trap (HC-LNT) catalyst and urea-selective catalytic reduction (urea-SCR) catalyst. The secondary injection method depends on the type of injector, injection pressure, atomization, and spraying technique. In addition, the catalyst reaction efficiency is directly affected by the distribution of injectors; hence, the uniformity index (UI) of the reductant is very important and is the basis for system optimization. The UI of the reductant is an indicator of the NOx conversion efficiency (NCE), and good UI values can reduce the need for a catalyst. Therefore, improving the UI can reduce the cost of producing a catalytic converter, which are expensive due to the high prices of the precious metals contained therein. Accordingly, measurement of the UI is an important process in the development of catalytic systems. Two of the commonly used methods for measuring the reductant UI are (i) measuring the exhaust emissions at many points located upstream/downstream of the catalytic converter and (ii) acquisition of a reductant distribution image on a section of the exhaust pipe upstream of the catalytic converter. The purpose of this study is to develop a system and measurement algorithms to measure the exothermic response distribution in the exhaust gas as the reductant passes through the catalytic converter of the SCR catalyst system using a set of thermocouples downstream of the SCR catalyst. The system is used to measure the reductant UI, which is applied in real-time to the actual SCR system, and the results are compared for various types of mixtures for various engine operating conditions and mixer types in terms of NCE.

  20. Adaptive Model Predictive Control of Diesel Engine Selective Catalytic Reduction (SCR) Systems

    Science.gov (United States)

    McKinley, Thomas L.

    2009-01-01

    Selective catalytic reduction or SCR is coming into worldwide use for diesel engine emissions reduction for on- and off-highway vehicles. These applications are characterized by broad operating range as well as rapid and unpredictable changes in operating conditions. Significant nonlinearity, input and output constraints, and stringent performance…

  1. Catalytic reduction of nitric oxide with ammonia over transition metal ion-exchanged Y zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Sciyama, T; Arakawa, T; Matsuda, T; Yamazoe, N; Takita, Y

    1975-01-01

    The catalytic reduction of nitric oxide with ammonia was studied over transition metal ion-exchanged Y zeolite (Me-Y) catalysts. The reaction products are nitrogen, nitrous oxide, and water in all cases. Selectivities to N/sub 2/ are 60 to 80% on all the cation exchanged zeolite catalysts exhibiting a relatively minor variation with the cationic species exchanged. The copper (II)-Y catalyst exhibits low temperature activity and has an unusual catalytic activity-temperature profile with a maximum at 120/sup 0/C. The catalytic activity is enhanced considerably when a second cation, especially cobalt (II) or iron (III) is coexchanged together with Cu (II) in Y zeolite.

  2. Multi-stage selective catalytic reduction of NOx in lean burn engine exhaust

    Energy Technology Data Exchange (ETDEWEB)

    Penetrante, B.M.; Hsaio, M.C.; Merritt, B.T.; Vogtlin, G.E. [Lawrence Livermore National Lab., CA (United States)

    1997-12-31

    Many studies suggest that the conversion of NO to NO{sub 2} is an important intermediate step in the selective catalytic reduction (SCR) of NO{sub x} to N{sub 2}. Some effort has been devoted to separating the oxidative and reductive functions of the catalyst in a multi-stage system. This method works fine for systems that require hydrocarbon addition. The hydrocarbon has to be injected between the NO oxidation catalyst and the NO{sub 2} reduction catalyst; otherwise, the first-stage oxidation catalyst will also oxidize the hydrocarbon and decrease its effectiveness as a reductant. The multi-stage catalytic scheme is appropriate for diesel engine exhausts since they contain insufficient hydrocarbons for SCR, and the hydrocarbons can be added at the desired location. For lean-burn gasoline engine exhausts, the hydrocarbons already present in the exhausts will make it necessary to find an oxidation catalyst that can oxidize NO to NO{sub 2} but not oxidize the hydrocarbon. A plasma can also be used to oxidize NO to NO{sub 2}. Plasma oxidation has several advantages over catalytic oxidation. Plasma-assisted catalysis can work well for both diesel engine and lean-burn gasoline engine exhausts. This is because the plasma can oxidize NO in the presence of hydrocarbons without degrading the effectiveness of the hydrocarbon as a reductant for SCR. In the plasma, the hydrocarbon enhances the oxidation of NO, minimizes the electrical energy requirement, and prevents the oxidation of SO{sub 2}. This paper discusses the use of multi-stage systems for selective catalytic reduction of NO{sub x}. The multi-stage catalytic scheme is compared to the plasma-assisted catalytic scheme.

  3. Catalytic properties of Ru-mordenite for NO reduction

    Czech Academy of Sciences Publication Activity Database

    Labhsetwar, NK.; Minamino, H.; Mukherjee, M.; Mitsuhashi, T.; Rayalu, S.; Dhakad, M.; Haneda, H.; Šubrt, Jan; Devotta, S.

    2007-01-01

    Roč. 261, č. 2 (2007), s. 213-217 ISSN 1381-1169 Grant - others:CSIR(IN) CORE(08) Institutional research plan: CEZ:AV0Z40320502 Keywords : NO reduction * catalyst * Ru-zeolite Subject RIV: CA - Inorganic Chemistry Impact factor: 2.707, year: 2007

  4. 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.)

  5. 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.)

  6. Calcium(ii)-catalyzed enantioselective conjugate additions of amines.

    Science.gov (United States)

    Uno, Brice E; Dicken, Rachel D; Redfern, Louis R; Stern, Charlotte M; Krzywicki, Greg G; Scheidt, Karl A

    2018-02-14

    The direct enantioselective chiral calcium(ii)·phosphate complex (Ca[CPA] 2 )-catalyzed conjugate addition of unprotected alkyl amines to maleimides was developed. This mild catalytic system represents a significant advance towards the general convergent asymmetric amination of α,β-unsaturated electrophiles, providing medicinally relevant chiral aminosuccinimide products in high yields and enantioselectivities. Furthermore, the catalyst can be reused directly from a previously chromatographed reaction and still maintain both high yield and selectivity.

  7. An efficient catalytic reductive amination: A facile one-pot access to ...

    Indian Academy of Sciences (India)

    An efficient catalytic reductive amination: A facile one-pot access to ... itors and in the manufacture of detergents and plastics.1 ... ammoniaborane/Ti(OiPr)4,5e ... demonstrated the first method for synthesis of 1,2- ... and column chromatography (Silica gel, n-hexane/ethyl .... supporting information at www.ias.ac.in/chemsci.

  8. COMPARISON OF WEST GERMAN AND U.S. FLUE GAS DESULFURIZATION AND SELECTIVE CATALYTIC REDUCTION COSTS

    Science.gov (United States)

    The report documents a comparison of the actual cost retrofitting flue gas desulfurization (FGD) and selective catalytic reduction (SCR) on Federal Republic of German (FRG) boilers to cost estimating procedures used in the U.S. to estimate the retrofit of these controls on U.S. b...

  9. Azeotropic distillation assisted fabrication of silver nanocages and their catalytic property for reduction of 4-nitrophenol.

    Science.gov (United States)

    Min, Jianzhong; Wang, Fei; Cai, Yunliang; Liang, Shuai; Zhang, Zhenwei; Jiang, Xingmao

    2015-01-14

    Monodisperse silver nanocages (AgNCs) with specific interiors were successfully synthesized by an azeotropic distillation (AD) assisted method and exhibited excellent catalytic activities for reduction of 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) due to the unique hollow morphology and small thickness of the silver shell.

  10. 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.)

  11. GENERIC VERIFICATION PROTOCOL FOR DETERMINATION OF EMISSIONS REDUCTIONS FROM SELECTIVE CATALYTIC REDUCTIONS CONTROL TECHNOLOGIES FOR HIGHWAY, NONROAD, AND STATIONARY USE DIESEL ENGINES

    Science.gov (United States)

    The protocol describes the Environmental Technology Verification (ETV) Program's considerations and requirements for verification of emissions reduction provided by selective catalytic reduction (SCR) technologies. The basis of the ETV will be comparison of the emissions and perf...

  12. Conformation and Catalytic Properties Studies of Candida rugosa Lip7 via Enantioselective Esterification of Ibuprofen in Organic Solvents and Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Xiang Li

    2013-01-01

    Full Text Available Enantioselective esterification of ibuprofen was conducted to evaluate the enzyme activity and ees of lipase from Candida rugosa (CRL7 in ten conventional organic solvents and three ionic liquids. Different alcohols were tested for selecting the most suitable acyl acceptor due to the fact that the structure of alcohols (branch and length of carbon chains; location of –OH functional group could affect the enzyme activity and ees. The results of alcohol and solvent selection revealed that 1-isooctanol and isooctane were the best substrate and reaction medium, respectively, because of the highest enzyme activity and ees. Compared with the control, conformational studies via FT-IR indicate that the variations of CRL7’s secondary structure elements are probably responsible for the differences of enzyme activity and ees in the organic solvents and ionic liquids. Moreover, the effects of reaction parameters, such as molar ratio, water content, temperature, and reaction time, in the selected reaction medium, were also examined.

  13. I.C. Engine emission reduction by copper oxide catalytic converter

    Science.gov (United States)

    Venkatesan, S. P.; Shubham Uday, Desai; Karan Hemant, Borana; Rajarshi Kushwanth Goud, Kagita; Lakshmana Kumar, G.; Pavan Kumar, K.

    2017-05-01

    The toxic gases emitted from diesel engines are more than petrol engines. Predicting the use of diesel engines, even more in future, this system is developed and can be used to minimize the harmful gases. Toxic gases include NOX, CO, HC and Smoke which are harmful to the atmosphere as well as to the human beings. The main aim of this work is to fabricate system, where the level of intensity of toxic gases is controlled through chemical reaction to more agreeable level. This system acts itself as an exhaust system; hence there is no needs to fit separate the silencer. The whole assembly is fitted in the exhaust pipe from engine. In this work, catalytic converter with copper oxide as a catalyst, by replacing noble catalysts such as platinum, palladium and rhodium is fabricated and fitted in the engine exhaust. With and without catalytic converter, the experimentations are carried out at different loads such as 0%, 25%, 50%, 75%, and 100% of maximum rated load. From the experimental results it is found that the maximum reduction is 32%, 61% and 21% for HC, NOx and CO respectively at 100% of maximum rated load when compared to that of without catalytic converter. This catalytic converter system is cash effective and more economical than the existing catalytic converter.

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

    Science.gov (United States)

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

    2010-08-03

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

  15. 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.)

  16. HYBRID SELECTIVE NON-CATALYTIC REDUCTION (SNCR)/SELECTIVE CATALYTIC REDUCTION (SCR) DEMONSTRATION FOR THE REMOVAL OF NOx FROM BOILER FLUE GASES; FINAL

    International Nuclear Information System (INIS)

    Jerry B. Urbas

    1999-01-01

    The U. S. Department of Energy (DOE), Electric Power Research Institute (EPRI), Pennsylvania Electric Energy Research Council, (PEERC), New York State Electric and Gas and GPU Generation, Inc. jointly funded a demonstration to determine the capabilities for Hybrid SNCR/SCR (Selective Non-Catalytic Reduction/Selective Catalytic Reduction) technology. The demonstration site was GPU Generation's Seward Unit No.5 (147MW) located in Seward Pennsylvania. The demonstration began in October of 1997 and ended in December 1998. DOE funding was provided through Grant No. DE-FG22-96PC96256 with T. J. Feeley as the Project Manager. EPRI funding was provided through agreements TC4599-001-26999 and TC4599-002-26999 with E. Hughes as the Project Manager. This project demonstrated the operation of the Hybrid SNCR/SCR NO(sub x) control process on a full-scale coal fired utility boiler. The hybrid technology was expected to provide a cost-effective method of reducing NO(sub x) while balancing capital and operation costs. An existing urea based SNCR system was modified with an expanded-duct catalyst to provide increased NO(sub x) reduction efficiency from the SNCR while producing increased ammonia slip levels to the catalyst. The catalyst was sized to reduce the ammonia slip to the air heaters to less than 2 ppm while providing equivalent NO(sub x) reductions. The project goals were to demonstrate hybrid technology is capable of achieving at least a 55% reduction in NO(sub x) emissions while maintaining less than 2ppm ammonia slip to the air heaters, maintain flyash marketability, verify the cost benefit and applicability of Hybrid post combustion technology, and reduce forced outages due to ammonium bisulfate (ABS) fouling of the air heaters. Early system limitations, due to gas temperature stratification, restricted the Hybrid NO(sub x) reduction capabilities to 48% with an ammonia slip of 6.1 mg/Nm(sup 3) (8 ppm) at the catalyst inlet. After resolving the stratification problem

  17. HYBRID SELECTIVE NON-CATALYTIC REDUCTION (SNCR)/SELECTIVE CATALYTIC REDUCTION (SCR) DEMONSTRATION FOR THE REMOVAL OF NOx FROM BOILER FLUE GASES

    Energy Technology Data Exchange (ETDEWEB)

    Jerry B. Urbas

    1999-05-01

    The U. S. Department of Energy (DOE), Electric Power Research Institute (EPRI), Pennsylvania Electric Energy Research Council, (PEERC), New York State Electric and Gas and GPU Generation, Inc. jointly funded a demonstration to determine the capabilities for Hybrid SNCR/SCR (Selective Non-Catalytic Reduction/Selective Catalytic Reduction) technology. The demonstration site was GPU Generation's Seward Unit No.5 (147MW) located in Seward Pennsylvania. The demonstration began in October of 1997 and ended in December 1998. DOE funding was provided through Grant No. DE-FG22-96PC96256 with T. J. Feeley as the Project Manager. EPRI funding was provided through agreements TC4599-001-26999 and TC4599-002-26999 with E. Hughes as the Project Manager. This project demonstrated the operation of the Hybrid SNCR/SCR NO{sub x} control process on a full-scale coal fired utility boiler. The hybrid technology was expected to provide a cost-effective method of reducing NO{sub x} while balancing capital and operation costs. An existing urea based SNCR system was modified with an expanded-duct catalyst to provide increased NO{sub x} reduction efficiency from the SNCR while producing increased ammonia slip levels to the catalyst. The catalyst was sized to reduce the ammonia slip to the air heaters to less than 2 ppm while providing equivalent NO{sub x} reductions. The project goals were to demonstrate hybrid technology is capable of achieving at least a 55% reduction in NO{sub x} emissions while maintaining less than 2ppm ammonia slip to the air heaters, maintain flyash marketability, verify the cost benefit and applicability of Hybrid post combustion technology, and reduce forced outages due to ammonium bisulfate (ABS) fouling of the air heaters. Early system limitations, due to gas temperature stratification, restricted the Hybrid NO{sub x} reduction capabilities to 48% with an ammonia slip of 6.1 mg/Nm{sup 3} (8 ppm) at the catalyst inlet. After resolving the stratification

  18. Enantioselective synthesis of almorexant via iridium-catalysed intramolecular allylic amidation

    NARCIS (Netherlands)

    Fananas Mastral, Martin; Teichert, Johannes F.; Fernandez-Salas, Jose Antonio; Heijnen, Dorus; Feringa, Ben L.

    2013-01-01

    An enantioselective synthesis of almorexant, a potent antagonist of human orexin receptors, is presented. The chiral tetrahydroisoquinoline core structure was prepared via iridium-catalysed asymmetric intramolecular allylic amidation. Further key catalytic steps of the synthesis include an oxidative

  19. Natural clinoptilolite exchanged with iron: characterization and catalytic activity in nitrogen monoxide reduction

    Directory of Open Access Journals (Sweden)

    Daria Tito-Ferro

    2016-12-01

    Full Text Available The aim of this work was to characterize the natural clinoptilolite from Tasajeras deposit, Cuba, modified by hydrothermal ion-exchange with solutions of iron (II sulfate and iron (III nitrate in acid medium. Besides this, its catalytic activity to reduce nitrogen monoxide with carbon monoxide/propene in the presence of oxygen was evaluated. The characterization was performed by Mössbauer and UV-Vis diffuse reflectance spectroscopies and adsorption measurements. The obtained results lead to conclude that in exchanged samples, incorporated divalent and trivalent irons are found in octahedral coordination. Both irons should be mainly in cationic extra-framework positions inside clinoptilolite channels as charge compensating cations, and also as iron oxy-hydroxides resulting from limited hydrolysis of these cations. The iron (III exchanged samples has a larger amount of iron oxy-hydroxides agglomerates. The iron (II exchanged samples have additionally iron (II sulfate adsorbed. The catalytic activity in the nitrogen monoxide reduction is higher in the exchanged zeolites than starting. Among all samples, those exchanged of iron (II has the higher catalytic activity. This lead to outline that, main catalytically active centers are associated with divalent iron.

  20. NOx Selective Catalytic Reduction (SCR) on Self-Supported V-W-doped TiO2 Nanofibers

    DEFF Research Database (Denmark)

    Marani, Debora; Silva, Rafael Hubert; Dankeaw, Apiwat

    2017-01-01

    Electrospun V–W–TiO2 catalysts, resulting in a solid solution of V and W in the anatase phase, are prepared as nonwoven nanofibers for NOx selective catalytic reduction (SCR). Preliminary catalytic characterization indicates their superior NOx conversion efficiency to the-state-of-the-art materia...

  1. 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...

  2. Nickel-catalyzed regio- and enantioselective aminolysis of 3,4-epoxy alcohols.

    Science.gov (United States)

    Wang, Chuan; Yamamoto, Hisashi

    2015-04-08

    The first catalytic regio- and enantioselective aminolysis of 3,4-epoxy alcohols has been accomplished. Under the catalysis of Ni(ClO4)2·6H2O, the C4 selective ring opening of various 3,4-epoxy alcohols proceeded in a stereospecific manner with high regioselectivities. Furthermore, with the Ni-BINAM catalytic system the enantioselective ring opening of 3,4-epoxy alcohols furnished various γ-hydroxy-δ-amino alcohols as products with complete regiocontrol and high enantioselectivities (up to 94% ee).

  3. 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 −}.

  4. Mean field approximation for the kinetics of the selective catalytic reduction of NO by ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Santos, M.; Bodanese, J.P. [Centro de Ensino Sao Jose, Universidade do Vale do Itajai (Brazil); S. Grandi, B.C. da [Departamento de Fisica, Universidade Federal de Santa Catarina, Florianopolis (Brazil)

    2007-04-15

    In this work we study a catalytic reaction model among three monomers in order to understand the chemical kinetics of the selective catalytic reduction of nitrogen oxide by ammonia (4NO+4NH{sub 3}+O{sub 2}{yields}4N{sub 2}+6H{sub 2}O). Our model takes into account the formation of the intermediate species in the global scheme of the reaction. In order to determine the dynamical behaviour of the model we used single site approximation method. In this approach we have observed that, depending on the values of the control parameters, the model presents an active or an inactive phase. In fact, the dynamical phase diagram of the model exhibits a first order line separating these two phases. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

    DEFF Research Database (Denmark)

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

    2015-01-01

    For the first time, the standard and fast selective catalytic reduction of NO by NH3 are described in a complete catalytic cycle, that is able to produce the correct stoichiometry, while only allowing adsorption and desorption of stable molecules. The standard SCR reaction is a coupling of the ac...... for standard SCR. Finally, the role of a nitrate/nitrite equilibrium and the possible in uence of Cu dimers and Brønsted sites are discussed, and an explanation is offered as to how a catalyst can be effective for SCR, while being a poor catalyst for NO oxidation to NO2....... spectroscopy (FTIR). A consequence of the reaction scheme is that all intermediates in fast SCR are also part of the standard SCR cycle. The calculated activation energy by density functional theory (DFT) indicates that the oxidation of an NO molecule by O2 to a bidentate nitrate ligand is rate determining...

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

    DEFF Research Database (Denmark)

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

    1996-01-01

    activity with respect to each species involved. An existing particle model, the Grain-Micrograin Model, which simulates sulphur capture on limestone under oxidizing conditions is considered in the modelling. Simulation results in good qualitative agreement with experimental data are obtained here......A theoretical study of the complex transient system of simultaneous sulphur capture and catalytic reactions of N-containing compounds taking place on a single limestone particle is conducted. The numerical technique developed previously by the authors (Kiil et al. 1994) based on collocation...... for the catalytic chemistry of NH3 during simultaneous sulphur capture on a Stevns Chalk particle. The reduction of NO by NH3 over CaSO4 (which is the product of the reaction between SO2, O2 and limestone) was found to be important because this reaction could explain the change in selectivity with increased solid...

  7. Selective catalytic reduction of nitric oxide by ammonia over Cu-exchanged Cuban natural zeolites

    International Nuclear Information System (INIS)

    Moreno-Tost, Ramon; Santamaria-Gonzalez, Jose; Rodriguez-Castellon, Enrique; Jimenez-Lopez, Antonio; Autie, Miguel A.; Glacial, Marisol Carreras; Gonzalez, Edel; Pozas, Carlos De las

    2004-01-01

    The catalytic selective reduction of NO over Cu-exchanged natural zeolites (mordenite (MP) and clinoptilolite (HC)) from Cuba using NH 3 as reducing agent and in the presence of excess oxygen was studied. Cu(II)-exchanged zeolites are very active catalysts, with conversions of NO of 95%, a high selectivity to N 2 at low temperatures, and exhibiting good water tolerance. The chemical state of the Cu(II) in exchanged zeolites was characterized by H 2 -TPR and XPS. Cu(II)-exchanged clinoptilolite underwent a severe deactivation in the presence of SO 2 . However, Cu(II)-exchanged mordenite not only maintained its catalytic activity, but even showed a slight improvement after 20h of reaction in the presence of 100ppm of SO 2

  8. Green synthesis of gold nanoparticles using aspartame and their catalytic activity for p-nitrophenol reduction

    Science.gov (United States)

    Wu, Shufen; Yan, Songjing; Qi, Wei; Huang, Renliang; Cui, Jing; Su, Rongxin; He, Zhimin

    2015-05-01

    We demonstrated a facile and environmental-friendly approach to form gold nanoparticles through the reduction of HAuCl4 by aspartame. The single-crystalline structure was illustrated by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The energy-dispersive X-ray spectroscopy (EDS) and Fourier transform infrared (FTIR) results indicated that aspartame played a pivotal role in the reduction and stabilization of the gold crystals. The crystals were stabilized through the successive hydrogen-bonding network constructed between the water and aspartame molecules. Additionally, gold nanoparticles synthesized through aspartame were shown to have good catalytic activity for the reduction of p-nitrophenol to p-aminophenol in the presence of NaBH4.

  9. Catalytic selective reduction of NO with ethylene over a series of copper catalysts on amorphous silicas

    International Nuclear Information System (INIS)

    Carniti, P.; Gervasini, A.; Modica, V.H.; Ravasio, N.

    2000-01-01

    Catalytic selective reduction of NO to N 2 was studied comparing a series of Cu-based catalysts (ca. 8wt.%) supported over amorphous pure and modified silicas: SiO 2 , SiO 2 -Al 2 O 3 , SiO 2 -TiO 2 , SiO 2 -ZrO 2 . The catalysts were prepared by the chemisorption-hydrolysis method which ensured the formation of a unique copper phase well dispersed over all supports, as confirmed by scanning electron micrographs (SEMs). Temperature-programmed reduction (TPR) analyses confirmed the presence of dispersed copper species which underwent complete reduction at a temperature of about 220C, independently of the support. It was found that the support affects the extent of NO reduction as well as the selectivity to N 2 formation. Maximum N 2 yield was found in the range 275-300C. The catalyst prepared over SiO 2 -Al 2 O 3 was the most active and selective with respect to the other silicas. Competitiveness factors (c.f.'s) as high as 13-20% in the temperature range 200-250C could be calculated. For all catalysts, the temperature of the N 2 peak maximum did not correspond to that of the maximum C 2 H 4 oxidation to CO 2 , suggesting the presence of two different sites for the oxidation and the reduction activity. On the catalyst prepared on SiO 2 -Al 2 O 3 , a kinetic interpretation of catalytic data collected at different contact times and temperatures permitted evaluating the ratio between kinetic coefficients as well as the difference between activation energies of NO reduction by C 2 H 4 and C 2 H 4 oxidation by O 2

  10. Selective catalytic reduction of sulfur dioxide to elemental sulfur. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Liu, W.; Flytzani-Stephanopoulos, M.; Sarofim, A.F.

    1995-06-01

    This project has investigated new metal oxide catalysts for the single stage selective reduction of SO{sub 2} to elemental sulfur by a reductant, such as CO. Significant progress in catalyst development has been made during the course of the project. We have found that fluorite oxides, CeO{sub 2} and ZrO{sub 2}, and rare earth zirconates such as Gd{sub 2}Zr{sub 2}O{sub 7} are active and stable catalysts for reduction Of SO{sub 2} by CO. More than 95% sulfur yield was achieved at reaction temperatures about 450{degrees}C or higher with the feed gas of stoichiometric composition. Reaction of SO{sub 2} and CO over these catalysts demonstrated a strong correlation of catalytic activity with the catalyst oxygen mobility. Furthermore, the catalytic activity and resistance to H{sub 2}O and CO{sub 2} poisoning of these catalysts were significantly enhanced by adding small amounts of transition metals, such as Co, Ni, Co, etc. The resulting transition metal-fluorite oxide composite catalyst has superior activity and stability, and shows promise in long use for the development of a greatly simplified single-step sulfur recovery process to treat variable and dilute SO{sub 2} concentration gas streams. Among various active composite catalyst systems the Cu-CeO{sub 2} system has been extensively studied. XRD, XPS, and STEM analyses of the used Cu-CeO{sub 2} catalyst found that the fluorite crystal structure of ceria was stable at the present reaction conditions, small amounts of copper was dispersed and stabilized on the ceria matrix, and excess copper oxide particles formed copper sulfide crystals of little contribution to catalytic activity. A working catalyst consisted of partially sulfated cerium oxide surface and partially sulfided copper clusters. The overall reaction kinetics were approximately represented by a first order equation.

  11. Surface coverage of Pt atoms on PtCo nanoparticles and catalytic kinetics for oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Rongzhong, E-mail: rongzhong.jiang@us.army.mi [Sensors and Electron Devices Directorate, U.S. Army Research Laboratory, 2800 Powder Mill Road, Adelphi, MD 20783-1197 (United States); Rong, Charles; Chu, Deryn [Sensors and Electron Devices Directorate, U.S. Army Research Laboratory, 2800 Powder Mill Road, Adelphi, MD 20783-1197 (United States)

    2011-02-01

    The surface coverage of Pt atoms on PtCo nanoparticles and its effect on catalytic kinetics for oxygen reduction were investigated. The PtCo nanoparticles with different surface coverage of Pt atoms were synthesized with various methods, including normal chemical method, microemulsion synthesis, and ultrasound-assisted microemulsion. A model of Pt atoms filling into a spherical nanoparticle was proposed to explain the relationship of surface metal atoms and nanoparticle size. The catalytic activity of the PtCo nano-particles is highly dependent on the synthetic methods, even if they have the same chemical composition. The PtCo nano-particles synthesized with ultrasound-assisted microemulsion showed the highest activity, which is attributed to an increase of active surface coverage of Pt atoms on the metal nanoparticles. The rate of oxygen reduction at 0.5 V (vs. SCE) catalyzed by the PtCo synthesized with ultrasound-assisted micro-emulsion was about four times higher than that of the PtCo synthesized with normal chemical method. As demonstrated with rotating-ring disk electrode measurement, the PtCo nano-particles can catalyze oxygen 4-electron reduction to water without intermediate H{sub 2}O{sub 2} detected.

  12. Enhanced Activity of Nanocrystalline Zeolites for Selective Catalytic Reduction of NOx

    International Nuclear Information System (INIS)

    Sarah C. Larson; Vicki H. Grassian

    2006-01-01

    Nanocrystalline zeolites with discrete crystal sizes of less than 100 nm have different properties relative to zeolites with larger crystal sizes. Nanocrystalline zeolites have improved mass transfer properties and very large internal and external surface areas that can be exploited for many different applications. The additional external surface active sites and the improved mass transfer properties of nanocrystalline zeolites offer significant advantages for selective catalytic reduction (SCR) catalysis with ammonia as a reductant in coal-fired power plants relative to current zeolite based SCR catalysts. Nanocrystalline NaY was synthesized with a crystal size of 15-20 nm and was thoroughly characterized using x-ray diffraction, electron paramagnetic resonance spectroscopy, nitrogen adsorption isotherms and Fourier Transform Infrared (FT-IR) spectroscopy. Copper ions were exchanged into nanocrystalline NaY to increase the catalytic activity. The reactions of nitrogen dioxides (NO x ) and ammonia (NH 3 ) on nanocrystalline NaY and CuY were investigated using FT-IR spectroscopy. Significant conversion of NO 2 was observed at room temperature in the presence of NH 3 as monitored by FT-IR spectroscopy. Copper-exchanged nanocrystalline NaY was more active for NO 2 reduction with NH 3 relative to nanocrystalline NaY

  13. Selective catalytic reduction system and process using a pre-sulfated zirconia binder

    Science.gov (United States)

    Sobolevskiy, Anatoly; Rossin, Joseph A.

    2010-06-29

    A selective catalytic reduction (SCR) process with a palladium catalyst for reducing NOx in a gas, using hydrogen as a reducing agent is provided. The process comprises contacting the gas stream with a catalyst system, the catalyst system comprising (ZrO.sub.2)SO.sub.4, palladium, and a pre-sulfated zirconia binder. The inclusion of a pre-sulfated zirconia binder substantially increases the durability of a Pd-based SCR catalyst system. A system for implementing the disclosed process is further provided.

  14. Development of a choronocoulometric method for determining traces of uranium using the catalytic nitrate reduction

    International Nuclear Information System (INIS)

    Cantagallo, M.I.C.; Gutz, I.G.R.

    1990-01-01

    With the aim of improving the sensitivity of the electroanalytical determination of uranium at trace levels. The uranium catalyzed reduction of nitrate on mercury electrode and the technique of chronocoulometry were used. Several experimental parameters were investigated (electrolyte composition, potential program, integration time, blank correction, temperature, previous separation) and adequate conditions were selected for the analytical determination. Under these conditions it was possible to exceed the best reported sensitivity for the catalytic determination, extending the detection limit to 3.10 -10 M. Exploratory study of the combination of this procedure with pre-concentration of uranium ions on the electrode revealed a detection limit ten limes lower. (author) [pt

  15. Hydrogen cyanide formation in selective catalytic reduction of nitrogen oxides over Cu/ZSM-5

    Energy Technology Data Exchange (ETDEWEB)

    Radtke, F; Koeppel, R; Baiker, A [Department of Chemical Engineering and Industrial Chemistry, Swiss Federal Institute of Technology, Zurich, (Switzerland)

    1994-01-06

    Hydrogen cyanide is formed over Cu/ZSM-5 during the selective catalytic reduction of NO[sub x] by either propylene or ethylene in the temperature range 450-600 K. Under the reaction conditions used (reactant feed: 973 ppm NO, 907 ppm propene or 1448 ppm ethylene, 2% oxygen, W/F=0.1 g s cm[sup -3]), the concentration of hydrogen cyanide reaches 20, respectively, 30 ppm, depending on whether ethylene or propene are used as hydrocarbons. In addition, significant N[sub 2]O formation is observed at temperatures lower than 700 K, independent of the hydrocarbon used

  16. Semi-catalytic reduction of secondary amides to imines and aldehydes.

    Science.gov (United States)

    Lee, Sun-Hwa; Nikonov, Georgii I

    2014-06-21

    Secondary amides can be reduced by silane HSiMe2Ph into imines and aldehydes by a two-stage process involving prior conversion of amides into iminoyl chlorides followed by catalytic reduction mediated by the ruthenium complex [Cp(i-Pr3P)Ru(NCCH3)2]PF6 (1). Alkyl and aryl amides bearing halogen, ketone, and ester groups were converted with moderate to good yields under mild reaction conditions to the corresponding imines and aldehydes. This procedure does not work for substrates bearing the nitro-group and fails for heteroaromatic amides. In the case of cyano substituted amides, the cyano group is reduced to imine.

  17. Gold Decorated Graphene for Rapid Dye Reduction and Efficient Electro Catalytic Oxidation of Ethanol

    Science.gov (United States)

    Siddhardha, R. S.; Kumar v, Lakshman; Kaniyoor, A.; Podila, R.; Kumar, V. S.; Venkataramaniah, K.; Ramaprabhu, S.; Rao, A.; Ramamurthy, S. S.; Clemson University Team; Sri Sathya Sai Institute of Higher Learning Team; IITMadras Team

    2013-03-01

    A well known disadvantage in fabrication of metal-graphene composite is the use of surfactants that strongly adsorb on the surface and reduce the performance of the catalyst. Here, we demonstrate a novel one pot synthesis of gold nanoparticles (AuNPs) by laser ablation of gold strip and simultaneous decoration of these on functionalized graphene derivatives. Not only the impregnation of AuNPs was linker free, but also the synthesis by itself was surfactant free. This resulted in in-situ decoration of pristine AuNPs on functionalized graphene derivatives. These materials were well characterized and tested for catalytic applications pertaining to dye reduction and electrooxidation. The catalytic reduction rates are 1.4 x 102 and 9.4x102 times faster for Rhodamine B and Methylene Blue dyes respectively, compared to earlier reports. The enhanced rate involves synergistic interplay of electronic relay between AuNPs and the dye, also charge transfer between the graphene system and dye. In addition, the onset potential for ethanol oxidation was found to be more negative ~ 100 mV, an indication of its promising application in direct ethanol fuel cells.

  18. Poly(N-isopropylacrylamide-co-methacrylic acid microgel stabilized copper nanoparticles for catalytic reduction of nitrobenzene

    Directory of Open Access Journals (Sweden)

    Farooqi Zahoor H.

    2015-09-01

    Full Text Available Poly(N-isopropylacrylamide-co-methacrylic acid microgels [p(NIPAM-co-MAAc] were synthesized by precipitation polymerization of N-isopropylacrylamide and methacrylic acid in aqueous medium. These microgels were characterized by dynamic light scattering and Fourier transform infrared spectroscopy. These microgels were used as micro-reactors for in situ synthesis of copper nanoparticles using sodium borohydride (NaBH4 as reducing agent. The hybrid microgels were used as catalysts for the reduction of nitrobenzene in aqueous media. The reaction was performed with different concentrations of cat­alyst and reducing agent. A linear relationship was found between apparent rate constant (kapp and amount of catalyst. When the amount of catalyst was increased from 0.13 to 0.76 mg/mL then kapp was increased from 0.03 to 0.14 min-1. Activation parameters were also determined by performing reaction at two different temperatures. The catalytic process has been discussed in terms of energy of activation, enthalpy of activation and entropy of activation. The synthesized particles were found to be stable even after 14 weeks and showed catalytic activity for the reduction of nitrobenzene.

  19. Preparation of silver nanoparticles/polydopamine functionalized polyacrylonitrile fiber paper and its catalytic activity for the reduction 4-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Shixiang, E-mail: shixianglu@bit.edu.cn [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Yu, Jianying; Cheng, Yuanyuan [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Wang, Qian; Barras, Alexandre [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Xu, Wenguo [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Szunerits, Sabine [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Cornu, David [Institut Européen des Membranes, UMR 5635, Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), CNRS, Université Montpellier 2, 276 rue de la Galéra, Montpellier 34000 (France); Boukherroub, Rabah, E-mail: rabah.boukherroub@iemn.univ-lille1.fr [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France)

    2017-07-31

    Graphical abstract: Illustration of the preparation of Ag nanoparticles coated paper and its catalytic application for 4-nitrophenol reduction into the corresponding 4-aminophenol. - Highlights: • Polyacrylonitrile paper was functionalized with polydopamine and Ag nanoparticles. • Polydopamine coating layer played both reductive and adhesive roles. • The composite material displayed good catalytic activity for 4-nitrophenol reduction. • The process was environmentally benign and facile. - Abstract: The study reports on the preparation of polyacrylonitrile fiber paper (PANFP) functionalized with polydopamine (PD) and silver nanoparticles (Ag NPs), named as Ag NPs/PD/PANFP. The composite material was obtained via a simple two-step chemical process. First, a thin polydopamine layer was coated onto the PANFP surface through immersion into an alkaline dopamine (pH 8.5) aqueous solution at room temperature. The reductive properties of polydopamine were further exploited for the deposition of Ag NPs. The morphology and chemical composition of the composite material were characterized using scanning electron microscopy (SEM), X-ray diffraction pattern (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic activity of the nanocomposite was evaluated for the reduction of 4-nitrophenol using sodium borohydride (NaBH{sub 4}) at room temperature. The Ag NPs/PD/PANFP displayed good catalytic performance with a full reduction of 4-nitrophenol into the corresponding 4-aminophenol within 30 min. Moreover, the composite material exhibited a good stability up to 4 cycles without a significant loss of its catalytic activity.

  20. Electrochemical preparation of iron cuboid nanoparticles and their catalytic properties for nitrite reduction

    International Nuclear Information System (INIS)

    Chen Yanxin; Chen Shengpei; Chen Qingsong; Zhou Zhiyou; Sun Shigang

    2008-01-01

    Iron cuboid nanoparticles supported on glassy carbon (denoted nm-Fe/GC) were prepared by electrochemical deposition under cyclic voltammetric (CV) conditions. The structure and composition of the Fe nanomaterials were characterized by scanning electron microscopy (SEM), selected area electron diffraction (SAED), X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDX). The results demonstrated that the Fe cuboid nanoparticles are dispersed discretely on GC substrate with an average size ca. 171 nm, and confirmed that the electrochemical synthesized nanocubes are single crystals of pure Fe. The catalytic properties of the Fe cuboid nanoparticles towards nitrite electroreduction were investigated, and enhanced electrocatalytic activity of the Fe nanocubes has been determined. In comparison with the data obtained on a bulk-Fe electrode, the onset potential of nitrite reduction on nm-Fe/GC is positively sifted by 100 mV, and the steady reduction current density is enhanced about 2.4-3.2 times

  1. Catalytic reduction of NO and N20 for CO on Co-ZSM-5

    International Nuclear Information System (INIS)

    Rios, Luis Alberto; Aristizabal, Gladys Liliana; Ruiz, Julio Fernando; Montes Consuelo

    1996-01-01

    Several catalysts with the help of ZSM-5 with Co were tested in the catalytic reduction of NO and N2O using CO like agent reducer and in presence of variable quantities of O2 The cobalt incorporated in the zeolite ZSM-5 for the methods of ionic exchange, impregnation and substitution. ZSM-5 exchanged with Co presented the highest conversions of NO (80% to 5OO oC), in presence of 3000 ppm of O2; When adding 25.700 ppm of O2 the conversion it diminished notably, that which shows an effect inhibitor of the O2. The substituted catalysts and impregnated they were less active for the reduction of the NO. With all the catalysts conversions of 70-90% were achieved for the N2O; Additionally, marked deactivation of the catalyst was not presented with the time

  2. Enantioselective Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds.

    Science.gov (United States)

    Hari, Durga Prasad; Waser, Jerome

    2017-06-28

    Enantioselective catalytic methods allowing the addition of both a nucleophile and an electrophile onto diazo compounds give a fast access into important building blocks. Herein, we report the highly enantioselective oxyalkynylation of diazo compounds using ethynylbenziodoxol-(on)e reagents and a simple copper bisoxazoline catalyst. The obtained α-benzoyloxy propargylic esters are useful building blocks, which are difficult to synthesize in enantiopure form using other methods. The obtained products could be efficiently transformed into vicinal diols and α-hydroxy propargylic esters without loss in enantiopurity.

  3. Effect of process parameters and injector position on the efficiency of NOx reduction by selective non catalytic reduction technique

    International Nuclear Information System (INIS)

    Hamid, A.; Mehmood, M.A.; Irfan, N.; Javed, M.T.; Waheed, K.

    2009-01-01

    An experimental investigation has been performed to study the effect of atomizer pressure dilution of the reducing reagent and the injector position on the efficiency or the NOx reduction by a selective non-catalytic reduction technique using urea as a reducing agent. Experiments were performed with a flow reactor in which flue gas was generated by the combustion of methane in air at stoichiometric amount of oxygen and the desired levels of initial NOx (400-450 ppm) were achieved by doping the flame with ammonia. The work was directed to investigate the effect of atomizer pressure, dilution of urea reagent and the injector position. The atomizer pressure was varied from 1 to 3bar and 20-25% increase in efficiency was observed by decreasing the pressure. Effect of dilution of urea solution was investigated by varying the strength of the solution from the 8 to 32% and 40-45% increase in the efficiency was observed. Effects of injector position was investigated by injecting the urea solution both in co current and counter current direction of the flue gases and 20-25% increase in the efficiency was observed in counter current direction. (author)

  4. Catalytically supported reduction of emissions from small-scale biomass furnace systems

    International Nuclear Information System (INIS)

    Hartmann, Ingo; Lenz, Volker; Schenker, Marian; Thiel, Christian; Kraus, Markus; Matthes, Mirjam; Roland, Ulf; Bindig, Rene; Einicke, Wolf-Dietrich

    2011-01-01

    The increased use of solid biomass in small combustion for generating heat from renewable energy sources is unfortunately associated with increased emissions of airborne pollutants. The reduction is possible on the one hand by the use of high-quality modern furnaces to the latest state of the art. On the other hand, several promising approaches method for retrofitting small-scale furnaces are currently being developed that will allow an effective emission reduction by the subsequent treatment of the exhaust gas. The overview of current available emission control technologies for small-scale biomass combustion plants shows that there is still considerable need for research on the sustainable production of heat from solid biofuels. The amendment to the 1st BImSchV provides a necessary drastic reduction of discharged pollutants from small-scale biomass furnaces. When using the fuel wood in modern central heating boilers the required limits can be met at full load. However, dynamic load changes can cause brief dramatic emission increases even with wood central heating boilers. Firebox and control optimization must contribute in the future to a further reduction of emissions. The typical simple single-room fireplaces like hand-fed wood stoves are suitable under type test conditions to comply the limit values. By contrast, in practical operation, the harmful gas emissions be exceeded without secondary measures normally. The performed experimental investigations show that a reduction of both CO and of organic compounds by catalytic combustion is possible. In addition to developing specially adapted catalysts, it is necessary to provide additional dust separation by combined processes, since conventional catalysts are not suitable for deposition and retention of particulate matter or would lose their activity due to dust accumulation on the active surface, when the catalyst would act as a filter at the same time. To enable sufficiently high reaction temperatures and thus a

  5. Selective catalytic reduction (SCR) NOx control for small natural gas-fired prime movers

    International Nuclear Information System (INIS)

    Shareef, G.S.; Stone, D.K.; Ferry, K.R.; Johnson, K.L.; Locke, K.S.

    1992-01-01

    The application of selective catalytic reduction (SCR) to small natural gas-fired prime movers at cogeneration facilities and compressor stations could possibly increase due to regulatory forces to limit NO x from such sources. The natural gas industry is presently without a current database with which to evaluate the cost and operating characteristics of SCR under the conditions anticipated for small prime movers. This paper presents the results from a two-phase study undertaken to document SCR applications with emphasis on SCR system performance and costs. The database of small natural gas-fired prime mover SCR experience, focusing on prime mover characterization, SCR system performance, and SCR system costs will be described. Result from analysis of performance and cost data will be discussed, including analytical tools developed to project SCR system performance and costs

  6. On the Pt(+) and Rh(+) Catalytic Activity in the Nitrous Oxide Reduction by Carbon Monoxide.

    Science.gov (United States)

    Rondinelli, F; Russo, N; Toscano, M

    2008-11-11

    Nitrous oxide activation by CO in the presence of platinum and rhodium monocations was elucidated by density functional methods for ground and first excited states. Platinum and rhodium cations fulfill the thermodynamic request for the oxygen-atom transport that allows the catalytic cycle to be completed, but actually, just the first one meaningfully improves the kinetics of the process. For both catalysts, the reaction pathways show the only activation barrier in correspondence of nitrogen release and monoxide cation formation. The kinetic analysis of the potential energy profile, in agreement with ICP/SIFT MS experimental data, indicates that platinum performs more in the reduction, while the whole process is not sufficiently fast in the case of rhodium ionic catalyst.

  7. Comparative study involving the uranium determination through catalytic reduction of nitrates and nitrides by using decoupled plasma nitridation (DPN)

    International Nuclear Information System (INIS)

    Aguiar, Marco Antonio Souza; Gutz, Ivano G. Rolf

    1999-01-01

    This paper reports a comparative study on the determination of uranium through the catalytic reduction of nitrate and nitride using the decoupled plasma nitridation. The uranyl ions are a good catalyst for the reduction of NO - 3 and NO - 2 ions on the surface of a hanging drop mercury electrode (HDME). The presence of NO - in a solution with p H = 3 presented a catalytic signal more intense than the signal obtained with NO - 3 (concentration ten times higher). A detection limit of 1x10 9 M was obtained using the technique of decoupled plasma nitridation (DPN), suggesting the development of a sensitive way for the determination of uranium in different matrixes

  8. Effects of a TiC substrate on the catalytic activity of Pt for NO reduction.

    Science.gov (United States)

    Chu, Xingli; Fu, Zhaoming; Li, Shasha; Zhang, Xilin; Yang, Zongxian

    2016-05-11

    Density functional theory calculations are used to elucidate the catalytic properties of a Pt monolayer supported on a TiC(001) substrate (Pt/TiC) toward NO reduction. It is found that the compound system of Pt/TiC has a good stability due to the strong Pt-TiC interaction. The diverse dissociation paths (namely the direct dissociation mechanism and the dimeric mechanism) are investigated. The transition state searching calculations suggest that NO has strong diffusion ability and small activation energy for dissociation on the Pt/TiC. For NO reduction on the Pt/TiC surface, we have found that the direct dissociation mechanisms (NO + N + O → NO2 + N and NO + N + O → N2 + O + O) are easier with a smaller dissociation barrier than those on the Pt(111) surface; and the dimeric process (NO + NO → (NO)2 → N2O + O → N2 + O + O) is considered to be dominant or significant with even a lower energy barrier than that of the direct dissociation. The results show that Pt/TiC can serve as an efficient catalyst for NO reduction.

  9. Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction.

    Science.gov (United States)

    Zitolo, Andrea; Ranjbar-Sahraie, Nastaran; Mineva, Tzonka; Li, Jingkun; Jia, Qingying; Stamatin, Serban; Harrington, George F; Lyth, Stephen Mathew; Krtil, Petr; Mukerjee, Sanjeev; Fonda, Emiliano; Jaouen, Frédéric

    2017-10-16

    Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN 4 C 12 , CoN 3 C 10,porp and CoN 2 C 5 . The O 2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O 2 -adsorption strength, we conclude that cobalt-based moieties bind O 2 too weakly for efficient O 2 reduction.Nitrogen-doped carbon materials with atomically dispersed iron or cobalt are promising for catalytic use. Here, the authors show that cobalt moieties have a higher redox potential, bind oxygen more weakly and are less active toward oxygen reduction than their iron counterpart, despite similar coordination.

  10. Low Temperature Selective Catalytic Reduction of Nitrogen Oxides in Production of Nitric Acid by the Use of Liquid

    Directory of Open Access Journals (Sweden)

    Kabljanac, Ž.

    2011-11-01

    Full Text Available This paper presents the application of low-temperature selective catalytic reduction of nitrous oxides in the tail gas of the dual-pressure process of nitric acid production. The process of selective catalytic reduction is carried out using the TiO2/WO3 heterogeneous catalyst applied on a ceramic honeycomb structure with a high geometric surface area per volume. The process design parameters for nitric acid production by the dual-pressure procedure in a capacity range from 75 to 100 % in comparison with designed capacity for one production line is shown in the Table 1. Shown is the effectiveness of selective catalytic reduction in the temperature range of the tail gas from 180 to 230 °C with direct application of liquid ammonia, without prior evaporation to gaseous state. The results of inlet and outlet concentrations of nitrous oxides in the tail gas of the nitric acid production process are shown in Figures 1 and 2. Figure 3 shows the temperature dependence of the selective catalytic reduction of nitrous oxides expressed as NO2in the tail gas of nitric acid production with the application of a constant mass flow of liquid ammonia of 13,0 kg h-1 and average inlet mass concentration of the nitrous oxides expressed as NO2of 800,0 mgm-3 during 100 % production capacity. The specially designed liquid-ammonia direct-dosing system along with the effective homogenization of the tail gas resulted in emission levels of nitrous oxides expressed as NO2 in tail gas ranging from 100,0 to 185,0 mg m-3. The applied low-temperature selective catalytic reduction of the nitrous oxides in the tail gases by direct use of liquid ammonia is shown in Figure 4. It is shown that low-temperature selective catalytic reduction with direct application of liquid ammonia opens a new opportunity in the reduction of nitrous oxide emissions during nitric acid production without the risk of dangerous ammonium nitrate occurring in the process of subsequent energy utilization of

  11. Catalytic pyrolysis of LDPE leads to valuable resource recovery and reduction of waste problems

    Energy Technology Data Exchange (ETDEWEB)

    Shah, Jasmin [Institute of Chemical Sciences, University of Peshawar, N.W.F.P. (Pakistan); Jan, M. Rasul [University of Malakand, Chakdara, N.W.F.P. (Pakistan); Mabood, Fazal [Department of Chemistry, University of Malakand, Chakdara, N.W.F.P. (Pakistan); Jabeen, Farah [Department of Chemistry, Sarhad University, N.W.F.P. (Pakistan)

    2010-12-15

    . This was further confirmed by Bromine number tests. The values of which lie in the range of 0.1-12.8 g/ml, which fall in the range for olefin mixture. Phenol and carbonyl contents were quantified using UV/Visible spectroscopy and the values lie in the range of 1-8920 {mu}g/ml and 5-169 {mu}g/ml for both phenols and carbonyls respectively. The components of different hydrocarbons in the oil mixture were separated by using column chromatography and fractional distillation followed by characterization with FT-IR spectroscopy. The interpretation of FT-IR spectra shows that catalytic pyrolysis of LDPE leads to the formation of a complex mixture of alkanes, alkenes, carbonyl group containing compounds like aldehydes, ketones, aromatic compounds and substituted aromatic compounds like phenols. It could be concluded, that catalytic pyrolysis of LDPE leads to valuable resource recovery and reduction of waste problem. (author)

  12. A novel green synthesis and characterization of Ag NPs with its ultra-rapid catalytic reduction of methyl green dye

    International Nuclear Information System (INIS)

    Junejo, Y.; Sirajuddin; Baykal, A.; Safdar, M.; Balouch, A.

    2014-01-01

    Ampicillin derived silver nanoparticles were synthesized in an aqueous medium. Particle size and shape were determined by Transmission electron microscopy which showed the monodispersed morphology. The Fourier transform infrared spectra were represented the interaction of Ampicillin with surface of Ampicillin derived silver nanoparticles. X-ray powder diffraction study gave crystalline nature of the Ampicillin derived silver nanoparticles which exhibited exceptional catalytic activity for the reduction of Methylene Green dye. However, complete reduction of dye was accomplished by Ampicillin derived silver nanoparticles within 4 min only. The catalytic performance of these nanoparticles was adsorbed on glass. They were recovered easily from reaction medium and reused with enhanced catalytic potential. Based upon these results it has been concluded that Ampicillin derived silver nanoparticles are novel, rapid and highly economical alternative for environmental safety against pollution by dyes and extendable for control of other reducible contaminants as well.

  13. Application of chronocoulomentry for trace levels uranium determination using catalytic nitrate reduction on mercury electrode

    International Nuclear Information System (INIS)

    Cantagallo, M.I.C.

    1988-01-01

    With the aim of improving the sensitivity of the electro-analytical determination of uranium at trace levels, the uranium catalyzed reduction of nitrate on mercury electrodes was used and the technique of chronocoulometry was compared with other voltammetric techniques. The catalytic process offers high sensitivity in comparison with uranyl reduction in absence of nitrate. The chronocoulometry, virtually unexplored for analytical applications, was found to be specially well suited for determinations based on this kind of electrode process, when using current integration times in the range of several seconds. Under these conditions the interference from diffusion controlled faradaic processes is reduced to a minimum. Several experimental parameters were investigated (eletrolyte composition, potential program, integration time, blank correction, temperature, previous separation) and adequate conditions were selected for the analytical determination of pure and real samples. The proposed method was applied and evaluated with real and, when necessary, an adapted liquid-liquid extraction procedure was used. Reference materials with complex matrices like rocks were first solubilized by hot digestion under pressure. The obtained results are in good agreement with the values obtained with other techniques such as X-ray fluorescence, mass spectrometry-isotope dilution and epithermal netron activation analysis. (author) [pt

  14. Efficient Catalytic Reduction of Hexavalent Chromium With Pd-decorated Carbon Nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Ji Dang; Choi, Hyun Chul [Chonnam National University, Gwangju (Korea, Republic of)

    2016-05-15

    Heavy metal pollution is currently a serious environmental issue. Chromium (Cr) and chromium compounds are commonly found in wastewater discharged by various industries such as wood preservation, leather tanning, electroplating, metal finishing, and the production of chemicals. Pd nanoparticles can easily be introduced into CNTs by performing DCC-activated amidation. Our TEM and XRD results indicate that well-dispersed metallic Pd nanoparticles are anchored on the surface of the amidated CNTs. The XPS results suggest that the Pd content of the sample is approximately 9.8 atomic %. In comparison with the commercial Pd catalyst, the prepared Pd-CNTs were demonstrated to exhibit good catalytic activity in the reduction of 4-NP by NaBH4. Moreover, the Pd-CNT catalyst can easily be separated by performing a simple filtration and reused over at least 10 cycles. This Pd-CNT catalyst is therefore believed to have significant potential for use as a reusable catalyst in the reduction of Cr(Vi)

  15. A fuzzy logic urea dosage controller design for two-cell selective catalytic reduction systems.

    Science.gov (United States)

    You, Kun; Wei, Lijiang; Jiang, Kai

    2017-12-22

    Diesel engines have dominated in the heavy-duty vehicular and marine power source. However, the induced air pollution is a big problem. As people's awareness of environmental protection increasing, the emission regulations of diesel-engine are becoming more stringent. In order to achieve the emission regulations, the after-treatment system is a necessary choice. Specifically, the selective catalytic reduction (SCR) system has been widely applied to reduce the NO X emissions of diesel engine. Different from single-cell SCR systems, the two-cell systems have various benefits from the modeling and control perspective. In this paper, the urea dosage controller design for two-cell SCR systems was investigated. Firstly, the two-cell SCR modeling was introduced. Based on the developed model, the design procedure for the fuzzy logic urea dosage controller was well addressed. Secondly, simulations and comparisons were employed via an experimental verification of the whole vehicle simulator. And the results showed that the designed controller simultaneously achieved high NO X reduction rate and low tail-pipe ammonia slip. Copyright © 2017 ISA. Published by Elsevier Ltd. All rights reserved.

  16. System and method for selective catalytic reduction of nitrogen oxides in combustion exhaust gases

    Science.gov (United States)

    Sobolevskiy, Anatoly; Rossin, Joseph A

    2014-04-08

    A multi-stage selective catalytic reduction (SCR) unit (32) provides efficient reduction of NOx and other pollutants from about 50-550.degree. C. in a power plant (19). Hydrogen (24) and ammonia (29) are variably supplied to the SCR unit depending on temperature. An upstream portion (34) of the SCR unit catalyzes NOx+NH.sub.3 reactions above about 200.degree. C. A downstream portion (36) catalyzes NOx+H.sub.2 reactions below about 260.degree. C., and catalyzes oxidation of NH.sub.3, CO, and VOCs with oxygen in the exhaust above about 200.degree. C., efficiently removing NOx and other pollutants over a range of conditions with low slippage of NH.sub.3. An ammonia synthesis unit (28) may be connected to the SCR unit to provide NH.sub.3 as needed, avoiding transport and storage of ammonia or urea at the site. A carbonaceous gasification plant (18) on site may supply hydrogen and nitrogen to the ammonia synthesis unit, and hydrogen to the SCR unit.

  17. Mesoporous Fe-containing ZSM-5 zeolite single crystal catalysts for selective catalytic reduction of nitric oxide by ammonia

    DEFF Research Database (Denmark)

    Kustov, Arkadii; Egeblad, Kresten; Kustova, Marina

    2007-01-01

    Mesoporous and conventional Fe-containing ZSM-5 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnationmethod and tested in NO selective catalytic reduction (SCR) with NH3. It was found that mesoporous Fe-ZSM-5 catalysts exhibit higher SCR activities than comparable conventional cataly...

  18. Validation of the catalytic properties of Cu-Os/13X using single fixed bed reactor in selective catalytic reduction of NO

    International Nuclear Information System (INIS)

    Oh, Kwang Seok; Woo, Seong Ihl

    2007-01-01

    Catalytic decomposition of NO over Cu-Os/13X has been carried out in a tubular fixed bed reactor at atmospheric pressure and the results were compared with literature data performed by high-throughput screening (HTS). The activity and durability of Cu-Os/13X prepared by conventional ion-exchange method have been investigated in the presence of H 2 O and SO 2 . It was found that Cu-Os/13X prepared by ion-exchange shows a high activity in a wide temperature range in selective catalytic reduction (SCR) of NO with C 3 H 6 compared to Cu/13X, proving the existence of more NO adsorption site on Cu-Os/13X. However, Cu-Os/13X exhibited low activity in the presence of water, and was quite different from the result reported in literature. SO 2 resistance is also low and does not recover its original activity when the SO 2 was blocked in the feed gas stream. This result suggested that catalytic activity between combinatorial screening and conventional testing should be compared to confirm the validity of high-throughput screening

  19. 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.

  20. Defect-meditated efficient catalytic activity toward p-nitrophenol reduction: A case study of nitrogen doped calcium niobate system

    International Nuclear Information System (INIS)

    Su, Yiguo; Huang, Shushu; Wang, Tingting; Peng, Liman; Wang, Xiaojing

    2015-01-01

    Graphical abstract: A series of nitrogen doped Ca 2 Nb 2 O 7 was successfully prepared via ion-exchange method, which was found to be an efficient and green noble-metal-free catalyst toward catalytic reduction of p-nitrophenol. - Highlights: • Nitrogen doped Ca 2 Nb 2 O 7 was found to be an efficient and green noble-metal-free catalyst toward catalytic reduction of p-nitrophenol. • Defective nitrogen and oxygen species were found to play synergetic roles in the reduction of p-nitrophenol. • Nitrogen doped Ca 2 Nb 2 O 7 showed photo-synergistic promotion effects toward p-nitrophenol reduction under UV light irradiation. - Abstract: This work reported on the synthesis of a series of nitrogen doped Ca 2 Nb 2 O 7 with tunable nitrogen content that were found to be efficient and green noble-metal-free catalysts toward catalytic reduction of p-nitrophenol. XPS and ESR results indicated that the introduction of nitrogen in Ca 2 Nb 2 O 7 gave rise to a large number of defective nitrogen and oxygen species. Defective nitrogen and oxygen species were found to play synergetic roles in the reduction of p-nitrophenol. The underlying mechanism is completely different from those reported for metallic nanoparticles. Moreover, the more negative conduction band edge potential enabled nitrogen doped Ca 2 Nb 2 O 7 to show photo-synergistic effects that could accelerate the reduction rate toward p-nitrophenol under UV light irradiation. This work may provide a strategy for tuning the catalytic performance by modulating the chemical composition, electronic structure as well as surface defect chemistry

  1. Ultra-fast catalytic reduction of dyes by ionic liquid recoverable and reusable mefenamic acid derived gold nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Hassan, Syeda Sara [National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro 76080 (Pakistan); Sirajuddin, E-mail: drsiraj03@yahoo.com [National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro 76080 (Pakistan); Solangi, Amber Rehana [National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro 76080 (Pakistan); Agheem, Mohammad Hassan [Center for Pure and Applied Geology, University of Sindh, Jamshoro 76080 (Pakistan); Junejo, Yasmeen; Kalwar, Nazar Hussain; Tagar, Zulfiqar Ali [National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro 76080 (Pakistan)

    2011-06-15

    Highlights: {yields} Gold nanoparticles (AuNps) have been fabricated by a simple chemical method. {yields} AuNps were capped successfully in one step by mefenamic acid (MA). {yields} MA capped AuNps catalytically reduced the mixture of 3 dyes in just 15 s. {yields} AuNps were recovered by ionic liquid and reused for dye(s) reduction effectively. - Abstract: We synthesized mefenamic acid (MA) derived gold nanoparticles (MA-AuNps) in aqueous solution (MA-Au sol). Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) of the sol at 1, 5, 15 and 60 min showed changes in size and shape of formed AuNps. Fourier Transform Infrared (FTIR) Spectroscopy revealed the interaction between AuNps and MA. Each Au sol exhibited exceptional catalytic activity for the reduction of Methylene Blue (MB), Rose Bengal (RB) and Eosin B (EB) dye individually as well as collectively. However, complete reduction of dye(s) was accomplished by Au sol of 5 min in just 15 s. The catalytic performance of Ma-Au sol was far superior to that adsorbed on glass. AuNps were recovered with the help of water insoluble room temperature ionic liquid and reused with enhanced catalytic potential. This finding is a novel, rapid and highly economical alternative for environmental safety against pollution by dyes and extendable for control of other reducible contaminants as well.

  2. Green and facile synthesis of fibrous Ag/cotton composites and their catalytic properties for 4-nitrophenol reduction

    Science.gov (United States)

    Li, Ziyu; Jia, Zhigang; Ni, Tao; Li, Shengbiao

    2017-12-01

    Natural cotton, featuring abundant oxygen-containing functional groups, has been utilized as a reductant to synthesize Ag nanoparticles on its surface. Through the facile and environment-friendly reduction process, the fibrous Ag/cotton composite (FAC) was conveniently synthesized. Various characterization techniques including XRD, XPS, TEM, SEM, EDS and FT-IR had been utilized to study the material microstructure and surface properties. The resulting FAC exhibited favorable activity on the catalytic reduction of 4-nitrophenol with high reaction rate. Moreover, the fibrous Ag/cotton composites were capable to form a desirable catalytic mat for catalyzing and simultaneous product separation. Reactants passing through the mat could be catalytically transformed to product, which is of great significance for water treatment. Such catalyst (FAC) was thus expected to have the potential as a highly efficient, cost-effective and eco-friendly catalyst for industrial applications. More importantly, this newly developed synthetic methodology could serve as a general tool to design and synthesize other metal/biomass composites catalysts for a wider range of catalytic applications.

  3. Ultra-fast catalytic reduction of dyes by ionic liquid recoverable and reusable mefenamic acid derived gold nanoparticles

    International Nuclear Information System (INIS)

    Hassan, Syeda Sara; Sirajuddin; Solangi, Amber Rehana; Agheem, Mohammad Hassan; Junejo, Yasmeen; Kalwar, Nazar Hussain; Tagar, Zulfiqar Ali

    2011-01-01

    Highlights: → Gold nanoparticles (AuNps) have been fabricated by a simple chemical method. → AuNps were capped successfully in one step by mefenamic acid (MA). → MA capped AuNps catalytically reduced the mixture of 3 dyes in just 15 s. → AuNps were recovered by ionic liquid and reused for dye(s) reduction effectively. - Abstract: We synthesized mefenamic acid (MA) derived gold nanoparticles (MA-AuNps) in aqueous solution (MA-Au sol). Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) of the sol at 1, 5, 15 and 60 min showed changes in size and shape of formed AuNps. Fourier Transform Infrared (FTIR) Spectroscopy revealed the interaction between AuNps and MA. Each Au sol exhibited exceptional catalytic activity for the reduction of Methylene Blue (MB), Rose Bengal (RB) and Eosin B (EB) dye individually as well as collectively. However, complete reduction of dye(s) was accomplished by Au sol of 5 min in just 15 s. The catalytic performance of Ma-Au sol was far superior to that adsorbed on glass. AuNps were recovered with the help of water insoluble room temperature ionic liquid and reused with enhanced catalytic potential. This finding is a novel, rapid and highly economical alternative for environmental safety against pollution by dyes and extendable for control of other reducible contaminants as well.

  4. Catalytic reduction of NOx in gasoline engine exhaust over copper- and nickel-exchanged X-zeolite catalysts

    International Nuclear Information System (INIS)

    Bhattacharyya, S.; Das, R.K.

    2001-01-01

    Catalytic removal of NO x in engine exhaust gases can be accomplished by non-selective reduction, selective reduction and decomposition. Noble metals are extensively used for non-selective reduction of NO x and up to 90% of engine NO x emissions can be reduced in a stoichiometric exhaust. This requirement of having the stoichiometric fuel-air ratio acts against efficiency improvement of engines. Selective NO x reduction in the presence of different reductants such as, NH 3 , urea or hydrocarbons, requires close control of the amount of reductant being injected which otherwise may be emitted as a pollutant. Catalytic decomposition is the best option for NO x removal. Nevertheless, catalysts which are durable, economic and active for NO x reduction at normal engine exhaust temperature ranges are still being investigated. Three catalysts based on X-zeolite have been developed by exchanging the Na+ ion with copper, nickel and copper-nickel metal ions and applied to the exhaust of a stationary gasoline engine to explore their potential for catalytic reduction of NO x under a wide range of engine and exhaust conditions. Some encouraging results have been obtained. The catalyst Cu-X exhibits much better NO x reduction performance at any temperature in comparison to Cu-Ni-X and Ni-X; while Cu-Ni-X catalyst exhibits slightly better performance than Ni-X catalyst. Maximum NO x efficiency achieved with Cu-X catalyst is 59.2% at a space velocity (sv) of 31 000 h -1 ; while for Cu-Ni-X and Ni-X catalysts the equivalent numbers are 60.4% and 56% respectively at a sv of 22 000 h -1 . Unlike noble metals, the doped X-zeolite catalysts exhibit significant NO x reduction capability for a wide range of air/fuel ratio and with a slower rate of decline as well with increase in air/fuel ratio. (author)

  5. Research and proposal on selective catalytic reduction reactor optimization for industrial boiler.

    Science.gov (United States)

    Yang, Yiming; Li, Jian; He, Hong

    2017-08-24

    The advanced computational fluid dynamics (CFD) software STAR-CCM+ was used to simulate a denitrification (De-NOx) project for a boiler in this paper, and the simulation result was verified based on a physical model. Two selective catalytic reduction (SCR) reactors were developed: reactor 1 was optimized and reactor 2 was developed based on reactor 1. Various indicators, including gas flow field, ammonia concentration distribution, temperature distribution, gas incident angle, and system pressure drop were analyzed. The analysis indicated that reactor 2 was of outstanding performance and could simplify developing greatly. Ammonia injection grid (AIG), the core component of the reactor, was studied; three AIGs were developed and their performances were compared and analyzed. The result indicated that AIG 3 was of the best performance. The technical indicators were proposed for SCR reactor based on the study. Flow filed distribution, gas incident angle, and temperature distribution are subjected to SCR reactor shape to a great extent, and reactor 2 proposed in this paper was of outstanding performance; ammonia concentration distribution is subjected to ammonia injection grid (AIG) shape, and AIG 3 could meet the technical indicator of ammonia concentration without mounting ammonia mixer. The developments above on the reactor and the AIG are both of great application value and social efficiency.

  6. Environmental and economic evaluation of selective non-catalytic reduction of nitrogen oxides

    Science.gov (United States)

    Parchevskii, V. M.; Shchederkina, T. E.; Proshina, A. O.

    2017-11-01

    There are two groups of atmosphere protecting measures: technology (primary) and treatment (secondary). When burning high-calorie low-volatile brands of coals in the furnaces with liquid slag removal to achieve emission standards required joint use of these two methods, for example, staged combustion and selective non-catalytic reduction recovery (SNCR). For the economically intelligent combination of these two methods it is necessary to have information not only about the environmental performance of each method, but also the operating costs per unit of reduced emission. The authors of this report are made an environmental-economic analysis of SNCR on boiler Π-50P Kashirskaya power station. The obtained results about the dependence of costs from the load of the boiler and the mass emissions of nitrogen oxides then approximates into empirical formulas, is named as environmental and economic characteristics, which is suitable for downloading into controllers and other control devices for subsequent implementation of optimal control of emissions to ensure compliance with environmental regulations at the lowest cost at any load of the boiler.

  7. A catalytic wet oxidation process for mixed waste volume reduction/recycling

    International Nuclear Information System (INIS)

    Dhooge, Patrick M.

    1992-01-01

    Mixed wastes have presented a challenge to treatment and destruction technologies. A recently developed catalytic wet oxidation method has promising characteristics for volume reduction and recycling of mixed wastes. The process utilizes iron (III) as an oxidant in the presence of homogeneous cocatalysts which increase organics' oxidation rates and the rate of oxidation of iron (II) by oxygen. The reaction is conducted in an aqueous mineral acid solution at temperatures of 373 - 573 deg K. The mineral acid should solvate a number of heavy metals, including U and Pu. Studies of reaction rates show that the process can oxidize a wide range of organic compounds including aromatics and chlorinated hydrocarbons. Rate constants in the range of 10 -7 to 10 -4 sec -1 , depending on the cocatalyst, acidity, type of anions, type of organic, temperature, and time. Activation energies ranged from 25. to 32. KJ/mole. Preliminary measurements of the extent of oxidation which could be obtained ranged from 80% for trichloroethylene to 99.8% for 1,2,4-trimethylbenzene; evidence was obtained that absorption by the fluorocarbon liners of the reaction bombs allowed some of the organics to escape exposure to the catalyst solution. The results indicate that complete oxidation of the organics used here, and presumably many others, can be achieved. (author)

  8. Synergetic Effects of Alcohol/Water Mixing on the Catalytic Reductive Fractionation of Poplar Wood

    Energy Technology Data Exchange (ETDEWEB)

    Renders, Tom; Van den Bosch, Sander; Vangeel, Thijs; Ennaert, Thijs; Koelewijn, Steven-Friso; Van den Bossche, Gil; Courtin, Christophe M.; Schutyser, Wouter; Sels, Bert F.

    2016-12-05

    One of the foremost challenges in lignocellulose conversion encompasses the integration of effective lignin valorization in current carbohydrate-oriented biorefinery schemes. Catalytic reductive fractionation (CRF) of lignocellulose offers a technology to simultaneously produce lignin-derived platform chemicals and a carbohydrate-enriched pulp via the combined action of lignin solvolysis and metal-catalyzed hydrogenolysis. Herein, the solvent (composition) plays a crucial role. In this contribution, we study the influence of alcohol/water mixtures by processing poplar sawdust in varying MeOH/water and EtOH/water blends. The results show particular effects that strongly depend on the applied water concentration. Low water concentrations enhance the removal of lignin from the biomass, while the majority of the carbohydrates are left untouched (scenario A). Contrarily, high water concentrations favor the solubilization of both hemicellulose and lignin, resulting in a more pure cellulosic residue (scenario B). For both scenarios, an evaluation was made to determine the most optimal solvent composition, based on two earlier introduced empirical efficiency descriptors (denoted LFDE and LFFE). According to these measures, 30 (A) and 70 vol % water (B) showed to be the optimal balance for both MeOH/water and EtOH/water mixtures. This successful implementation of alcohol/water mixtures allows operation under milder processing conditions in comparison to pure alcohol solvents, which is advantageous from an industrial point of view.

  9. Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants

    Energy Technology Data Exchange (ETDEWEB)

    Constance L. Senior [Reaction Engineering International, Salt Lake City, UT (United States)

    2006-01-15

    A kinetic model for predicting the amount of mercury (Hg) oxidation across selective catalytic reduction (SCR) systems in coal-fired power plants was developed and tested. The model incorporated the effects of diffusion within the porous SCR catalyst and the competition between ammonia and Hg for active sites on the catalyst. Laboratory data on Hg oxidation in simulated flue gas and slipstream data on Hg oxidation in flue gas from power plants were modeled. The model provided good fits to the data for eight different catalysts, both plate and monolith, across a temperature range of 280-420{sup o}C, with space velocities varying from 1900 to 5000 hr{sup -1}. Space velocity, temperature, hydrochloric acid content of the flue gas, ratio of ammonia to nitric oxide, and catalyst design all affected Hg oxidation across the SCR catalyst. The model can be used to predict the impact of coal properties, catalyst design, and operating conditions on Hg oxidation across SCRs. 20 refs., 9 figs., 2 tabs.

  10. INVESTIGATION OF AMMONIA ADSORPTION ON FLY ASH DUE TO INSTALLATION OF SELECTIVE CATALYTIC REDUCTION SYSTEMS

    Energy Technology Data Exchange (ETDEWEB)

    G.F. Brendel; J.E. Bonetti; R.F. Rathbone; R.N. Frey Jr.

    2000-11-01

    This report summarizes an investigation of the potential impacts associated with the utilization of selective catalytic reduction (SCR) systems at coal-fired power plants. The study was sponsored by the U.S. Department of Energy Emission Control By-Products Consortium, Dominion Generation, the University of Kentucky Center for Applied Energy Research and GAI Consultants, Inc. SCR systems are effective in reducing nitrogen oxides (NOx) emissions as required by the Clean Air Act (CAA) Amendments. However, there may be potential consequences associated with ammonia contamination of stack emissions and combustion by-products from these systems. Costs for air quality, landfill and pond environmental compliance may increase significantly and the marketability of ash may be seriously reduced, which, in turn, may also lead to increased disposal costs. The potential impacts to air, surface water, groundwater, ash disposal, ash utilization, health and safety, and environmental compliance can not be easily quantified based on the information presently available. The investigation included: (1) a review of information and data available from published and unpublished sources; (2) baseline ash characterization testing of ash samples produced from several central Appalachian high-volatile bituminous coals from plants that do not currently employ SCR systems in order to characterize the ash prior to ammonia exposure; (3) an investigation of ammonia release from fly ash, including leaching and thermal studies; and (4) an evaluation of the potential impacts on plant equipment, air quality, water quality, ash disposal operations, and ash marketing.

  11. 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

  12. Emission reduction from a diesel engine fueled by pine oil biofuel using SCR and catalytic converter

    Science.gov (United States)

    Vallinayagam, R.; Vedharaj, S.; Yang, W. M.; Saravanan, C. G.; Lee, P. S.; Chua, K. J. E.; Chou, S. K.

    2013-12-01

    In this work, we propose pine oil biofuel, a renewable fuel obtained from the resins of pine tree, as a potential substitute fuel for a diesel engine. Pine oil is endowed with enhanced physical and thermal properties such as lower viscosity and boiling point, which enhances the atomization and fuel/air mixing process. However, the lower cetane number of the pine oil hinders its direct use in diesel engine and hence, it is blended in suitable proportions with diesel so that the ignition assistance could be provided by higher cetane diesel. Since lower cetane fuels are prone to more NOX formation, SCR (selective catalyst reduction), using urea as reducing agent, along with a CC (catalytic converter) has been implemented in the exhaust pipe. From the experimental study, the BTE (brake thermal efficiency) was observed to be increased as the composition of pine oil increases in the blend, with B50 (50% pine oil and 50% diesel) showing 7.5% increase over diesel at full load condition. The major emissions such as smoke, CO, HC and NOX were reduced by 70.1%, 67.5%, 58.6% and 15.2%, respectively, than diesel. Further, the average emissions of B50 with SCR and CC assembly were observed to be reduced, signifying the positive impact of pine oil biofuel on atmospheric environment. In the combustion characteristics front, peak heat release rate and maximum in-cylinder pressure were observed to be higher with longer ignition delay.

  13. Evaluation of mechanical properties in metal wire mesh supported selective catalytic reduction (SCR) catalyst structures

    Science.gov (United States)

    Rajath, S.; Siddaraju, C.; Nandakishora, Y.; Roy, Sukumar

    2018-04-01

    The objective of this research is to evaluate certain specific mechanical properties of certain stainless steel wire mesh supported Selective catalytic reduction catalysts structures wherein the physical properties of the metal wire mesh and also its surface treatments played vital role thereby influencing the mechanical properties. As the adhesion between the stainless steel wire mesh and the catalyst material determines the bond strength and the erosion resistance of catalyst structures, surface modifications of the metal- wire mesh structure in order to facilitate the interface bonding is therefore very important to realize enhanced level of mechanical properties. One way to enhance such adhesion properties, the stainless steel wire mesh is treated with the various acids, i.e., chromic acid, phosphoric acid including certain mineral acids and combination of all those in various molar ratios that could generate surface active groups on metal surface that promotes good interface structure between the metal- wire mesh and metal oxide-based catalyst material and then the stainless steel wire mesh is dipped in the glass powder slurry containing some amount of organic binder. As a result of which the said catalyst material adheres to the metal-wire mesh surface more effectively that improves the erosion profile of supported catalysts structure including bond strength.

  14. Catalytic reduction of emissions from small-scale combustion of biomass

    International Nuclear Information System (INIS)

    Berg, Magnus; Gustavsson, Patrik; Berge, Niklas

    1998-01-01

    This report covers a study on the prospect of using catalytic techniques for the abatement of emissions from small-scale combustion of biomass. The results show that there is a great potential for catalytic techniques and that the emissions of primarily CO and unburned hydrocarbons can be reduced but also that indirectly the emissions of NO x can be reduced. The aim of the project was to methodically indicate the requirement that both the catalyst and the stove must meet to enable the development of low emission stoves utilising this technique. The project should also aim at the development of catalysts that meet these requirements and apply the technique on small-scale stoves. By experimental work these appliances have been evaluated and conclusions drawn on the optimisation of the technique. The project has been performed in close collaboration between TPS Termiska Processer AB, Department of Chemical Technology at KTH, Perstorp AB and CTC-PARCA AB. The development of new catalysts have been conduc ted by KTH in collaboration with Perstorp while the work performed by TPS have been directed towards the integration of the monolithic catalysts in two different stoves that have been supplied by CTC. In one of these stoves a net based catalyst developed by KATATOR have also been tested. Within the project it has been verified experimentally that in a wood fired stove a reduction of the CO-emissions of 60% can be achieved for the monolithic catalysts. This reduction could be achieved even without any optimisation of the design. Experiments in a smaller scale and under well controlled conditions have shown that almost 100% reduction of CO can be achieved. The parameters that limits the conversion over the catalyst, and thereby prevents that the targeted low emissions can be reached, have been identified as: * Short residence time, * Mass transport limitations caused by the large channel width, * Uneven temperature profile over the catalyst, and * Insufficient mixing

  15. Oxygen Reduction Reaction for Generating H2 O2 through a Piezo-Catalytic Process over Bismuth Oxychloride.

    Science.gov (United States)

    Shao, Dengkui; Zhang, Ling; Sun, Songmei; Wang, Wenzhong

    2018-02-09

    Oxygen reduction reaction (ORR) for generating H 2 O 2 through green pathways have gained much attention in recent years. Herein, we introduce a piezo-catalytic approach to obtain H 2 O 2 over bismuth oxychloride (BiOCl) through an ORR pathway. The piezoelectric response of BiOCl was directly characterized by piezoresponse force microscopy (PFM). The BiOCl exhibits efficient catalytic performance for generating H 2 O 2 (28 μmol h -1 ) only from O 2 and H 2 O, which is above the average level of H 2 O 2 produced by solar-to-chemical processes. A piezo-catalytic mechanism was proposed: with ultrasonic waves, an alternating electric field will be generated over BiOCl, which can drive charge carriers (electrons) to interact with O 2 and H 2 O, then to form H 2 O 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Copper(II)/amine synergistically catalyzed enantioselective alkylation of cyclic N-acyl hemiaminals with aldehydes.

    Science.gov (United States)

    Sun, Shutao; Mao, Ying; Lou, Hongxiang; Liu, Lei

    2015-07-07

    The first catalytic asymmetric alkylation of N-acyl quinoliniums with aldehydes has been described. A copper/amine synergistic catalytic system has been developed, allowing the addition of functionalized aldehydes to a wide range of electronically varied N-acyl quinoliniums in good yields with excellent enantiocontrol. The synergistic catalytic system was also effective for N-acyl dihydroisoquinoliniums and β-caboliniums, demonstrating the general applicability of the protocol in the enantioselective alkylation of diverse cyclic N-acyl hemiaminals.

  17. Catalytic conversion of CO, NO and SO2 on supported sulfide catalysts. Part 2. Catalytic reduction of NO and SO2 by CO

    International Nuclear Information System (INIS)

    Zhuang, S.-X.; Yamazaki, M.; Omata, K.; Takahashi, Y.; Yamada, M.

    2001-01-01

    To investigate the possibility of simultaneous catalytic reduction of NO and SO 2 by CO, reactions of NO, NO-CO, and NO-SO 2 -CO were performed on γ-alumina-supported sulfides of transition metals including Co, Mo, CoMo and FeMo. NO was decomposed into N 2 O and N 2 accompanied with the formation of SO 2 ; this serious oxidation of lattice sulfur resulted in the deactivation of the catalysts. The addition of CO to the NO stream suppressed SO 2 formation and yielded COS instead. A stoichiometric conversion of NO and CO to N 2 and CO 2 was observed above 350C on the CoMo and the FeMo catalysts. Although the CO addition lengthened catalyst life, it was not enough to maintain activity. After the NO-CO reaction, an XPS analysis showed the growth of Mo 6+ and SO 4 2- peaks, especially for the sulfided FeMo/Al 2 O 3 ; the FeMo catalyst underwent strong oxidation in the NO-CO reaction. The NO and the NO-CO reactions proceeded non-catalytically, consuming catalyst lattice sulfur to yield SO 2 or COS. The addition of SO 2 in the NO-CO system enabled in situ regeneration of the catalysts; the catalysts oxidized through abstraction of lattice sulfur experienced anew reduction and sulfurization through the SO 2 -CO reaction at higher temperature. NO and SO 2 were completely and catalytically converted at 400C on the sulfided CoMo/Al 2 O 3 . By contrast, the sulfided FeMo/Al 2 O 3 was easily oxidized by NO and hardly re-sulfided under the test conditions. Oxidation states of the metals before and after the reactions were determined. Silica and titania-supported CoMo catalysts were also evaluated to study support effects

  18. Does Density of Cationic Sites Affect Catalytic Activity of Co Zeolites in Selective Catalytic Reduction of NO with Methane?

    Czech Academy of Sciences Publication Activity Database

    Dědeček, Jiří; Kaucký, Dalibor; Wichterlová, Blanka

    2002-01-01

    Roč. 18, 3/4 (2002), s. 283-290 ISSN 1022-5528 R&D Projects: GA AV ČR IBS4040016 Institutional research plan: CEZ:AV0Z4040901 Keywords : Co zeolites * ZSM-5 * NO reduction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.648, year: 2002

  19. NOx formation and selective non-catalytic reduction (SNCR) in a fluidized bed combustor of biomass

    International Nuclear Information System (INIS)

    Mahmoudi, Shiva; Baeyens, Jan; Seville, Jonathan P.K.

    2010-01-01

    Caledonian Paper (CaPa) is a major paper mill, located in Ayr, Scotland. For its steam supply, it previously relied on the use of a Circulating Fluidized Bed Combustor (CFBC) of 58 MW th , burning coal, wood bark and wastewater treatment sludge. It currently uses a bubbling fluidized bed combustor (BFBC) of 102 MW th to generate steam at 99 bar, superheated to 465 o C. The boiler is followed by steam turbines and a 15 kg/s steam circuit into the mill. Whereas previously coal, wood bark and wastewater treatment sludge were used as fuel, currently only plantation wood (mainly spruce), demolition wood, wood bark and sludge are used. Since these biosolids contain nitrogen, fuel NO x is formed at the combustion temperature of 850-900 o C. NO x emissions (NO + NO 2 ) vary on average between 300 and 600 mg/Nm 3 (dry gas). The current emission standard is 350 mg/Nm 3 but will be reduced in the future to a maximum of 233 mg/Nm 3 for stand-alone biomass combustors of capacity between 50 and 300 MW th according to the EU LCP standards. NO x abatement is therefore necessary. In the present paper we firstly review the NO x formation mechanisms, proving that for applications of fluidized bed combustion, fuel NO x is the main consideration, and the contribution of thermal NO x to the emissions insignificant. We then assess the deNO x techniques presented in the literature, with an updated review and special focus upon the techniques that are applicable at CaPa. From these techniques, Selective Non-catalytic Reduction (SNCR) using ammonia or urea emerges as the most appropriate NO x abatement solution. Although SNCR deNO x is a selective reduction, the reactions of NO x reduction by NH 3 in the presence of oxygen, and the oxidation of NH 3 proceed competitively. Both reactions were therefore studied in a lab-scale reactor and the results were transformed into design equations starting from the respective reaction kinetics. An overall deNO x yield can then be predicted for any

  20. Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

    Science.gov (United States)

    Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

    2011-07-12

    A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

  1. Enhanced catalytic activity over MIL-100(Fe) loaded ceria catalysts for the selective catalytic reduction of NO{sub x} with NH{sub 3} at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Peng [School of Environmental Science and Technology, Dalian University of Technology, Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), Dalian 116024 (China); Sun, Hong [School of Environmental & Chemical Engineering, Dalian Jiaotong University, Dalian 116028 (China); Quan, Xie, E-mail: quanxie@dlut.edu.cn [School of Environmental Science and Technology, Dalian University of Technology, Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), Dalian 116024 (China); Chen, Shuo [School of Environmental Science and Technology, Dalian University of Technology, Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), Dalian 116024 (China)

    2016-01-15

    Highlights: • Nano-ceria was successfully encapsulated into MIL-100(Fe) for the SCR of NO{sub x}. • The incorporated ceria in MIL-100(Fe) showed high content of chemisorbed oxygen. • The added ceria into MIL-100(Fe) improved the formation of adsorbed NO{sub 2} species. • The addition of ceria into MIL-100(Fe) enhanced SCR activity at low temperature. - Abstract: The development of catalysts for selective catalytic reduction (SCR) reactions that are highly active at low temperatures and show good resistance to SO{sub 2} and H{sub 2}O is still a challenge. In this study, we have designed and developed a high-performance SCR catalyst based on nano-sized ceria encapsulated inside the pores of MIL-100(Fe) that combines excellent catalytic power with a metal organic framework architecture synthesized by the impregnation method (IM). Transmission electron microscopy (TEM) revealed the encapsulation of ceria in the cavities of MIL-100(Fe). The prepared IM-CeO{sub 2}/MIL-100(Fe) catalyst shows improved catalytic activity both at low temperatures and throughout a wide temperature window. The temperature window for 90% NO{sub x} conversion ranges from 196 to 300 °C. X-ray photoelectron spectroscopy (XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) analysis indicated that the nano-sized ceria encapsulated inside MIL-100(Fe) promotes the production of chemisorbed oxygen on the catalyst surface, which greatly enhances the formation of the NO{sub 2} species responsible for fast SCR reactions.

  2. ADVANCED BYPRODUCT RECOVERY: DIRECT CATALYTIC REDUCTION OF SO2 TO ELEMENTAL SULFUR; FINAL

    International Nuclear Information System (INIS)

    Robert S. Weber

    1999-01-01

    Arthur D. Little, Inc., together with its commercialization partner, Engelhard Corporation, and its university partner Tufts, investigated a single-step process for direct, catalytic reduction of sulfur dioxide from regenerable flue gas desulfurization processes to the more valuable elemental sulfur by-product. This development built on recently demonstrated SO(sub 2)-reduction catalyst performance at Tufts University on a DOE-sponsored program and is, in principle, applicable to processing of regenerator off-gases from all regenerable SO(sub 2)-control processes. In this program, laboratory-scale catalyst optimization work at Tufts was combined with supported catalyst formulation work at Engelhard, bench-scale supported catalyst testing at Arthur D. Little and market assessments, also by Arthur D. Little. Objectives included identification and performance evaluation of a catalyst which is robust and flexible with regard to choice of reducing gas. The catalyst formulation was improved significantly over the course of this work owing to the identification of a number of underlying phenomena that tended to reduce catalyst selectivity. The most promising catalysts discovered in the bench-scale tests at Tufts were transformed into monolith-supported catalysts at Engelhard. These catalyst samples were tested at larger scale at Arthur D. Little, where the laboratory-scale results were confirmed, namely that the catalysts do effectively reduce sulfur dioxide to elemental sulfur when operated under appropriate levels of conversion and in conditions that do not contain too much water or hydrogen. Ways to overcome those limitations were suggested by the laboratory results. Nonetheless, at the end of Phase I, the catalysts did not exhibit the very stringent levels of activity or selectivity that would have permitted ready scale-up to pilot or commercial operation. Therefore, we chose not to pursue Phase II of this work which would have included further bench-scale testing

  3. ADVANCED BYPRODUCT RECOVERY: DIRECT CATALYTIC REDUCTION OF SO2 TO ELEMENTAL SULFUR

    Energy Technology Data Exchange (ETDEWEB)

    Robert S. Weber

    1999-05-01

    Arthur D. Little, Inc., together with its commercialization partner, Engelhard Corporation, and its university partner Tufts, investigated a single-step process for direct, catalytic reduction of sulfur dioxide from regenerable flue gas desulfurization processes to the more valuable elemental sulfur by-product. This development built on recently demonstrated SO{sub 2}-reduction catalyst performance at Tufts University on a DOE-sponsored program and is, in principle, applicable to processing of regenerator off-gases from all regenerable SO{sub 2}-control processes. In this program, laboratory-scale catalyst optimization work at Tufts was combined with supported catalyst formulation work at Engelhard, bench-scale supported catalyst testing at Arthur D. Little and market assessments, also by Arthur D. Little. Objectives included identification and performance evaluation of a catalyst which is robust and flexible with regard to choice of reducing gas. The catalyst formulation was improved significantly over the course of this work owing to the identification of a number of underlying phenomena that tended to reduce catalyst selectivity. The most promising catalysts discovered in the bench-scale tests at Tufts were transformed into monolith-supported catalysts at Engelhard. These catalyst samples were tested at larger scale at Arthur D. Little, where the laboratory-scale results were confirmed, namely that the catalysts do effectively reduce sulfur dioxide to elemental sulfur when operated under appropriate levels of conversion and in conditions that do not contain too much water or hydrogen. Ways to overcome those limitations were suggested by the laboratory results. Nonetheless, at the end of Phase I, the catalysts did not exhibit the very stringent levels of activity or selectivity that would have permitted ready scale-up to pilot or commercial operation. Therefore, we chose not to pursue Phase II of this work which would have included further bench-scale testing

  4. Chemiluminescence analyzer of NOx as a high-throughput screening tool in selective catalytic reduction of NO

    International Nuclear Information System (INIS)

    Oh, Kwang Seok; Woo, Seong Ihl

    2011-01-01

    A chemiluminescence-based analyzer of NO x gas species has been applied for high-throughput screening of a library of catalytic materials. The applicability of the commercial NO x analyzer as a rapid screening tool was evaluated using selective catalytic reduction of NO gas. A library of 60 binary alloys composed of Pt and Co, Zr, La, Ce, Fe or W on Al 2 O 3 substrate was tested for the efficiency of NO x removal using a home-built 64-channel parallel and sequential tubular reactor. The NO x concentrations measured by the NO x analyzer agreed well with the results obtained using micro gas chromatography for a reference catalyst consisting of 1 wt% Pt on γ-Al 2 O 3 . Most alloys showed high efficiency at 275 °C, which is typical of Pt-based catalysts for selective catalytic reduction of NO. The screening with NO x analyzer allowed to select Pt-Ce (X) (X=1–3) and Pt–Fe (2) as the optimal catalysts for NO x removal: 73% NO x conversion was achieved with the Pt–Fe (2) alloy, which was much better than the results for the reference catalyst and the other library alloys. This study demonstrates a sequential high-throughput method of practical evaluation of catalysts for the selective reduction of NO.

  5. Photo catalytic reduction of benzophenone on TiO2: Effect of preparation method and reaction conditions

    International Nuclear Information System (INIS)

    Albiter E, E.; Valenzuela Z, M. A.; Alfaro H, S.; Flores V, S. O.; Rios B, O.; Gonzalez A, V. J.; Cordova R, I.

    2010-01-01

    The photo catalytic reduction of benzophenone was studied focussing on improving the yield to benzhydrol. TiO 2 was synthesized by means of a hydrothermal technique. TiO 2 (Degussa TiO 2 -P25) was used as a reference. Catalysts were characterized by X-ray diffraction and nitrogen physisorption. The photo catalytic reduction was carried out in a batch reactor at 25 C under nitrogen atmosphere, acetonitrile as solvent and isopropanol as electron donor. A 200 W Xe-Hg lamp (λ= 360 nm) was employed as irradiation source. The chemical composition of the reaction system was determined by HPLC. Structural and textural properties of the synthesized TiO 2 depended on the type of acid used during sol formation step. Using HCl, a higher specific surface area and narrower pore size distribution of TiO 2 was obtained in comparison with acetic acid. As expected, the photochemical reduction of benzophenone yielded benzopinacol as main product, whereas, benzhydrol is only produced in presence of TiO 2 (i.e. photo catalytic route). In general, the hydrothermally synthesized catalysts were less active and with a lower yield to benzhydrol. The optimal reaction conditions to highest values of benzhydrol yield (70-80%) were found at 2 g/L (catalyst loading) and 0.5 m M of initial concentration of benzophenone, using commercial TiO 2 -P25. (Author)

  6. Photo catalytic reduction of benzophenone on TiO{sub 2}: Effect of preparation method and reaction conditions

    Energy Technology Data Exchange (ETDEWEB)

    Albiter E, E.; Valenzuela Z, M. A.; Alfaro H, S.; Flores V, S. O.; Rios B, O.; Gonzalez A, V. J.; Cordova R, I., E-mail: mavalenz@ipn.m [IPN, Escuela Superior de Ingenieria Quimica e Industrias Extractivas, Laboratorio de Catalisis y Materiales, Zacatenco, 07738 Mexico D. F. (Mexico)

    2010-07-01

    The photo catalytic reduction of benzophenone was studied focussing on improving the yield to benzhydrol. TiO{sub 2} was synthesized by means of a hydrothermal technique. TiO{sub 2} (Degussa TiO{sub 2}-P25) was used as a reference. Catalysts were characterized by X-ray diffraction and nitrogen physisorption. The photo catalytic reduction was carried out in a batch reactor at 25 C under nitrogen atmosphere, acetonitrile as solvent and isopropanol as electron donor. A 200 W Xe-Hg lamp ({lambda}= 360 nm) was employed as irradiation source. The chemical composition of the reaction system was determined by HPLC. Structural and textural properties of the synthesized TiO{sub 2} depended on the type of acid used during sol formation step. Using HCl, a higher specific surface area and narrower pore size distribution of TiO{sub 2} was obtained in comparison with acetic acid. As expected, the photochemical reduction of benzophenone yielded benzopinacol as main product, whereas, benzhydrol is only produced in presence of TiO{sub 2} (i.e. photo catalytic route). In general, the hydrothermally synthesized catalysts were less active and with a lower yield to benzhydrol. The optimal reaction conditions to highest values of benzhydrol yield (70-80%) were found at 2 g/L (catalyst loading) and 0.5 m M of initial concentration of benzophenone, using commercial TiO{sub 2}-P25. (Author)

  7. Electrochemical characterization of praseodymia doped zircon. Catalytic effect on the electrochemical reduction of molecular oxygen in polar organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Domenech, Antonio, E-mail: antonio.domenech@uv.es [Departament de Quimica Analitica, Universitat de Valencia, Dr. Moliner, 50, 46100 Burjassot, Valencia (Spain); Montoya, Noemi; Alarcon, Javier [Departament de Quimica Inorganica, Universitat de Valencia, Dr. Moliner, 50, 46100 Burjassot, Valencia (Spain)

    2011-08-01

    Highlights: > Electrochemical characterization of Pr centers in praseodymia-doped zircon. > Study of the catalytic effect on the reduction of peroxide radical anion in nonaqueous solvents. > Assessment of non-uniform distribution of Pr centers in the zircon grains. - Abstract: The voltammetry of microparticles and scanning electrochemical microscopy methodologies are applied to characterize praseodymium centers in praseodymia-doped zircon (Pr{sub x}Zr{sub (1-y)}Si{sub (1-z)}O{sub 4}; y + z = x; 0.02 < x < 0.10) specimens prepared via sol-gel synthetic routes. In contact with aqueous electrolytes, two overlapping Pr-centered cathodic processes, attributable to the Pr (IV) to Pr (III) reduction of Pr centers in different sites are obtained. In water-containing, air-saturated acetone and DMSO solutions as solvent, Pr{sub x}Zr{sub (1-y)}Si{sub (1-z)}O{sub 4} materials produce a significant catalytic effect on the electrochemical reduction of peroxide radical anion electrochemically generated. These electrochemical features denote that most of the Pr centers are originally in its 4+ oxidation state in the parent Pr{sub x}Zr{sub (1-y)}Si{sub (1-z)}O{sub 4} specimens. The variation of the catalytic performance of such specimens with potential scan rate, water concentration and Pr loading suggests that Pr is not uniformly distributed within the zircon grains, being concentrated in the outer region of such grains.

  8. Catalytic Destruction of a Surrogate Organic Hazardous Air Pollutant as a Potential Co-benefit for Coal-fired Selective Catalyst Reduction Systems

    Science.gov (United States)

    Catalytic destruction of benzene (C6H6), a surrogate for organic hazardous air pollutants (HAPs) produced from coal combustion, was investigated using a commercial selective catalytic reduction (SCR) catalyst for evaluating the potential co-benefit of the SCR technology for reduc...

  9. Ni0 encapsulated in N-doped carbon nanotubes for catalytic reduction of highly toxic hexavalent chromium

    Science.gov (United States)

    Yao, Yunjin; Zhang, Jie; Chen, Hao; Yu, Maojing; Gao, Mengxue; Hu, Yi; Wang, Shaobin

    2018-05-01

    N-doped carbon nanotubes encapsulating Ni0 nanoparticles (Ni@N-C) were fabricated via thermal reduction of dicyandiamide and NiCl2·6H2O, and used to remove CrVI in polluted water. The resultant products present an excellent catalytic activity for CrVI reduction using formic acid under relatively mild conditions. The CrVI reduction efficiency of Ni@N-C was significantly affected by the preparation conditions including the mass of nickel salt and synthesis temperatures. The impacts of several reaction parameters, such as initial concentrations of CrVI and formic acid, solution pH and temperatures, as well as inorganic anions in solution on CrVI reduction efficiency were also evaluated in view of scalable industrial applications. Owing to the synergistic effects amongst tubes-coated Ni0, doped nitrogen, oxygen containing groups, and the configuration of carbon nanotubes, Ni@N-C catalysts exhibit excellent catalytic activity and recyclable capability for CrVI reduction. Carbon shell can efficiently protect inner Ni0 core and N species from corrosion and subsequent leaching, while Ni0 endows the Ni@N-C catalysts with ferromagnetism, so that the composites can be easily separated via a permanent magnet. This study opens up an avenue for design of N-doped carbon nanotubes encapsulating Ni0 nanoparticles with high CrVI removal efficiency and magnetic recyclability as low-cost catalysts for industrial applications.

  10. Ultra-fast catalytic reduction of dyes by ionic liquid recoverable and reusable mefenamic acid derived gold nanoparticles.

    Science.gov (United States)

    Hassan, Syeda Sara; Sirajuddin; Solangi, Amber Rehana; Agheem, Mohammad Hassan; Junejo, Yasmeen; Kalwar, Nazar Hussain; Tagar, Zulfiqar Ali

    2011-06-15

    We synthesized mefenamic acid (MA) derived gold nanoparticles (MA-AuNps) in aqueous solution (MA-Au sol). Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) of the sol at 1, 5, 15 and 60 min showed changes in size and shape of formed AuNps. Fourier Transform Infrared (FTIR) Spectroscopy revealed the interaction between AuNps and MA. Each Au sol exhibited exceptional catalytic activity for the reduction of Methylene Blue (MB), Rose Bengal (RB) and Eosin B (EB) dye individually as well as collectively. However, complete reduction of dye(s) was accomplished by Au sol of 5 min in just 15s. The catalytic performance of Ma-Au sol was far superior to that adsorbed on glass. AuNps were recovered with the help of water insoluble room temperature ionic liquid and reused with enhanced catalytic potential. This finding is a novel, rapid and highly economical alternative for environmental safety against pollution by dyes and extendable for control of other reducible contaminants as well. Copyright © 2011 Elsevier B.V. All rights reserved.

  11. Exploring asymmetric catalytic transformations

    NARCIS (Netherlands)

    Guduguntla, Sureshbabu

    2017-01-01

    In Chapter 2, we report a highly enantioselective synthesis of β-alkyl-substituted alcohols through a one-pot Cu- catalyzed asymmetric allylic alkylation with organolithium reagents followed by reductive ozonolysis. The synthesis of γ-alkyl-substituted alcohols was also achieved through Cu-catalyzed

  12. A DFT exploration of the enantioselective rearrangement of cyclohexene oxide to cyclohexenol

    DEFF Research Database (Denmark)

    Brandt, Peter; Norrby, Per-Ola; Andersson, Pher G.

    2003-01-01

    In this paper, we present computational results for the (1S,3R,4R)-3-(pyrrolidinyl)-methyl-2-azabicyclo[2.2.1]heptane mediated rearrangement of cyclohexene oxide. The results nicely explain the differences in enantioselectivities between catalytic and stoichiometric mode between different ligands...

  13. Pt skin coated hollow Ag-Pt bimetallic nanoparticles with high catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Fu, Tao; Huang, Jianxing; Lai, Shaobo; Zhang, Size; Fang, Jun; Zhao, Jinbao

    2017-10-01

    The catalytic activity and stability of electrocatalyst is critical for the commercialization of fuel cells, and recent reports reveal the great potential of the hollow structures with Pt skin coat for developing high-powered electrocatalysts due to their highly efficient utilization of the Pt atoms. Here, we provide a novel strategy to prepare the Pt skin coated hollow Ag-Pt structure (Ag-Pt@Pt) of ∼8 nm size at room temperature. As loaded on the graphene, the Ag-Pt@Pt exhibits a remarkable mass activity of 0.864 A/mgPt (at 0.9 V, vs. reversible hydrogen electrode (RHE)) towards oxygen reduction reaction (ORR), which is 5.30 times of the commercial Pt/C catalyst, and the Ag-Pt@Pt also shows a better stability during the ORR catalytic process. The mechanism of this significant enhancement can be attributed to the higher Pt utilization and the unique Pt on Ag-Pt surface structure, which is confirmed by the density functional theory (DFT) calculations and other characterization methods. In conclusion, this original work offers a low-cost and environment-friendly method to prepare a high active electrocatalyst with cheaper price, and this work also discloses the correlation between surface structures and ORR catalytic activity for the hollow structures with Pt skin coat, which can be instructive for designing novel advanced electrocatalysts for fuel cells.

  14. Efficient selective catalytic reduction of NO by novel carbon-doped metal catalysts made from electroplating sludge.

    Science.gov (United States)

    Zhang, Jia; Zhang, Jingyi; Xu, Yunfeng; Su, Huimin; Li, Xiaoman; Zhou, Ji Zhi; Qian, Guangren; Li, Li; Xu, Zhi Ping

    2014-10-07

    Electroplating sludges, once regarded as industrial wastes, are precious resources of various transition metals. This research has thus investigated the recycling of an electroplating sludge as a novel carbon-doped metal (Fe, Ni, Mg, Cu, and Zn) catalyst, which was different from a traditional carbon-supported metal catalyst, for effective NO selective catalytic reduction (SCR). This catalyst removed >99.7% NO at a temperature as low as 300 °C. It also removed NO steadily (>99%) with a maximum specific accumulative reduced amount (MSARA) of 3.4 mmol/g. Gas species analyses showed that NO removal was accompanied by evolving N2 and CO2. Moreover, in a wide temperature window, the sludge catalyst showed a higher CO2 selectivity (>99%) than an activated carbon-supported metal catalyst. Structure characterizations revealed that carbon-doped metal was transformed to metal oxide in the sludge catalyst after the catalytic test, with most carbon (2.33 wt %) being consumed. These observations suggest that NO removal over the sludge catalyst is a typical SCR where metals/metal oxides act as the catalytic center and carbon as the reducing reagent. Therefore, our report probably provides an opportunity for high value-added utilizations of heavy-metal wastes in mitigating atmospheric pollutions.

  15. 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.

  16. Impact of selective catalytic reduction systems on the operation of coal and oil fired boilers and downstream equipment

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2006-07-01

    The history of the development of selective catalytic reduction (SCR) technology has clearly demonstrated that whenever the technology arrives in a new region of the world new challenges are met. This paper discusses some of these historical challenges and their particular solutions in some detail. The paper shows that the design of successful SCR systems is extremely site-specific, but that the technology continues to evolve to meet these continuously changing demands. Most recently the increased power of CFD technology has enabled SCR to meet the more stringent North American emissions criteria through optimal fluid dynamic design. 4 figs.

  17. Catalytic reduction of emissions from small scale wood combustion. State of the art

    Energy Technology Data Exchange (ETDEWEB)

    Hargitai, T.; Silversand, F.A. [Katator AB, Lund (Sweden)

    1998-12-31

    Small-scale combustion of big-fuel often results in excessive emissions of volatile organic compounds (VOC), polyaromatic compounds (PAM) and carbon monoxide (CO). These compounds have a negative impact on human health and urban air quality. The predominant volatile organic compounds present in flue gases from big-fuel combustion are propylene, ethylene, butadiene, methanol, ethanol, methane, phenol and benzene. The poor combustion performance of some wood stoves has in certain cases led to legislation against small-scale combustion of big-fuel in urban areas. Catalytic cleaning is one very efficient way of decreasing the environmental impacts of big-fuel combustion. Several studies concerning catalytic purification of flue gases from big-fuel combustion have been presented over the years. Several problems must be addressed when designing a catalyst for this application: Clogging problems from deposition of ashes and particulates in the catalyst; Catalyst poisoning by sulphur, phosphorus, alkali metals etc.; Catalyst fouling due to deposition of ashes and particulates; Catalyst overheating at high flue-gas temperatures and Poor catalyst performance during start-up Most studies have been focused on monolith-type catalysts and- the conversion of CO, VOC and PAH typically is above 80 %. The observed problems are associated with increased pressure drop due to catalyst clogging and decreased catalyst performance due to fouling and poisoning. In most cases precious metals, preferably Pt. have been used as active combustion catalyst. Precious metals have a high activity for the combustion of CO and hydrocarbons and a fair stability against poisoning with compounds present in flue gases from big-fuel, e.g. sulphur and alkali metals. The majority of the studies on precious metals have been focused on Pt. Rh and Pd, which are especially active in catalytic combustion. Some metal oxides are used in catalytic combustion, especially at low temperatures (e.g. in VOC abatement

  18. Catalytic reduction of 4-nitrophenol using gold nanoparticles biosynthesized by cell-free extracts of Aspergillus sp. WL-Au

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Wenli; Qu, Yuanyuan, E-mail: qyy@dlut.edu.cn; Pei, Xiaofang; Li, Shuzhen; You, Shengnan; Wang, Jingwei; Zhang, Zhaojing; Zhou, Jiti

    2017-01-05

    Highlights: • A green process for AuNPs synthesis was achieved by fungus Aspergillus. • Uniform spherical AuNPs with well dispersity and stability were biosynthesized. • The biogenic AuNPs possessed remarkable catalytic activities for 4-NP reduction. - Abstract: A facile one-pot eco-friendly process for synthesis of gold nanoparticles (AuNPs) with high catalytic activity was achieved using cell-free extracts of Aspergillus sp. WL-Au as reducing, capping and stabilizing agents. The surface plasmon resonance band of UV–vis spectrum at 532 nm confirmed the presence of AuNPs. Transmission electron microscopy images showed that quite uniform spherical AuNPs were synthesized and the average size of nanoparticles increased from 4 nm to 29 nm with reaction time. X-ray diffraction analysis verified the formation of nano-crystalline gold particles. Fourier transform infrared spectra showed the presence of functional groups on the surface of biosynthesized AuNPs, such as O−H, N−H, C=O, C−H, C−OH and C−O−C groups, which increased the stability of AuNPs. The biogenic AuNPs could serve as a highly efficient catalyst for 4-nitrophenol reduction. The reaction rate constant was linearly correlated with the concentration of AuNPs, which increased from 0.59 min{sup −1} to 1.51 min{sup −1} with the amount of AuNPs increasing form 1.46 × 10{sup −6} to 17.47 × 10{sup −6} mmol. Moreover, the as-synthesized AuNPs exhibited a remarkable normalized catalytic activity (4.04 × 10{sup 5} min{sup −1} mol{sup −1}), which was much higher than that observed for AuNPs synthesized by other biological and conventional chemical methods.

  19. Catalytic reduction of 4-nitrophenol using gold nanoparticles biosynthesized by cell-free extracts of Aspergillus sp. WL-Au

    International Nuclear Information System (INIS)

    Shen, Wenli; Qu, Yuanyuan; Pei, Xiaofang; Li, Shuzhen; You, Shengnan; Wang, Jingwei; Zhang, Zhaojing; Zhou, Jiti

    2017-01-01

    Highlights: • A green process for AuNPs synthesis was achieved by fungus Aspergillus. • Uniform spherical AuNPs with well dispersity and stability were biosynthesized. • The biogenic AuNPs possessed remarkable catalytic activities for 4-NP reduction. - Abstract: A facile one-pot eco-friendly process for synthesis of gold nanoparticles (AuNPs) with high catalytic activity was achieved using cell-free extracts of Aspergillus sp. WL-Au as reducing, capping and stabilizing agents. The surface plasmon resonance band of UV–vis spectrum at 532 nm confirmed the presence of AuNPs. Transmission electron microscopy images showed that quite uniform spherical AuNPs were synthesized and the average size of nanoparticles increased from 4 nm to 29 nm with reaction time. X-ray diffraction analysis verified the formation of nano-crystalline gold particles. Fourier transform infrared spectra showed the presence of functional groups on the surface of biosynthesized AuNPs, such as O−H, N−H, C=O, C−H, C−OH and C−O−C groups, which increased the stability of AuNPs. The biogenic AuNPs could serve as a highly efficient catalyst for 4-nitrophenol reduction. The reaction rate constant was linearly correlated with the concentration of AuNPs, which increased from 0.59 min −1 to 1.51 min −1 with the amount of AuNPs increasing form 1.46 × 10 −6 to 17.47 × 10 −6 mmol. Moreover, the as-synthesized AuNPs exhibited a remarkable normalized catalytic activity (4.04 × 10 5 min −1 mol −1 ), which was much higher than that observed for AuNPs synthesized by other biological and conventional chemical methods.

  20. Catalytic reduction of 4-nitrophenol over Ni-Pd nanodimers supported on nitrogen-doped reduced graphene oxide

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Lijun, E-mail: liulj@wtu.edu.cn [College of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430073, People' s Republic of China (China); Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Chen, Ruifen; Liu, Weikai [College of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430073, People' s Republic of China (China); Wu, Jiamin [Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Gao, Di, E-mail: gaod@pitt.edu [Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States)

    2016-12-15

    Catalytic reduction of toxic 4-nitrophenol to 4-aminophenol over magnetically recoverable nanocatalysts has attracted much attention. Herein, we report a Ni-Pd/NrGO catalyst through the growth of Ni-Pd nanodimers (NDs) on nitrogen-doped reduced graphene oxide (NrGO). The Ni-Pd NDs show a heterogeneous nanostructure with Ni and Pd subparts contacting with each other, remarkably different from the frequently-observed core/shell nanoparticles (NPs) or nanoalloy. The formation of Ni-Pd NDs follows an initial deposition of Pd NPs on the graphene and in-situ catalytic generation of Ni subparts over the newly-generated Pd NPs. The resulting Ni-Pd/NrGO exhibits a superior catalytic activity towards the reduction of 4-nitrophenol at room temperature with a high rate constant (3400 s{sup -1} g{sup -1}) and a low activated energy (29.1 kJ mol{sup -1}) as compared to unsupported Ni-Pd NDs and supported monometallic catalysts. The conversion rate of 4-NP is calculated to be 99.5% and the percent yield (%) of 4-AP is as high as 99.1%. A synergistic catalysis mechanism is rationally proposed, which is ascribed to the electronic modification of Ni-Pd metals due to the strong metal/support interaction (SMSI) effect as well as the electron transfer between Ni and Pd. The hybrid catalyst shows soft ferromagnetic properties and can be magnetically separated and recycled without obvious loss of activity.

  1. AuPd Bimetallic Nanocrystals Embedded in Magnetic Halloysite Nanotubes: Facile Synthesis and Catalytic Reduction of Nitroaromatic Compounds

    Directory of Open Access Journals (Sweden)

    Lei Jia

    2017-10-01

    Full Text Available In this research, a facile and effective approach was developed for the preparation of well-designed AuPd alloyed catalysts supported on magnetic halloysite nanotubes (HNTs@Fe3O4@AuPd. The microstructure and the magnetic properties of HNTs@Fe3O4@AuPd were confirmed by transmission electron microscopy (TEM, high resolution TEM (HRTEM, energy-dispersive X-ray spectroscopy (EDS, and vibrating sample magnetometry (VSM analyses. The catalysts, fabricated by a cheap, environmentally friendly, and simple surfactant-free formation process, exhibited high activities during the reduction of 4-nitrophenol and various other nitroaromatic compounds. Moreover, the catalytic activities of the HNTs@Fe3O4@AuPd nanocatalysts were tunable via adjusting the atomic ratio of AuPd during the synthesis. As compared with the monometallic nanocatalysts (HNTs@Fe3O4@Au and HNTs@Fe3O4@Pd, the bimetallic alloyed HNTs@Fe3O4@AuPd nanocatalysts exhibited excellent catalytic activities toward the reduction of 4-nitrophenol (4-NP to 4-aminophenol. Furthermore, the as-obtained HNTs@Fe3O4@AuPd can be recycled several times, while retaining its functionality due to the stability and magnetic separation property.

  2. Effect of selective catalytic reduction (SCR) on fine particle emission from two coal-fired power plants in China

    Science.gov (United States)

    Li, Zhen; Jiang, Jingkun; Ma, Zizhen; Wang, Shuxiao; Duan, Lei

    2015-11-01

    Nitrogen oxides (NOx) emission abatement of coal-fired power plants (CFPPs) requires large-scaled installation of selective catalytic reduction (SCR), which would reduce secondary fine particulate matter (PM2.5) (by reducing nitrate aerosol) in the atmosphere. However, our field measurement of two CFPPs equipped with SCR indicates a significant increase of SO42- and NH4+ emission in primary PM2.5, due to catalytic enhancement of SO2 oxidation to SO3 and introducing of NH3 as reducing agent. The subsequent formation of (NH4)2SO4 or NH4HSO4 aerosol is commonly concentrated in sub-micrometer particulate matter (PM1) with a bimodal pattern. The measurement at the inlet of stack also showed doubled primary PM2.5 emission by SCR operation. This effect should therefore be considered when updating emission inventory of CFPPs. By rough estimation, the enhanced primary PM2.5 emission from CFPPs by SCR operation would offset 12% of the ambient PM2.5 concentration reduction in cities as the benefit of national NOx emission abatement, which should draw attention of policy-makers for air pollution control.

  3. Abroma augusta Linn bark extract-mediated green synthesis of gold nanoparticles and its application in catalytic reduction

    Science.gov (United States)

    Das, Subhajit; Bag, Braja Gopal; Basu, Ranadhir

    2015-10-01

    The bark extract of Abroma augusta Linn is rich in medicinally important phytochemicals including antioxidants and polyphenols. First one step green synthesis of gold nanoparticles (AuNPs) has been described utilizing the bark extract of Abroma augusta L. and chloroauric acid under very mild reaction conditions. The phytochemicals present in the bark extract acted both as a reducing as well as a stabilizing agent, and no additional stabilizing and capping agents were needed. Detailed characterizations of the stabilized AuNPs were carried out by surface plasmon resonance spectroscopy, high resolution transmission electron microscopy, and X-ray diffraction studies. The catalytic activity of the freshly synthesized gold nanoparticles has been demonstrated for the sodium borohydride reduction of 4-nitrophenol to 4-aminophenol, and the kinetics of the reduction reaction have been studied spectrophotometrically.

  4. Selective catalytic reduction of nitric oxide with acetaldehyde over NaY zeolite catalyst in lean exhaust feed

    International Nuclear Information System (INIS)

    Schmieg, Steven J.; Cho, Byong K.; Oh, Se H.

    2004-01-01

    Steady-state selective catalytic reduction (SCR) of nitric oxide (NO) was investigated under simulated lean-burn conditions using acetaldehyde (CH 3 CHO) as the reductant. This work describes the influence of catalyst space velocity and the impact of nitric oxide, acetaldehyde, oxygen, sulfur dioxide, and water on NO x reduction activity over NaY zeolite catalyst. Results indicate that with sufficient catalyst volume 90% NO x conversion can be achieved at temperatures relevant to light-duty diesel exhaust (150-350C). Nitric oxide and acetaldehyde react to form N 2 , HCN, and CO 2 . Oxygen is necessary in the exhaust feed stream to oxidize NO to NO 2 over the catalyst prior to reduction, and water is required to prevent catalyst deactivation. Under conditions of excess acetaldehyde (C 1 :N>6:1) and low temperature ( x conversion is apparently very high; however, the NO x conversion steadily declines with time due to catalytic oxidation of some of the stored (adsorbed) NO to NO 2 , which can have a significant impact on steady-state NO x conversion. With 250ppm NO in the exhaust feed stream, maximum NO x conversion at 200C can be achieved with =400ppm of acetaldehyde, with higher acetaldehyde concentrations resulting in production of acetic acid and breakthrough of NO 2 causing lower NO x conversion levels. Less acetaldehyde is necessary at lower NO concentrations, while more acetaldehyde is required at higher temperatures. Sulfur in the exhaust feed stream as SO 2 can cause slow deactivation of the catalyst by poisoning the adsorption and subsequent reaction of nitric oxide and acetaldehyde, particularly at low temperature

  5. Application of Phosphine-Phosphite Ligands in the Iridium Catalyzed Enantioselective Hydrogenation of 2-Methylquinoline

    Directory of Open Access Journals (Sweden)

    Miguel Rubio

    2010-10-01

    Full Text Available The hydrogenation of 2-methylquinoline with Ir catalysts based on chiral phosphine-phosphites has been investigated. It has been observed that the reaction is very sensitive to the nature of the ligand. Optimization of the catalyst, allowed by the highly modular structure of these phosphine-phosphites, has improved the enantioselectivity of the reaction up to 73% ee. The influence of additives in this reaction has also been investigated. Contrary to the beneficial influence observed in related catalytic systems, iodine has a deleterious effect in the present case. Otherwise, aryl phosphoric acids produce a positive impact on catalyst activity without a decrease on enantioselectivity.

  6. Enantioselective biotransformations of nitriles in organic synthesis.

    Science.gov (United States)

    Wang, Mei-Xiang

    2015-03-17

    The hydration and hydrolysis of nitriles are valuable synthetic methods used to prepare carboxamides and carboxylic acids. However, chemical hydration and hydrolysis of nitriles involve harsh reaction conditions, have low selectivity, and generate large amounts of waste. Therefore, researchers have confined the scope of these reactions to simple nitrile substrates. However, biological transformations of nitriles are highly efficient, chemoselective, and environmentally benign, which has led synthetic organic chemists and biotechologists to study these reactions in detail over the last two decades. In nature, biological systems degrade nitriles via two distinct pathways: nitrilases catalyze the direct hydrolysis of nitriles to afford carboxylic acids with release of ammonia, and nitrile hydratases catalyze the conversion of nitriles into carboxamides, which then furnish carboxylic acids via hydrolysis in the presence of amidases. Researchers have subsequently developed biocatalytic methods into useful industrial processes for the manufacture of commodity chemicals, including acrylamide. Since the late 1990s, research by my group and others has led to enormous progress in the understanding and application of enantioselective biotransformations of nitriles in organic synthesis. In this Account, I summarize the important advances in enantioselective biotransformations of nitriles and amides, with a primary focus on research from my laboratory. I describe microbial whole-cell-catalyzed kinetic resolution of various functionalized nitriles, amino- and hydroxynitriles, and nitriles that contain small rings and the desymmetrization of prochiral and meso dinitriles and diamides. I also demonstrate how we can apply the biocatalytic protocol to synthesize natural products and bioactive compounds. These nitrile biotransformations offer an attractive and unique protocol for the enantioselective synthesis of polyfunctionalized organic compounds that are not readily obtainable by

  7. Tuning and Switching Enantioselectivity of Asymmetric Carboligation in an Enzyme through Mutational Analysis of a Single Hot Spot.

    Science.gov (United States)

    Wechsler, Cindy; Meyer, Danilo; Loschonsky, Sabrina; Funk, Lisa-Marie; Neumann, Piotr; Ficner, Ralf; Brodhun, Florian; Müller, Michael; Tittmann, Kai

    2015-12-01

    Enantioselective bond making and breaking is a hallmark of enzyme action, yet switching the enantioselectivity of the reaction is a difficult undertaking, and typically requires extensive screening of mutant libraries and multiple mutations. Here, we demonstrate that mutational diversification of a single catalytic hot spot in the enzyme pyruvate decarboxylase gives access to both enantiomers of acyloins acetoin and phenylacetylcarbinol, important pharmaceutical precursors, in the case of acetoin even starting from the unselective wild-type protein. Protein crystallography was used to rationalize these findings and to propose a mechanistic model of how enantioselectivity is controlled. In a broader context, our studies highlight the efficiency of mechanism-inspired and structure-guided rational protein design for enhancing and switching enantioselectivity of enzymatic reactions, by systematically exploring the biocatalytic potential of a single hot spot. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Contribution of gold nanoparticles to the catalytic DNA strand displacement in leakage reduction and signal amplification.

    Science.gov (United States)

    Wang, Bei; Zhou, Xiang; Yao, Dongbao; Sun, Xianbao; He, Miao; Wang, Xiaojing; Yin, Xue; Liang, Haojun

    2017-10-03

    A new model using a gold nanoparticle (AuNP)-DNA system to constrain leakage and improve efficiency of catalytic toehold-mediated strand displacement reactions was outlined. A 10-bp spacer on AuNPs and fourfold amount of fuels were determined for good performance of this model with an optimized toehold strategy. After the reaction at 25 °C for 10 h, a 258 pM target could be identified, which is a remarkable improvement compared with the traditional AuNP-DNA system without fuel. Moreover, this model was also studied to differentiate specific single nucleotide polymorphism on target with superior selection factors. This model may help by introducing a proposition of target detection to guide further investigation.

  9. Boosting catalytic activity of metal nanoparticles for 4-nitrophenol reduction: Modification of metal naoparticles with poly(diallyldimethylammonium chloride)

    Energy Technology Data Exchange (ETDEWEB)

    You, Jyun-Guo; Shanmugam, Chandirasekar [Department of Chemistry, National Sun Yat-sen University, Taiwan (China); Liu, Yao-Wen; Yu, Cheng-Ju [Department of Applied Physics and Chemistry, University of Taipei, Taiwan (China); Tseng, Wei-Lung, E-mail: tsengwl@mail.nsysu.edu.tw [Department of Chemistry, National Sun Yat-sen University, Taiwan (China); School of Pharmacy, College of Pharmacy, Kaohsiung Medical University, Taiwan (China); Center for Nanoscience and Nanotechnology, National Sun Yat-sen University, Taiwan (China)

    2017-02-15

    Highlights: • The choice of capping ligand determines catalytic activity of metal nanocatalysts. • PDDA-capped metal nanoparticles electrostatically interact with 4-NP and BH4{sup −}. • PDDA-capped metal nanoparticles have good recyclability and large scalability. • PDDA-capped Pd nanoparticles show the highest rate constant and activity parameter. - Abstract: Most of the previously reported studies have focused on the change in the size, morphology, and composition of metal nanocatalysts for improving their catalytic activity. Herein, we report poly(diallyldimethylammonium chloride) [PDDA]-stabilized nanoparticles (NPs) of platinum (Pt) and palladium (Pd) as highly active and efficient catalysts for hydrogenation of 4-nitrophenol (4-NP) in the presence of NaBH4. PDDA-stabilized Pt and Pd NPs possessed similar particle size and same facet with citrate-capped Pt and Pd NPs, making this study to investigate the inter-relationship between catalytic activity and surface ligand without the consideration of the effects of particle size and facet. Compared to citrate-capped Pt and Pd NPs, PDDA-stabilized Pt and Pd NPs exhibited excellent pH and salt stability. PDDA could serve as an electron acceptor for metal NPs to produce the net positive charges on the metal surface, which provide strong electrostatic attraction with negatively charged nitrophenolate and borohydride ions. The activity parameter and rate constant of PDDA-stabilized metal NPs were higher than those of citrate-capped metal NPs. Compared to the previously reported Pd nanomaterials for the catalysis of NaBH4-mediated reduction of 4-NP, PDDA-stabilized Pd NPs exhibited the extremely high activity parameter (195 s{sup −1} g{sup −1}) and provided excellent scalability and reusability.

  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. Enantioselective Copper-Catalyzed Carboetherification of Unactivated Alkenes**

    Science.gov (United States)

    Bovino, Michael T.; Liwosz, Timothy W.; Kendel, Nicole E.; Miller, Yan; Tyminska, Nina

    2014-01-01

    Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein is reported a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols that terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition state calculations support a cis-oxycupration stereochemistry-determining step. PMID:24798697

  12. Catalytic reduction of organic dyes at gold nanoparticles impregnated silica materials: influence of functional groups and surfactants

    International Nuclear Information System (INIS)

    Azad, Uday Pratap; Ganesan, Vellaichamy; Pal, Manas

    2011-01-01

    Gold nanoparticles (Au NPs) in three different silica based sol–gel matrixes with and without surfactants are prepared. They are characterized by UV–vis absorbance and transmission electron microscopic (TEM) studies. The size and shape of Au NPs varied with the organo-functional group present in the sol–gel matrix. In the presence of mercaptopropyl functionalized organo-silica, large sized (200–280 nm) spherical Au NPs are formed whereas in the presence of aminopropyl functionalized organo-silica small sized (5–15 nm) Au NPs are formed inside the tube like organo-silica. Further, it is found that Au NPs act as efficient catalyst for the reduction of organic dyes. The catalytic rate constant is evaluated from the decrease in absorbance of the dye molecules. Presence of cationic or anionic surfactants greatly influences the catalytic reaction. The other factors like hydrophobicity of the organic dyes, complex formation of the dyes with anionic surfactants, repulsion between dyes and cationic surfactant, adsorption of dyes on the Au NPs also play important role on the reaction rate.

  13. Catalytic reduction of organic dyes at gold nanoparticles impregnated silica materials: influence of functional groups and surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Azad, Uday Pratap; Ganesan, Vellaichamy, E-mail: velganesh@yahoo.com; Pal, Manas [Banaras Hindu University, Department of Chemistry, Faculty of Science (India)

    2011-09-15

    Gold nanoparticles (Au NPs) in three different silica based sol-gel matrixes with and without surfactants are prepared. They are characterized by UV-vis absorbance and transmission electron microscopic (TEM) studies. The size and shape of Au NPs varied with the organo-functional group present in the sol-gel matrix. In the presence of mercaptopropyl functionalized organo-silica, large sized (200-280 nm) spherical Au NPs are formed whereas in the presence of aminopropyl functionalized organo-silica small sized (5-15 nm) Au NPs are formed inside the tube like organo-silica. Further, it is found that Au NPs act as efficient catalyst for the reduction of organic dyes. The catalytic rate constant is evaluated from the decrease in absorbance of the dye molecules. Presence of cationic or anionic surfactants greatly influences the catalytic reaction. The other factors like hydrophobicity of the organic dyes, complex formation of the dyes with anionic surfactants, repulsion between dyes and cationic surfactant, adsorption of dyes on the Au NPs also play important role on the reaction rate.

  14. Graphene oxide nanoplatforms to enhance catalytic performance of iron phthalocyanine for oxygen reduction reaction in bioelectrochemical systems

    Science.gov (United States)

    Costa de Oliveira, Maida Aysla; Mecheri, Barbara; D'Epifanio, Alessandra; Placidi, Ernesto; Arciprete, Fabrizio; Valentini, Federica; Perandini, Alessando; Valentini, Veronica; Licoccia, Silvia

    2017-07-01

    We report the development of electrocatalysts based on iron phthalocyanine (FePc) supported on graphene oxide (GO), obtained by electrochemical oxidation of graphite in aqueous solution of LiCl, LiClO4, and NaClO4. Structure, surface chemistry, morphology, and thermal stability of the prepared materials were investigated by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, atomic force microscopy (AFM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The catalytic activity toward oxygen reduction reaction (ORR) at neutral pH was evaluated by cyclic voltammetry. The experimental results demonstrate that the oxidation degree of GO supports affects the overall catalytic activity of FePc/GO, due to a modulation effect of the interaction between FePc and the basal plane of GO. On the basis of electrochemical, spectroscopic, and morphological investigations, FePc/GO_LiCl was selected to be assembled at the cathode side of a microbial fuel cell prototype, demonstrating a good electrochemical performance in terms of voltage and power generation.

  15. Comparative catalytic reduction of 4-nitrophenol by polyacrylamide-gold nanocomposite synthesized by hydrothermal autoclaving and conventional heating routes

    Science.gov (United States)

    Salaheldin, Hosam I.

    2017-12-01

    Gold nanoparticles (AuNPs) in polymeric polyacrylamide (PAAm) matrix were synthesized using conventional heating and autoclaving thermal techniques. The synthesized Au/PAAm nanocomposite was characterized using UV-vis spectroscopy and high-resolution transmission electron microscopy. The size of the synthesized particles was approximately 6.37 nm and 8.19 nm with the conventional heating and autoclaving thermal techniques, respectively. Electron diffraction x-ray spectroscopy and the Fourier transformation infrared spectroscopy were used for the composition and elemental studies, which confirmed that the Au metallic atoms were synthesized and embedded within a PAAm matrix via a coordination bond between the carbonyl (-CONH2) group and the metallic NPs. X-ray diffraction confirmed the crystalline nature of the fabricated AuNPs with face centered cubic of nanocrystals. The catalytic activity of the as-prepared Au/PAAm nanocomposite for the reduction of 4-nitrophenol to 4-aminophenol was studied in the presence of sodium borohydrate. The synthesized AuNPs had an effective catalytic activity; the smaller NPs synthesized NPs with the conventional heating technique had a higher reaction kinetic rate in comparation with those synthesized with the autoclaving technique. Therefore, the Au/PAAm nanocomposite can be widely used as an eco-friendly, non-toxic, a fast and cost-effective product to remove versatile organic pollutants such as aromatic nitro compounds.

  16. A facile approach to fabricate Au nanoparticles loaded SiO{sub 2} microspheres for catalytic reduction of 4-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Mingyi, E-mail: mingyitjucu@163.com [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Huang, Guanbo, E-mail: gbhuang2007@hotmail.com [Department of Chemistry, School of Science, Tianjin University, Tianjin 300072 (China); Li, Xianxian; Pang, Xiaobo [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Qiu, Haixia [Department of Chemistry, School of Science, Tianjin University, Tianjin 300072 (China)

    2015-07-15

    Hydrophilic and biocompatible macromolecules were used to improve and simplify the process for the fabrication of core/shell SiO{sub 2}@Au composite particles. The influence of polymers on the morphology of SiO{sub 2}@Au particles with different size of SiO{sub 2} cores was analyzed by transmission electron microscopy and scanning electron microscopy. The optical property of the SiO{sub 2}@Au particles was studied with UV–Vis spectroscopy. The results indicate that the structure and composition of macromolecules affect the morphology of Au layers on SiO{sub 2} microspheres. The SiO{sub 2}@Au particles prepared in the presence of polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP) have thin and complete Au nanoshells owing to their inducing act in preferential growth of Au nanoparticles along the surface of SiO{sub 2} microspheres. SiO{sub 2}@Au particles can be also prepared from SiO{sub 2} microspheres modified with 3-aminopropyltrimethoxysilane in the presence of PVA or PVP. This offers a simple way to fabricate a Au layer on SiO{sub 2} or other microspheres. The SiO{sub 2}@Au particles demonstrated high catalytic activity in the reduction of 4-nitrophenol. - Highlights: • Facile direct deposition method for Au nanoparticles on silica microspheres. • Influence of different types of macromolecule on the formation of Au shell. • High catalytic performance of Au nanoparticles on silica microspheres.

  17. A facile approach to fabricate Au nanoparticles loaded SiO2 microspheres for catalytic reduction of 4-nitrophenol

    International Nuclear Information System (INIS)

    Tang, Mingyi; Huang, Guanbo; Li, Xianxian; Pang, Xiaobo; Qiu, Haixia

    2015-01-01

    Hydrophilic and biocompatible macromolecules were used to improve and simplify the process for the fabrication of core/shell SiO 2 @Au composite particles. The influence of polymers on the morphology of SiO 2 @Au particles with different size of SiO 2 cores was analyzed by transmission electron microscopy and scanning electron microscopy. The optical property of the SiO 2 @Au particles was studied with UV–Vis spectroscopy. The results indicate that the structure and composition of macromolecules affect the morphology of Au layers on SiO 2 microspheres. The SiO 2 @Au particles prepared in the presence of polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP) have thin and complete Au nanoshells owing to their inducing act in preferential growth of Au nanoparticles along the surface of SiO 2 microspheres. SiO 2 @Au particles can be also prepared from SiO 2 microspheres modified with 3-aminopropyltrimethoxysilane in the presence of PVA or PVP. This offers a simple way to fabricate a Au layer on SiO 2 or other microspheres. The SiO 2 @Au particles demonstrated high catalytic activity in the reduction of 4-nitrophenol. - Highlights: • Facile direct deposition method for Au nanoparticles on silica microspheres. • Influence of different types of macromolecule on the formation of Au shell. • High catalytic performance of Au nanoparticles on silica microspheres

  18. Reduções enantiosseletivas de cetonas utilizando-se fermento de pão Enantioselective reductions of ketones using baker's yeast

    Directory of Open Access Journals (Sweden)

    José Augusto R. Rodrigues

    2001-12-01

    Full Text Available Baker's yeast has been successful employed to reduce carbonyl compounds carrying appropriated substituents at distances under the electronic influence of the keto group. High yields and enantiomeric excess (ee were obtained with 1,2-alkanedione, 1,2-alkanedione (2-O-methyloxime and 1,3-alkanedione. Potential chiral building blocks were obtained and applied for stereoselective synthesis of valuable compounds. Evidence for a free radical chain process was obtained with baker's yeast reduction of a-iodoacetophenone using radical inhibitors.

  19. 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.

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

    Science.gov (United States)

    None

    2017-07-25

    A system according to the principles of the present disclosure includes an air/fuel ratio determination module and an emission level determination module. The air/fuel ratio determination module determines an air/fuel ratio based on input from an air/fuel ratio sensor positioned downstream from a three-way catalyst that is positioned upstream from a selective catalytic reduction (SCR) catalyst. The emission level determination module selects one of a predetermined value and an input based on the air/fuel ratio. The input is received from a nitrogen oxide sensor positioned downstream from the three-way catalyst. The emission level determination module determines an ammonia level based on the one of the predetermined value and the input received from the nitrogen oxide sensor.

  1. Anisotropic electrical conduction and reduction in dangling-bond density for polycrystalline Si films prepared by catalytic chemical vapor deposition

    Science.gov (United States)

    Niikura, Chisato; Masuda, Atsushi; Matsumura, Hideki

    1999-07-01

    Polycrystalline Si (poly-Si) films with high crystalline fraction and low dangling-bond density were prepared by catalytic chemical vapor deposition (Cat-CVD), often called hot-wire CVD. Directional anisotropy in electrical conduction, probably due to structural anisotropy, was observed for Cat-CVD poly-Si films. A novel method to separately characterize both crystalline and amorphous phases in poly-Si films using anisotropic electrical conduction was proposed. On the basis of results obtained by the proposed method and electron spin resonance measurements, reduction in dangling-bond density for Cat-CVD poly-Si films was achieved using the condition to make the quality of the included amorphous phase high. The properties of Cat-CVD poly-Si films are found to be promising in solar-cell applications.

  2. Size Control of Iron Oxide Nanoparticles Using Reverse Microemulsion Method: Morphology, Reduction, and Catalytic Activity in CO Hydrogenation

    Directory of Open Access Journals (Sweden)

    Mohammad Reza Housaindokht

    2013-01-01

    Full Text Available Iron oxide nanoparticles were prepared by microemulsion method and evaluated in Fischer-Tropsch synthesis. The precipitation process was performed in a single-phase microemulsion operating region. Different HLB values of surfactant were prepared by mixing of sodium dodecyl sulfate (SDS and Triton X-100. Transmission electron microscopy (TEM, surface area, pore volume, average pore diameter, pore size distribution, and XRD patterns were used to analyze size distribution, shape, and structure of precipitated hematite nanoparticles. Furthermore, temperature programmed reduction (TPR and catalytic activity in CO hydrogenation were implemented to assess the performance of the samples. It was found that methane and CO2 selectivity and also the syngas conversion increased as the HLB value of surfactant decreased. In addition, the selectivity to heavy hydrocarbons and chain growth probability (α decreased by decreasing the catalyst crystal size.

  3. Carbothermal reduction of Ti-modified IRMOF-3: an adaptable synthetic method to support catalytic nanoparticles on carbon.

    Science.gov (United States)

    Kim, Jongsik; McNamara, Nicholas D; Her, Theresa H; Hicks, Jason C

    2013-11-13

    This work describes a novel method for the preparation of titanium oxide nanoparticles supported on amorphous carbon with nanoporosity (Ti/NC) via the post-synthetic modification of a Zn-based MOF with an amine functionality, IRMOF-3, with titanium isopropoxide followed by its carbothermal pyrolysis. This material exhibited high purity, high surface area (>1000 m(2)/g), and a high dispersion of metal oxide nanoparticles while maintaining a small particle size (~4 nm). The material was shown to be a promising catalyst for oxidative desulfurization of diesel using dibenzothiophene as a model compound as it exhibited enhanced catalytic activity as compared with titanium oxide supported on activated carbon via the conventional incipient wetness impregnation method. The formation mechanism of Ti/NC was also proposed based on results obtained when the carbothermal reduction temperature was varied.

  4. Reduction of nitrogen oxides from simulated exhaust gas by using plasma-catalytic process

    International Nuclear Information System (INIS)

    Mok, Young Sun; Koh, Dong Jun; Shin, Dong Nam; Kim, Kyong Tae

    2004-01-01

    Removal of nitrogen oxides (NO x ) using a nonthermal plasma reactor (dielectric-packed bed reactor) combined with monolith V 2 O 5 /TiO 2 catalyst was investigated. The effect of initial NO x concentration, feed gas flow rate (space velocity), humidity, and reaction temperature on the removal of NO x was examined. The plasma reactor used can be energized by either ac or pulse voltage. An attempt was made to utilize the electrical ignition system of an internal combustion engine as a high-voltage pulse generator for the plasma reactor. When the plasma reactor was energized by the electrical ignition system, NO was readily oxidized to NO 2 . Performance was as good as with ac energization. Increasing the fraction of NO 2 in NO x , which is the main role of the plasma reactor, largely enhanced the NO x removal efficiency. In the plasma-catalytic reactor, the increases in initial NO x concentration, space velocity (feed gas flow rate) and humidity lowered the NO x removal efficiency. However, the reaction temperature in the range up to 473 K did not significantly affect the NO x removal efficiency in the presence of plasma discharge

  5. Exo selective enantioselective nitrone cycloadditions.

    Science.gov (United States)

    Sibi, Mukund P; Ma, Zhihua; Jasperse, Craig P

    2004-01-28

    We have developed a novel method for accessing exo adducts with high enantioselectivity in nitrone cycloadditions to enoates. Pyrazolidinones proved to be effective achiral templates in the cycloadditions, providing exo adducts typically in >15:1 selectivity and 90-98% ee. The use of Lewis acids that form square planar complexes, such as copper triflate, was important for obtaining high exo selectivity.

  6. Cyclopalladated complexes in enantioselective catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Dunina, Valeria V; Gorunova, Olga N; Zykov, P A; Kochetkov, Konstantin A

    2011-01-31

    The results of the use of optically active palladacycles in enantioselective catalysis of [3,3]-sigmatropic rearrangements, aldol condensation, the Michael reaction and cross-coupling are analyzed. Reactions with allylic substrates or reagents and some other transformations are considered.

  7. Asymmetric NHC-catalyzed aza-Diels-Alder reactions: Highly enantioselective route to α-amino acid derivatives and DFT calculations

    KAUST Repository

    Yang, Limin

    2014-08-01

    A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study showed that cis-TSa, formed from a top face approach of oxodiazene to cis-IIa, is the most favorable transition state and is consistent with the experimental observations. © 2014 American Chemical Society.

  8. Structural basis for high substrate-binding affinity and enantioselectivity of 3-quinuclidinone reductase AtQR

    International Nuclear Information System (INIS)

    Hou, Feng; Miyakawa, Takuya; Kataoka, Michihiko; Takeshita, Daijiro; Kumashiro, Shoko; Uzura, Atsuko; Urano, Nobuyuki; Nagata, Koji; Shimizu, Sakayu; Tanokura, Masaru

    2014-01-01

    Highlights: • Crystal structure of AtQR has been determined at 1.72 Å. • NADH binding induces the formation of substrate binding site. • AtQR possesses a conserved hydrophobic wall for stereospecific binding of substrate. • Additional Glu197 residue is critical to the high binding affinity. - Abstract: (R)-3-Quinuclidinol, a useful compound for the synthesis of various pharmaceuticals, can be enantioselectively produced from 3-quinuclidinone by 3-quinuclidinone reductase. Recently, a novel NADH-dependent 3-quinuclidionone reductase (AtQR) was isolated from Agrobacterium tumefaciens, and showed much higher substrate-binding affinity (>100 fold) than the reported 3-quinuclidionone reductase (RrQR) from Rhodotorula rubra. Here, we report the crystal structure of AtQR at 1.72 Å. Three NADH-bound protomers and one NADH-free protomer form a tetrameric structure in an asymmetric unit of crystals. NADH not only acts as a proton donor, but also contributes to the stability of the α7 helix. This helix is a unique and functionally significant part of AtQR and is related to form a deep catalytic cavity. AtQR has all three catalytic residues of the short-chain dehydrogenases/reductases family and the hydrophobic wall for the enantioselective reduction of 3-quinuclidinone as well as RrQR. An additional residue on the α7 helix, Glu197, exists near the active site of AtQR. This acidic residue is considered to form a direct interaction with the amine part of 3-quinuclidinone, which contributes to substrate orientation and enhancement of substrate-binding affinity. Mutational analyses also support that Glu197 is an indispensable residue for the activity

  9. Structural basis for high substrate-binding affinity and enantioselectivity of 3-quinuclidinone reductase AtQR

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Feng; Miyakawa, Takuya [Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657 (Japan); Kataoka, Michihiko [Division of Applied Life Sciences, Graduate School of Life and Environmental Sciences, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai 559-8531 (Japan); Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502 (Japan); Takeshita, Daijiro [Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657 (Japan); Kumashiro, Shoko [Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502 (Japan); Uzura, Atsuko [Research and Development Center, Nagase and Co., Ltd., 2-2-3 Muratani, Nishi-ku, Kobe 651-2241 (Japan); Urano, Nobuyuki [Division of Applied Life Sciences, Graduate School of Life and Environmental Sciences, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai 559-8531 (Japan); Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502 (Japan); Nagata, Koji [Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657 (Japan); Shimizu, Sakayu [Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502 (Japan); Faculty of Bioenvironmental Science, Kyoto Gakuen University, Sogabe-cho, Kameoka 621-8555 (Japan); Tanokura, Masaru, E-mail: amtanok@mail.ecc.u-tokyo.ac.jp [Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657 (Japan)

    2014-04-18

    Highlights: • Crystal structure of AtQR has been determined at 1.72 Å. • NADH binding induces the formation of substrate binding site. • AtQR possesses a conserved hydrophobic wall for stereospecific binding of substrate. • Additional Glu197 residue is critical to the high binding affinity. - Abstract: (R)-3-Quinuclidinol, a useful compound for the synthesis of various pharmaceuticals, can be enantioselectively produced from 3-quinuclidinone by 3-quinuclidinone reductase. Recently, a novel NADH-dependent 3-quinuclidionone reductase (AtQR) was isolated from Agrobacterium tumefaciens, and showed much higher substrate-binding affinity (>100 fold) than the reported 3-quinuclidionone reductase (RrQR) from Rhodotorula rubra. Here, we report the crystal structure of AtQR at 1.72 Å. Three NADH-bound protomers and one NADH-free protomer form a tetrameric structure in an asymmetric unit of crystals. NADH not only acts as a proton donor, but also contributes to the stability of the α7 helix. This helix is a unique and functionally significant part of AtQR and is related to form a deep catalytic cavity. AtQR has all three catalytic residues of the short-chain dehydrogenases/reductases family and the hydrophobic wall for the enantioselective reduction of 3-quinuclidinone as well as RrQR. An additional residue on the α7 helix, Glu197, exists near the active site of AtQR. This acidic residue is considered to form a direct interaction with the amine part of 3-quinuclidinone, which contributes to substrate orientation and enhancement of substrate-binding affinity. Mutational analyses also support that Glu197 is an indispensable residue for the activity.

  10. Identification of intrinsic catalytic activity for electrochemical reduction of water molecules to generate hydrogen

    KAUST Repository

    Shinagawa, Tatsuya

    2015-01-01

    Insufficient hydronium ion activities at near-neutral pH and under unbuffered conditions induce diffusion-limited currents for hydrogen evolution, followed by a reaction with water molecules to generate hydrogen at elevated potentials. The observed constant current behaviors at near neutral pH reflect the intrinsic electrocatalytic reactivity of the metal electrodes for water reduction. This journal is © the Owner Societies.

  11. AuCu@Pt Nanoalloys for Catalytic Application in Reduction of 4-Nitrophenol

    Directory of Open Access Journals (Sweden)

    Sadia Mehmood

    2016-01-01

    Full Text Available To enhance and optimize nanocatalyst ability for nitrophenol (4-NP reduction reaction we look beyond Au-metal nanoparticles and describe a new class of Au nanoalloys with controlled composition for core of AuCu-metals and Pt-metal shell. The reduction of 4-NP was investigated in aqueous media spectroscopically on 7.8 nm Au nanospheres (AuNSs, 8.3 nm AuCuNSs, and 9.1 nm AuCu@Pt core-shell NSs in diameter. The rate constants of the catalyzed reaction at room temperature, activation energies, and entropies of activation of reactions catalyzed by the AuCu@Pt core-shell NSs are found to have different values to those of the pure metal NSs. The results strongly support the proposal that catalysis by nanoparticles is taking place efficiently on the surface of NSs. These core-shell nanocatalysts exhibited stability throughout the reduction reaction and proved that heterogonous type mechanisms are most likely to be dominant in nanoalloy based catalysis if the surface of the NSs is not defected upon shell incorporation.

  12. Theophylline-assisted, eco-friendly synthesis of PtAu nanospheres at reduced graphene oxide with enhanced catalytic activity towards Cr(VI) reduction.

    Science.gov (United States)

    Hu, Ling-Ya; Chen, Li-Xian; Liu, Meng-Ting; Wang, Ai-Jun; Wu, Lan-Ju; Feng, Jiu-Ju

    2017-05-01

    Theophylline as a naturally alkaloid is commonly employed to treat asthma and chronic obstructive pulmonary disorder. Herein, a facile theophylline-assisted green approach was firstly developed for synthesis of PtAu nanospheres/reduced graphene oxide (PtAu NSs/rGO), without any surfactant, polymer, or seed involved. The obtained nanocomposites were applied for the catalytic reduction and removal of highly toxic chromium (VI) using formic acid as a model reductant at 50°C, showing the significantly enhanced catalytic activity and improved recyclability when compared with commercial Pt/C (50%) and home-made Au nanocrystals supported rGO (Au NCs/rGO). It demonstrates great potential applications of the catalyst in wastewater treatment and environmental protection. The eco-friendly route provides a new platform to fabricate other catalysts with enhanced catalytic activity. Copyright © 2016 Elsevier Inc. All rights reserved.

  13. The influence of a silica pillar in lamellar tetratitanate for selective catalytic reduction of NOx using NH3

    International Nuclear Information System (INIS)

    Nogueira da Cunha, Beatriz; Gonçalves, Alécia Maria; Gomes da Silveira, Rafael; Urquieta-González, Ernesto A.; Magalhães Nunes, Liliane

    2015-01-01

    Highlights: • Potassium ions significantly affected the SCR. • The introduction of silica in the catalyst promotes the NH 3 -SCR reaction. • The catalysts activities were not significantly influenced by SO 2 addition. - Abstract: Silica-pillared layered titanate (SiO 2 –Ti 4 O 9 ) was prepared by intercalating organosilanes into the interlayers of a layered K 2 Ti 4 O 9 followed by calcination at 500 °C. The lamellar titanates produced were used as a support to prepare vanadium catalysts (1 and 2 wt%) through wet impregnation for selective catalytic reduction (SCR) of NO. The catalysts were characterized using nitrogen adsorption (BET), X-ray diffraction (XRD), temperature programmed reduction (H 2 -TPR), nuclear magnetic resonance ( 29 Si NMR), and infrared spectroscopy (FT-IR). Reduction of NO by NH 3 was studied in a fixed-bed reactor packed with the catalysts and fed a mixture comprising 1% NH 3 , 1% NO, 10% O 2 , and 34 ppm SO 2 (when used) in helium. The results demonstrate that activity is correlated with the support, i.e., with acidic strength of catalysts. The potassium in the support, K 2 Ti 4 O 9 , significantly affected the reaction and level of vanadium species reduction. The catalyst (1VSiT) with 1 wt% vanadium impregnated on the SiO 2 –Ti 4 O 9 support reduced ∼80% of the NO. Approximately the same conversion rate was generated on the catalyst (2VSiT) with 2 wt% vanadium using the same support. The increased NH 3 adsorption demonstrate that introduction of silica in the catalyst promotes the NH 3 -SCR reaction. More importantly, 2VSiT and 1VSiT were strongly resistant to SO 2 poisoning

  14. Real-world exhaust temperature profiles of on-road heavy-duty diesel vehicles equipped with selective catalytic reduction.

    Science.gov (United States)

    Boriboonsomsin, Kanok; Durbin, Thomas; Scora, George; Johnson, Kent; Sandez, Daniel; Vu, Alexander; Jiang, Yu; Burnette, Andrew; Yoon, Seungju; Collins, John; Dai, Zhen; Fulper, Carl; Kishan, Sandeep; Sabisch, Michael; Jackson, Doug

    2018-09-01

    On-road heavy-duty diesel vehicles are a major contributor of oxides of nitrogen (NO x ) emissions. In the US, many heavy-duty diesel vehicles employ selective catalytic reduction (SCR) technology to meet the 2010 emission standard for NO x . Typically, SCR needs to be at least 200°C before a significant level of NO x reduction is achieved. However, this SCR temperature requirement may not be met under some real-world operating conditions, such as during cold starts, long idling, or low speed/low engine load driving activities. The frequency of vehicle operation with low SCR temperature varies partly by the vehicle's vocational use. In this study, detailed vehicle and engine activity data were collected from 90 heavy-duty vehicles involved in a range of vocations, including line haul, drayage, construction, agricultural, food distribution, beverage distribution, refuse, public work, and utility repair. The data were used to create real-world SCR temperature and engine load profiles and identify the fraction of vehicle operating time that SCR may not be as effective for NO x control. It is found that the vehicles participated in this study operate with SCR temperature lower than 200°C for 11-70% of the time depending on their vocation type. This implies that real-world NO x control efficiency could deviate from the control efficiency observed during engine certification. Copyright © 2018 Elsevier B.V. All rights reserved.

  15. Experimental investigation of N2O formation in selective non-catalytic NOx reduction processes performed in stoker boiler

    Directory of Open Access Journals (Sweden)

    Krawczyk Piotr

    2016-12-01

    Full Text Available Stoker fired boiler plants are common throughout Eastern Europe. Increasingly strict emission standards will require application of secondary NOx abatement systems on such boilers. Yet operation of such systems, in addition to reducing NOx emissions, may also lead to emission of undesirable substances, for example N2O. This paper presents results of experimental tests concerning N2O formation in the selective non-catalytic NOx emission reduction process (SNCR in a stoker boiler (WR 25 type. Obtained results lead to an unambiguous conclusion that there is a dependency between the NOx and N2O concentrations in the exhaust gas when SNCR process is carried out in a coal-fired stoker boiler. Fulfilling new emission standards in the analysed equipment will require 40–50% reduction of NOx concentration. It should be expected that in such a case the N2O emission will be approximately 55–60 mg/m3, with the NOx to N2O conversion factor of about 40%.

  16. 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.

  17. Synergistic effect of Nitrogen-doped hierarchical porous carbon/graphene with enhanced catalytic performance for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Dewang; Yuan, Wenjing; Li, Cun; Song, Jiming; Xie, Anjian, E-mail: anjx@163.com; Shen, Yuhua, E-mail: s_yuhua@163.com

    2017-01-30

    Graphical abstract: This work demonstrates an example for turning rubbish into valuable products and addresses the disposal issue of waste biomass simultaneously for environment clean. And the typical sample exhibits excellent catalytic performance toward ORR, which is similar to that of commercial Pt/C. - Highlights: • This work demonstrates an example for turning rubbish into valuable products and addresses the disposal issue of waste biomass. • The HPC/RGO composite not only prevents the aggregation of RGO, but also takes advantage of the synergy between them. • This method was accessible, without using any activator, which is an effective strategy for the large scale application of FCs. - Abstract: Developing efficient and economical catalysts for the oxygen reduction reaction (ORR) is important to promote the commercialization of fuel cells. Here, we report a simple and environmentally friendly method to prepare nitrogen (N) –doped hierarchical porous carbon (HPC)/reduced graphene oxide (RGO) composites by reusing waste biomass (pomelo peel) coupled with graphene oxide (GO). This method is green, low-cost and without using any acid or alkali activator. The typical sample (N-HPC/RGO-1) contains 5.96 at.% nitrogen and larger BET surface area (1194 m{sup 2}/g). Electrochemical measurements show that N-HPC/RGO-1 exhibits not only a relatively positive onset potential and high current density, but also considerable methanol tolerance and long-term durability in alkaline media as well as in acidic media. The electron transfer number is close to 4, which means that it is mostly via a four-electron pathway toward ORR. The excellent catalytic performance of N-HPC/RGO-1 is due to the synergistic effect of the inherent interwoven network structure of HPC, the good electrical conductivity of RGO, and the heteroatom doping for the composite. More importantly, this work demonstrates a good example for turning discarded rubbish into valuable functional products and

  18. Catalytic reduction of nitrate and nitrite ions by hydrogen : investigation of the reaction mechanism over Pd and Pd-Cu catalysts

    NARCIS (Netherlands)

    Ilinitch, OM; Nosova, LV; Gorodetskii, VV; Ivanov, VP; Trukhan, SN; Gribov, EN; Bogdanov, SV; Cuperus, FP

    2000-01-01

    The catalytic behavior of mono- and bimetallic catalysts with Pd and/or Cu supported over gamma-Al2O3 in the reduction of aqueous nitrate and nitrite ions by hydrogen was investigated. The composition of the supported metal catalysts was analysed using secondary ion mass spectroscopy (SIMS) and

  19. Substantial Humic Acid Adsorption to Activated Carbon Air Cathodes Produces a Small Reduction in Catalytic Activity.

    Science.gov (United States)

    Yang, Wulin; Watson, Valerie J; Logan, Bruce E

    2016-08-16

    Long-term operation of microbial fuel cells (MFCs) can result in substantial degradation of activated carbon (AC) air-cathode performance. To examine a possible role in fouling from organic matter in water, cathodes were exposed to high concentrations of humic acids (HA). Cathodes treated with 100 mg L(-1) HA exhibited no significant change in performance. Exposure to 1000 mg L(-1) HA decreased the maximum power density by 14% (from 1310 ± 30 mW m(-2) to 1130 ± 30 mW m(-2)). Pore blocking was the main mechanism as the total surface area of the AC decreased by 12%. Minimization of external mass transfer resistances using a rotating disk electrode exhibited only a 5% reduction in current, indicating about half the impact of HA adsorption was associated with external mass transfer resistance and the remainder was due to internal resistances. Rinsing the cathodes with deionized water did not restore cathode performance. These results demonstrated that HA could contribute to cathode fouling, but the extent of power reduction was relatively small in comparison to large mass of humics adsorbed. Other factors, such as biopolymer attachment, or salt precipitation, are therefore likely more important contributors to long-term fouling of MFC cathodes.

  20. DNA-Accelerated Copper Catalysis of Friedel-Crafts Conjugate Addition/Enantioselective Protonation Reactions in Water

    NARCIS (Netherlands)

    García-Fernández, Almudena; Megens, Rik P.; Villarino, Lara; Roelfes, Gerard

    2016-01-01

    DNA-induced rate acceleration has been identified as one of the key elements for the success of the DNA-based catalysis concept. Here we report on a novel DNA-based catalytic Friedel-Crafts conjugate addition/enantioselective protonation reaction in water, which represents the first example of a

  1. A Mild and Convenient Method for the Reduction of Carbonyl Compounds with NaBH4 in the Presence of Catalytic Amounts of MoCl5

    International Nuclear Information System (INIS)

    Zeynizadeh, Behzad; Yahyaei, Saiedeh

    2003-01-01

    NaBH 4 with catalytic amounts of MoCl 5 can readily reduce a variety of carbonyl compounds such as aldehydes, ketones, acyloins, α-diketones and conjugated enones to their corresponding alcohols in good to excellent yields. Reduction reactions were performed under aprotic condition in CH 3 CN at room temperature or reflux. In addition, the chemoselective reduction of aldehydes over ketones was accomplished successfully with this reducing system

  2. Catalytic reduction of NOx with H2/CO/CH4 over PdMOR catalysts

    International Nuclear Information System (INIS)

    Pieterse, Johannis A.Z.; Booneveld, Saskia

    2007-01-01

    Conversion of NO x with reducing agents H 2 , CO and CH 4 , with and without O 2 , H 2 O, and CO 2 were studied with catalysts based on MOR zeolite loaded with palladium and cerium. The catalysts reached high NO x to N 2 conversion with H 2 and CO (>90% conversion and N 2 selectivity) range under lean conditions. The formation of N 2 O is absent in the presence of both H 2 and CO together with oxygen in the feed, which will be the case in lean engine exhaust. PdMOR shows synergic co-operation between H 2 and CO at 450-500 K. The positive effect of cerium is significant in the case of H 2 and CH 4 reducing agent but is less obvious with H 2 /CO mixture and under lean conditions. Cerium lowers the reducibility of Pd species in the zeolite micropores. The catalysts showed excellent stability at temperatures up to 673 K in a feed with 2500 ppm CH 4 , 500 ppm NO, 5% O 2 , 10% H 2 O (0-1% H 2 ), N 2 balance but deactivation is noticed at higher temperatures. Combining results of the present study with those of previous studies it shows that the PdMOR-based catalysts are good catalysts for NO x reduction with H 2 , CO, hydrocarbons, alcohols and aldehydes under lean conditions at temperatures up to 673 K. (author)

  3. Screening of catalytic oxygen reduction reaction activity of metal-doped graphene by density functional theory

    International Nuclear Information System (INIS)

    Chen, Xin; Chen, Shuangjing; Wang, Jinyu

    2016-01-01

    Highlights: • The screened M-G structures are very thermodynamically stable, and the stability is even higher than that of the corresponding bulk metal surfaces. • The binding energies of ORR intermediates suggest that they are not linear dependence, which are different form the cases found on some metal-based catalysts. • The Au-, Co-, and Ag-G structures could be used as the ORR catalysts. - Abstract: Graphene doping is a promising direction for developing effective oxygen reduction reaction (ORR) catalysts. In this paper, we computationally investigated the ORR performance of 10 kinds of metal-doped graphene (M-G) catalysts, namely, Al-, Si-, Mn-, Fe-, Co-, Ni-, Pd-, Ag-, Pt-, and Au-G. The results shown that the binding energies of the metal atoms incorporated into the graphene vacancy are higher than their bulk cohesive energies, indicating the formed M-G catalysts are even more stable than the corresponding bulk metal surfaces, and thus avoid the metals dissolution in the reaction environment. We demonstrated that the linear relation among the binding energies of the ORR intermediates that found on metal-based materials does not hold for the M-G catalysts, therefore a single binding energy of intermediate alone is not sufficient to evaluate the ORR activity of an arbitrary catalyst. By analysis of the detailed ORR processes, we predicted that the Au-, Co-, and Ag-G materials can be used as the ORR catalysts.

  4. Technology Roadmap: Energy and GHG reductions in the chemical industry via catalytic processes

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2013-06-01

    The chemical industry is a large energy user; but chemical products and technologies also are used in a wide array of energy saving and/or renewable energy applications so the industry has also an energy saving role. The chemical and petrochemical sector is by far the largest industrial energy user, accounting for roughly 10% of total worldwide final energy demand and 7% of global GHG emissions. The International Council of Chemical Associations (ICCA) has partnered with the IEA and DECHEMA (Society for Chemical Engineering and Biotechnology) to describe the path toward further improvements in energy efficiency and GHG reductions in the chemical sector. The roadmap looks at measures needed from the chemical industry, policymakers, investors and academia to press on with catalysis technology and unleash its potential around the globe. The report uncovers findings and best practice opportunities that illustrate how continuous improvements and breakthrough technology options can cut energy use and bring down greenhouse gas (GHG) emission rates. Around 90% of chemical processes involve the use of catalysts – such as added substances that increase the rate of reaction without being consumed by it – and related processes to enhance production efficiency and reduce energy use, thereby curtailing GHG emission levels. This work shows an energy savings potential approaching 13 exajoules (EJ) by 2050 – equivalent to the current annual primary energy use of Germany.

  5. Selective catalytic reduction system and process for control of NO.sub.x emissions in a sulfur-containing gas stream

    Science.gov (United States)

    Sobolevskiy, Anatoly

    2015-08-11

    An exhaust gas treatment process, apparatus, and system for reducing the concentration of NOx, CO and hydrocarbons in a gas stream, such as an exhaust stream (29), via selective catalytic reduction with ammonia is provided. The process, apparatus and system include a catalytic bed (32) having a reducing only catalyst portion (34) and a downstream reducing-plus-oxidizing portion (36). Each portion (34, 36) includes an amount of tungsten. The reducing-plus-oxidizing catalyst portion (36) advantageously includes a greater amount of tungsten than the reducing catalyst portion (36) to markedly limit ammonia salt formation.

  6. 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

  7. Evaluating the Catalytic Effects of Carbon Materials on the Photocatalytic Reduction and Oxidation Reactions of TiO2

    International Nuclear Information System (INIS)

    Khan, Gulzar; Kim, Young Kwang; Choi, Sung Kyu; Han, Dong Suk; Abdelwahab, Ahmed; Park, Hyunwoong

    2013-01-01

    TiO 2 composites with seven different carbon materials (activated carbons, graphite, carbon fibers, single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene oxides, and reduced graphene oxides) that are virgin or treated with nitric acid are prepared through an evaporation method. The photocatalytic activities of the as-prepared samples are evaluated in terms of H 2 production from aqueous methanol solution (photo-catalytic reduction: PCR) and degradation of aqueous pollutants (phenol, methylene blue, and rhodamine B) (photocatalytic oxidation: PCO) under AM 1.5-light irradiation. Despite varying effects depending on the kinds of carbon materials and their surface treatment, composites typically show enhanced PCR activity with maximum 50 times higher H 2 production as compared to bare TiO 2 . Conversely, the carbon-induced synergy effects on PCO activities are insignificant for all three substrates. Colorimetric quantification of hydroxyl radicals supports the absence of carbon effects. However, platinum deposition on the binary composites displays the enhanced effect on both PCR and PCO reactions. These differing effects of carbon materials on PCR and PCO reactions of TiO 2 are discussed in terms of physicochemical properties of carbon materials, coupling states of TiO 2 /carbon composites, interfacial charge transfers. Various surface characterizations of composites (UV-Vis diffuse reflectance, SEM, FTIR, surface area, electrical conductivity, and photoluminescence) are performed to gain insight on their photocatalytic redox behaviors

  8. 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.

  9. 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.

  10. Model predictive control of a lean-burn gasoline engine coupled with a passive selective catalytic reduction system

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Pingen [Tennessee Technological University (TTU); Lin, Qinghua [Tennessee Technological University (TTU); Prikhodko, Vitaly Y. [ORNL

    2017-10-01

    Lean-burn gasoline engines have demonstrated 10–20% engine efficiency gain over stoichiometric engines and are widely considered as a promising technology for meeting the 54.5 miles-per-gallon (mpg) Corporate Average Fuel Economy standard by 2025. Nevertheless, NOx emissions control for lean-burn gasoline for meeting the stringent EPA Tier 3 emission standards has been one of the main challenges towards the commercialization of highly-efficient lean-burn gasoline engines in the United States. Passive selective catalytic reduction (SCR) systems, which consist of a three-way catalyst and SCR, have demonstrated great potentials of effectively reducing NOx emissions for lean gasoline engines but may cause significant fuel penalty due to ammonia generation via rich engine combustion. The purpose of this study is to develop a model-predictive control (MPC) scheme for a lean-burn gasoline engine coupled with a passive SCR system to minimize the fuel penalty associated with passive SCR operation while satisfying stringent NOx and NH3 emissions requirements. Simulation results demonstrate that the MPC-based control can reduce the fuel penalty by 47.7% in a simulated US06 cycle and 32.0% in a simulated UDDS cycle, compared to the baseline control, while achieving over 96% deNOx efficiency and less than 15 ppm tailpipe ammonia slip. The proposed MPC control can potentially enable high engine efficiency gain for highly-efficient lean-burn gasoline engine while meeting the stringent EPA Tier 3 emission standards.

  11. 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

  12. The enantioselective total synthesis of (+)-clusianone.

    Science.gov (United States)

    Horeischi, Fiene; Guttroff, Claudia; Plietker, Bernd

    2015-02-11

    (+)-Clusianone, an exo-type B PPAP with reported anti-HIV and chemoprotective activities, was synthesized in eleven steps with 97% ee starting from acetylacetone. An enantioselective decarboxylative Tsuji-Trost-allylation and a Ru-catalyzed ring-closing metathesis-decarboxylative allylation were used to control both diastereo- and enantioselectivity.

  13. Synthesis of 3-fluoro-3-aryl oxindoles: Direct enantioselective α arylation of amides

    KAUST Repository

    Wu, Linglin; Falivene, Laura; Drinkel, Emma E.; Grant, Sharday; Linden, Anthony; Cavallo, Luigi; Dorta, Reto

    2012-01-01

    Modus operandi: Catalytic access to the title compounds through a new asymmetric α-arylation protocol is reported (see scheme). These products are formed in good yields and excellent enantioselectivities by using a new and easily synthesized chiral N-heterocyclic carbene (NHC) ligand. Advanced DFT calculations reveal the properties of the NHC ligand and the mode of operation of the catalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. An iron/amine-catalyzed cascade process for the enantioselective functionalization of allylic alcohols.

    Science.gov (United States)

    Quintard, Adrien; Constantieux, Thierry; Rodriguez, Jean

    2013-12-02

    Three is a lucky number: An enantioselective transformation of allylic alcohols into β-chiral saturated alcohols has been developed by combining two distinct metal- and organocatalyzed catalytic cycles. This waste-free triple cascade process merges an iron-catalyzed borrowing-hydrogen step with an aminocatalyzed nucleophilic addition reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Synthesis of 3-fluoro-3-aryl oxindoles: Direct enantioselective α arylation of amides

    KAUST Repository

    Wu, Linglin

    2012-02-06

    Modus operandi: Catalytic access to the title compounds through a new asymmetric α-arylation protocol is reported (see scheme). These products are formed in good yields and excellent enantioselectivities by using a new and easily synthesized chiral N-heterocyclic carbene (NHC) ligand. Advanced DFT calculations reveal the properties of the NHC ligand and the mode of operation of the catalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Catalytic reduction of methane/unburned hydrocarbons in smoke from lean-burn gas engines

    International Nuclear Information System (INIS)

    Wit, Jan de.

    1999-01-01

    The aim of this project has been: To describe the flue gas conditions of typical stationary gas engines for cogeneration; To evaluate the predominant causes of deactivation of oxidation catalysts under realistic operation conditions; To develop improved long-term stable oxidation catalysts; To evaluate alternative catalyst-based methane reduction technologies. Most gas engines for stationary purposes are efficient lean-burn gas engines. Both the high efficiency and the very lean operation lead to low exhaust temperatures. However, there is now a tendency to design engines with un-cooled exhaust manifolds. This leads to higher shaft efficiency and increases the exhaust temperature. Exhaust gas composition and temperatures during continuous operation and start/stops are given in this report. Analyses have been made of catalyst samples to find predominant causes for oxidation catalyst deactivation. The analyses have shown that the presence of sulphur dioxide in the flue gas causes sulphur poisoning on the active catalyst surface. This effect is dependent on both the catalyst formulation and the catalyst support material composition. Neither sintering, nor other poisoning components than sulphur have been on the examined catalyst samples. The sulphur dioxide in the exhaust is a result of the sulphur in the odorisation additive used in the natural gas (approx. 10 mg/n 3 m THT) and of the sulphur present in combusted lubrication oil. These sources leads to a level of approx. 0.3 - 0.6 ppm (vol) SO 2 in the exhaust gas. Based on a large number of laboratory tests, a new oxidation catalyst formulation has been developed and successfully tested over 5000 hours of operation at a commercial cogeneration plant. This long-term testing has been additionally supplemented by short-term testings at test sites to see performance under other operation conditions. It has been shown that a rise in flue gas temperature (from e.g. 450 deg. C) will significantly reduce the necessary

  17. Characterization and reaction studies of dimeric molybdenum(III) complexes with bridging dithiolate ligands. Catalytic reduction of acetylene to ethylene

    International Nuclear Information System (INIS)

    DuBois, M.R.; Haltiwanger, R.C.; Miller, D.J.; Glatzmaier, G.

    1979-01-01

    The complexes [C 5 H 5 MoSC/sub n/H/sub 2n/S] 2 (where n = 2 and 3) have been prepared by the reaction of ethylene sulfide and propylene sulfide, respectively, with C 5 H 5 MoH(CO) 3 or with [C 5 H 5 Mo(CO) 3 ] 2 . Cyclic voltammetry shows that each complex undergoes two reversible oxidations at 0.13 and 0.79 V vs. SCE (in acetonitrile with 0.1 M Bu 4 NBF 4 ). Both the one-electron and two-electron oxidation products have been synthesized and characterized by spectral and magnetic data. Electrochemical data for the oxidized complexes support the conclusion that the complexes have the same gross structural features in all three oxidation states. A single crystal of the monocation [C 5 H 5 MoSC 3 H 6 S] 2 BF 4 has been characterized by an x-ray diffraction study. The compound crystallizes in the space group C2/c with a = 18.266 (1) A, b = 9.206 (4) A, c = 12.911 (5) A, β = 100.83 (3) 0 , and V = 2128 A 3 . The metal ions of the cation are bridged by two 1,2-propanedithiolate ligands. The four sulfur atoms of these ligands form a plane which bisects the metal-metal distance. The neutral dimeric complexes undergo a unique reaction with alkenes and alkynes in which the hydrocarbon portion of the bridging dithiolate ligands is exchanged. The reaction has been characterized with olefinswith both electron-withdrawing and electron-donating substituents. When [C 5 H 5 MoSC 2 H 4 S] 2 (1) is reacted with acetylene at 25 0 C, ethene is produced and the complex [C 5 H 5 MoSC 2 H 2 S] 2 is isolated. The latter complex is reduced by hydrogen (2 atm) at 60 0 C to re-form 1. The utility of these reactions in the catalytic reduction of acetylene to ethylene has been investigated. The role of the sulfur ligands in this catalytic cycle is discussed. 50 references, 2 figures, 5 tables

  18. 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.

  19. Drastic reduction in the surface recombination velocity of crystalline silicon passivated with catalytic chemical vapor deposited SiNx films by introducing phosphorous catalytic-doped layer

    International Nuclear Information System (INIS)

    Thi, Trinh Cham; Koyama, Koichi; Ohdaira, Keisuke; Matsumura, Hideki

    2014-01-01

    We improve the passivation property of n-type crystalline silicon (c-Si) surface passivated with a catalytic chemical vapor deposited (Cat-CVD) Si nitride (SiN x ) film by inserting a phosphorous (P)-doped layer formed by exposing c-Si surface to P radicals generated by the catalytic cracking of PH 3 molecules (Cat-doping). An extremely low surface recombination velocity (SRV) of 2 cm/s can be achieved for 2.5 Ω cm n-type (100) floating-zone Si wafers passivated with SiN x /P Cat-doped layers, both prepared in Cat-CVD systems. Compared with the case of only SiN x passivated layers, SRV decreases from 5 cm/s to 2 cm/s. The decrease in SRV is the result of field effect created by activated P atoms (donors) in a shallow P Cat-doped layer. Annealing process plays an important role in improving the passivation quality of SiN x films. The outstanding results obtained imply that SiN x /P Cat-doped layers can be used as promising passivation layers in high-efficiency n-type c-Si solar cells.

  20. Pt-Ag cubic nanocages with wall thickness less than 2 nm and their enhanced catalytic activity toward oxygen reduction.

    Science.gov (United States)

    Sun, Xiaojun; Yang, Xuan; Zhang, Yun; Ding, Yong; Su, Dong; Qin, Dong

    2017-10-12

    We report a facile synthesis of Pt-Ag nanocages with walls thinner than 2 nm by depositing a few atomic layers of Pt as conformal shells on Ag nanocubes and then selectively removing the Ag template via wet etching. In a typical process, we inject a specific volume of aqueous H 2 PtCl 6 into a mixture of Ag nanocubes, ascorbic acid (H 2 Asc), NaOH, and poly(vinylpyrrolidone) in water under ambient conditions. At an initial pH of 11.9, the Pt(iv) precursor is quickly reduced by an ascorbate monoanion, a strong reducing agent derived from the neutralization of H 2 Asc with NaOH. The newly formed Pt atoms are deposited onto the edges and then corners and side faces of Ag nanocubes, leading to the generation of Ag@Pt core-shell nanocubes with a conformal Pt shell of approximately three atomic layers (or, about 0.6 nm in thickness) when 0.4 mL of 0.2 mM H 2 PtCl 6 is involved. After the selective removal of Ag in the core using an etchant based on a mixture of Fe(NO 3 ) 3 and HNO 3 , we transform the core-shell nanocubes into Pt-Ag alloy nanocages with an ultrathin wall thickness of less than 2 nm. We further demonstrate that the as-obtained nanocages with a composition of Pt 42 Ag 58 exhibit an enhanced catalytic activity toward the oxygen reduction reaction, with a mass activity of 0.30 A mg -1 and a specific activity of 0.93 mA cm -2 , which are 1.6 and 2.5 times, respectively, greater than those of a commercial Pt/C catalyst.

  1. Selective Catalytic Reduction (SCR) for mobile application - heavy duty diesel; Selektive Katalytische Reduktion (SCR) fuer die mobile Anwendung - LKW

    Energy Technology Data Exchange (ETDEWEB)

    Huennekes, E.; Neubauer, T. [Engelhard Technologies GmbH, Hannover (Germany); Roth, S.A.; Patchett, J.A. [Engelhard Corp., R and D, Iselin, NJ (United States)

    2006-07-01

    Different system configurations of particulate and NOx control via selective catalytic reduction (SCR) were discussed. Advantages and disadvantages were described and the final choice of the optimum system will strongly depend on the application, the market (US, EU) and the system costs. Especially when considering low temperature NOx control, the optimum adjustment of the NO{sub 2}/NO{sub x} ratio in front of an SCR system plays an important role. When generating NO2 over an oxidation catalyst, the resulting NO{sub 2}/NO{sub x} ratio strongly depends on temperature and space velocity. Steady state data show an optimum NO{sub 2}/NO{sub x} ratio between 35 and 60% at temperatures about 240 C. Three DOC systems in front of an SCR system were investigated with the purpose to generate high, low and optimum NO{sub 2}/NO{sub x} ratios. The fast SCR reaction at 1:1 NO: NO2 with NH{sub 3} is the preferred reaction pathway until either NO or NO{sub 2} are consumed. The benefit of an optimum designed DOC system can be seen in the transient response after a sudden increase in urea dosing. The time for the optimum designed system to reach maximum NO{sub x} conversion is much shorter compared with systems having excess NO or NO{sub 2} Ammonia oxidation catalysts (AMOX) are effective means in controlling ammonia from SCR systems. To be effective, AMOX must have selectivity to nitrogen over N{sub 2}O and NO{sub x}. (orig.)

  2. Effects of Particle Filters and Selective Catalytic Reduction on In-Use Heavy-Duty Diesel Truck Emissions

    Science.gov (United States)

    Preble, C.; Cados, T.; Harley, R.; Kirchstetter, T.

    2016-12-01

    Heavy-duty diesel trucks (HDDT) are a major source of nitrogen oxides (NOx) and black carbon (BC) in urban environments, contributing to persistent ozone and particulate matter air quality problems. Diesel particle filters (DPFs) and selective catalytic reduction (SCR) systems that target PM and NOx emissions, respectively, have recently become standard equipment on new HDDT. DPFs can also be installed on older engines as a retrofit device. Previous work has shown that DPF and SCR systems can reduce NOx and BC emissions by up to 70% and 90%, respectively, compared to modern trucks without these after-treatment controls (Preble et al., ES&T 2015). DPFs can have the undesirable side-effect of increasing ultrafine particle (UFP) and nitrogen dioxide (NO2) emissions. While SCR systems can partially mitigate DPF-related NO2 increases, these systems can emit nitrous oxide (N2O), a potent greenhouse gas. We report new results from a study of HDDT emissions conducted in fall 2015 at the Port of Oakland and Caldecott Tunnel in California's San Francisco Bay Area. We report pollutant emission factors (g kg-1) for emitted NOx, NO2, BC, PM2.5, UFP, and N2O on a truck-by-truck basis. Using a roadside license plate recognition system, we categorize each truck by its engine model year and installed after-treatment controls. From this, we develop emissions profiles for trucks with and without DPF and SCR. We evaluate the effectiveness of these devices as a function of their age to determine whether degradation is an issue. We also compare the emission profiles of trucks traveling at low speeds along a level, arterial road en route to the port and at high speeds up a 4% grade highway approaching the tunnel. Given the climate impacts of BC and N2O, we also examine the global warming potential of emissions from trucks with and without DPF and SCR.

  3. Anodically-grown TiO_2 nanotubes: Effect of the crystallization on the catalytic activity toward the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Sacco, Adriano; Garino, Nadia; Lamberti, Andrea; Pirri, Candido Fabrizio; Quaglio, Marzia

    2017-01-01

    Highlights: • Anodically-grown TiO_2 nanotubes as catalysts for the oxygen reduction reaction. • Amorphous NTs compared to thermal- and vapor-treated crystalline nanostructures. • The selection of the crystallization conditions leads to performance similar to Pt. - Abstract: In this work we investigated the behavior of TiO_2 nanotube (NT) arrays, grown by anodic oxidation of Ti foil, as catalysts for the oxygen reduction reaction (ORR) in alkaline water solution. In particular, as-grown amorphous NTs were compared to crystalline anatase nanostructures, obtained following two different procedures, namely thermal and vapor-induced crystallizations. The catalytic activity of these materials toward the ORR was evaluated by cyclic voltammetry measurements. ORR polarization curves, combined with the rotating disk technique, indicated a predominant four-electrons reduction path, especially for crystalline samples. The effect of the structural characteristics of the investigated materials on the catalytic activity was analyzed in details by electrochemical impedance spectroscopy. The catalytic performance of the crystalline NTs is only slightly lower with respect to the reference material for fuel cell applications, namely platinum, but is in line with other cost-effective catalysts recently proposed in the literature. However, if compared to the larger part of these low-cost catalysts, anodically-grown TiO_2 NTs are characterized by a synthesis route which is highly reproducible and easily up-scalable.

  4. Anodically-grown TiO{sub 2} nanotubes: Effect of the crystallization on the catalytic activity toward the oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Sacco, Adriano, E-mail: adriano.sacco@iit.it [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Garino, Nadia [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Lamberti, Andrea, E-mail: andrea.lamberti@polito.it [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Pirri, Candido Fabrizio [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Quaglio, Marzia [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy)

    2017-08-01

    Highlights: • Anodically-grown TiO{sub 2} nanotubes as catalysts for the oxygen reduction reaction. • Amorphous NTs compared to thermal- and vapor-treated crystalline nanostructures. • The selection of the crystallization conditions leads to performance similar to Pt. - Abstract: In this work we investigated the behavior of TiO{sub 2} nanotube (NT) arrays, grown by anodic oxidation of Ti foil, as catalysts for the oxygen reduction reaction (ORR) in alkaline water solution. In particular, as-grown amorphous NTs were compared to crystalline anatase nanostructures, obtained following two different procedures, namely thermal and vapor-induced crystallizations. The catalytic activity of these materials toward the ORR was evaluated by cyclic voltammetry measurements. ORR polarization curves, combined with the rotating disk technique, indicated a predominant four-electrons reduction path, especially for crystalline samples. The effect of the structural characteristics of the investigated materials on the catalytic activity was analyzed in details by electrochemical impedance spectroscopy. The catalytic performance of the crystalline NTs is only slightly lower with respect to the reference material for fuel cell applications, namely platinum, but is in line with other cost-effective catalysts recently proposed in the literature. However, if compared to the larger part of these low-cost catalysts, anodically-grown TiO{sub 2} NTs are characterized by a synthesis route which is highly reproducible and easily up-scalable.

  5. Fabrication and characterisation of gold nano-particle modified polymer monoliths for flow-through catalytic reactions and their application in the reduction of hexacyanoferrate

    International Nuclear Information System (INIS)

    Floris, Patrick; Twamley, Brendan; Nesterenko, Pavel N.; Paull, Brett; Connolly, Damian

    2014-01-01

    Polymer monoliths in capillary (100 μm i.d.) and polypropylene pipette tip formats (vol: 20 μL) were modified with gold nano-particles (AuNP) and subsequently used for flow-through catalytic reactions. Specifically, methacrylate monoliths were modified with amine-reactive monomers using a two-step photografting method and then reacted with ethylenediamine to provide amine attachment sites for the subsequent immobilisation of 4 nm, 7 nm or 16 nm AuNP. This was achieved by flushing colloidal suspensions of gold nano-particles through each aminated polymer monolith which resulted in a multi-point covalent attachment of gold via the lone pair of electrons on the nitrogen of the free amine groups. Field emission scanning electron microscopy and scanning capacitively coupled conductivity detection was used to characterise the surface coverage of AuNP on the monoliths. The catalytic activity of AuNP immobilised on the polymer monoliths in both formats was then demonstrated using the reduction of Fe(III) to Fe(II) by sodium borohydride as a model reaction by monitoring the reduction in absorbance of the hexacyanoferrate (III) complex at 420 nm. Catalytic activity was significantly enhanced on monoliths modified with smaller AuNP with almost complete reduction (95 %) observed when using monoliths agglomerated with 7 nm AuNPs. (author)

  6. Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

    KAUST Repository

    Ahmed, Syud M.; Poater, Albert; Childers, M. Ian; Widger, Peter C B; Lapointe, Anne M.; Lobkovsky, Emil B.; Coates, Geoffrey W.; Cavallo, Luigi

    2013-01-01

    The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

  7. Enantioselective functionalization of allylic C-H bonds following a strategy of functionalization and diversification.

    Science.gov (United States)

    Sharma, Ankit; Hartwig, John F

    2013-11-27

    We report the enantioselective functionalization of allylic C-H bonds in terminal alkenes by a strategy involving the installation of a temporary functional group at the terminal carbon atom by C-H bond functionalization, followed by the catalytic diversification of this intermediate with a broad scope of reagents. The method consists of a one-pot sequence of palladium-catalyzed allylic C-H bond oxidation under neutral conditions to form linear allyl benzoates, followed by iridium-catalyzed allylic substitution. This overall transformation forms a variety of chiral products containing a new C-N, C-O, C-S, or C-C bond at the allylic position in good yield with a high branched-to-linear selectivity and excellent enantioselectivity (ee ≤97%). The broad scope of the overall process results from separating the oxidation and functionalization steps; by doing so, the scope of nucleophile encompasses those sensitive to direct oxidative functionalization. The high enantioselectivity of the overall process is achieved by developing an allylic oxidation that occurs without acid to form the linear isomer with high selectivity. These allylic functionalization processes are amenable to an iterative sequence leading to (1,n)-functionalized products with catalyst-controlled diastereo- and enantioselectivity. The utility of the method in the synthesis of biologically active molecules has been demonstrated.

  8. Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

    KAUST Repository

    Ahmed, Syud M.

    2013-12-18

    The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

  9. Catalytic stereoselective synthesis of highly substituted indanones via tandem Nazarov cyclization and electrophilic fluorination trapping.

    Science.gov (United States)

    Nie, Jing; Zhu, Hong-Wei; Cui, Han-Feng; Hua, Ming-Qing; Ma, Jun-An

    2007-08-02

    A new catalytic stereoselective tandem transformation via Nazarov cyclization/electrophilic fluorination has been accomplished. This sequence is efficiently catalyzed by a Cu(II) complex to afford fluorine-containing 1-indanone derivatives with two new stereocenters with high diastereoselectivity (trans/cis up to 49/1). Three examples of catalytic enantioselective tandem transformation are presented.

  10. Enantioselective copper-catalyzed carboetherification of unactivated alkenes.

    Science.gov (United States)

    Bovino, Michael T; Liwosz, Timothy W; Kendel, Nicole E; Miller, Yan; Tyminska, Nina; Zurek, Eva; Chemler, Sherry R

    2014-06-16

    Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein reported is a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, thus yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition-state calculations support a cis-oxycupration stereochemistry-determining step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Reductive decarboxylation of bicyclic prolinic systems: a new approach to the enantioselective synthesis of the Geissman-Waiss lactone. X-ray structure determination of a key lactone intermediate

    Directory of Open Access Journals (Sweden)

    Ambrósio João Carlos L.

    2003-01-01

    Full Text Available Two concise and enantioselective syntheses of the necine base precursors (1R,5R-N-Cbz and N-Boc-2-oxa-6-azabicyclo[3.3.0]octan-3-ones (Geissman-Waiss lactones were carried out from two enantiomerically pure endocyclic five-membered enecarbamates with overall yields of 23% and 26%, respectively. The synthetic strategy made use of a highly effective and stereoselective [2+2]cycloaddition of enantiomerically pure endocyclic enecarbamates with dichloroketene, as well as an efficient decarboxylation step of a bicyclic alpha-amino acid employing Boger's acyl selenide protocol employing tributyltin hydride. Interesting aspects concerning the regiochemical outcome of Baeyer-Villiger oxidations of bicyclic cyclobutanones are also reported, in which the usual stereoelectronic bias of Baeyer-Villiger oxidation seems to be counterbalanced by steric effects on the putative Criegee intermediate.

  12. Catalytic reduction of NO{sub x} in gasoline engine exhaust over copper- and nickel-exchanged X-zeolite catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Bhattacharyya, S. [Indian Inst. of Technology, Kharagpur (India). Dept. of Mechanical Engineering; Das, R.K. [Indian School of Mines, Dhanbad (India). Dept. of Engineering and Mining Machinery

    2001-10-11

    Catalytic removal of NO{sub x} in engine exhaust gases can be accomplished by non-selective reduction, selective reduction and decomposition. Noble metals are extensively used for non-selective reduction of NO{sub x} and up to 90% of engine NO{sub x} emissions can be reduced in a stoichiometric exhaust. This requirement of having the stoichiometric fuel-air ratio acts against efficiency improvement of engines. Selective NO{sub x} reduction in the presence of different reductants such as, NH{sub 3}, urea or hydrocarbons, requires close control of the amount of reductant being injected which otherwise may be emitted as a pollutant. Catalytic decomposition is the best option for NO{sub x} removal. Nevertheless, catalysts which are durable, economic and active for NO{sub x} reduction at normal engine exhaust temperature ranges are still being investigated. Three catalysts based on X-zeolite have been developed by exchanging the Na+ ion with copper, nickel and copper-nickel metal ions and applied to the exhaust of a stationary gasoline engine to explore their potential for catalytic reduction of NO{sub x} under a wide range of engine and exhaust conditions. Some encouraging results have been obtained. The catalyst Cu-X exhibits much better NO{sub x} reduction performance at any temperature in comparison to Cu-Ni-X and Ni-X; while Cu-Ni-X catalyst exhibits slightly better performance than Ni-X catalyst. Maximum NO{sub x} efficiency achieved with Cu-X catalyst is 59.2% at a space velocity (sv) of 31 000 h{sup -1}; while for Cu-Ni-X and Ni-X catalysts the equivalent numbers are 60.4% and 56% respectively at a sv of 22 000 h{sup -1}. Unlike noble metals, the doped X-zeolite catalysts exhibit significant NO{sub x} reduction capability for a wide range of air/fuel ratio and with a slower rate of decline as well with increase in air/fuel ratio. (author)

  13. Enantioselective synthesis of tetrafluorinated ribose and fructose.

    Science.gov (United States)

    Linclau, Bruno; Boydell, A James; Timofte, Roxana S; Brown, Kylie J; Vinader, Victoria; Weymouth-Wilson, Alexander C

    2009-02-21

    A perfluoroalkylidene lithium mediated cyclisation approach for the enantioselective synthesis of a tetrafluorinated aldose (ribose) and of a tetrafluorinated ketose (fructose), both in the furanose and in the pyranose form, is described.

  14. Kinetic investigation on enantioselective hydrolytic resolution of ...

    African Journals Online (AJOL)

    Kinetic investigation on enantioselective hydrolytic resolution of epichlorohydrin by crude epoxide hydrolase from domestic duck liver. X Ling, D Lu, J Wang, J Chen, L Ding, J Chen, H Chai, P Ouyang ...

  15. 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.)

  16. Enantioselective addition of nitrones to activated cyclopropanes.

    Science.gov (United States)

    Sibi, Mukund P; Ma, Zhihua; Jasperse, Craig P

    2005-04-27

    In this paper, we demonstrate the first examples of chiral Lewis acid catalysis in the formation of tetrahydro-1,2-oxazines with very high enantioselectivity starting with diactivated cyclopropanes and nitrones (>90% yields and ee). Reactions with racemic substituted cyclopropanes provide approximately 1:1 diastereomeric tetrahydro-1,2-oxazine products with high enantioselectivity. Mechanistic information for the formation of the tetrahydro-1,2-oxazines is also detailed.

  17. Liquid-phase pulsed laser ablation synthesis of graphitized carbon-encapsulated palladium core–shell nanospheres for catalytic reduction of nitrobenzene to aniline

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yu-jin; Ma, Rory; Reddy, D. Amaranatha; Kim, Tae Kyu, E-mail: tkkim@pusan.ac.kr

    2015-12-01

    Graphical abstract: - Highlights: • Graphitized carbon-encapsulated palladium core–shell nanospheres fabricated by laser ablation. • Physical characterizations of synthesized Pd@C nanospheres. • Assessments of catalytic performance of Pd@C nanospheres for the reduction of nitrobenzene to aniline. • Significant improvement of the catalytic activity due to the graphitized carbon-layered structure and the high specific surface area. - Abstract: Graphitized carbon-encapsulated palladium (Pd) core–shell nanospheres were produced via pulsed laser ablation of a solid Pd foil target submerged in acetonitrile. The microstructural features and optical properties of these nanospheres were characterized via high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy. Microstructural analysis indicated that the core–shell nanostructures consisted of single-crystalline cubic metallic Pd spheres that serve as the core material, over which graphitized carbon was anchored as a heterogeneous shell. The absorbance spectrum of the synthesized nanostructures exhibited a broad (absorption) band at ∼264 nm; this band corresponded to the typical inter-band transition of a metallic system and resulted possibly from the absorbance of the ionic Pd{sup 2+}. The catalytic properties of the Pd and Pd@C core–shell nanostructures were investigated using the reduction of nitrobenzene to aniline by an excess amount of NaBH{sub 4} in an aqueous solution at room temperature, as a model reaction. Owing to the graphitized carbon-layered structure and the high specific surface area, the resulting Pd@C nanostructures exhibited higher conversion efficiencies than their bare Pd counterparts. In fact, the layered structure provided access to the surface of the Pd nanostructures for the hydrogenation reaction, owing to the synergistic effect between graphitized carbon and the nanostructures. Their

  18. Liquid-phase pulsed laser ablation synthesis of graphitized carbon-encapsulated palladium core–shell nanospheres for catalytic reduction of nitrobenzene to aniline

    International Nuclear Information System (INIS)

    Kim, Yu-jin; Ma, Rory; Reddy, D. Amaranatha; Kim, Tae Kyu

    2015-01-01

    Graphical abstract: - Highlights: • Graphitized carbon-encapsulated palladium core–shell nanospheres fabricated by laser ablation. • Physical characterizations of synthesized Pd@C nanospheres. • Assessments of catalytic performance of Pd@C nanospheres for the reduction of nitrobenzene to aniline. • Significant improvement of the catalytic activity due to the graphitized carbon-layered structure and the high specific surface area. - Abstract: Graphitized carbon-encapsulated palladium (Pd) core–shell nanospheres were produced via pulsed laser ablation of a solid Pd foil target submerged in acetonitrile. The microstructural features and optical properties of these nanospheres were characterized via high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy. Microstructural analysis indicated that the core–shell nanostructures consisted of single-crystalline cubic metallic Pd spheres that serve as the core material, over which graphitized carbon was anchored as a heterogeneous shell. The absorbance spectrum of the synthesized nanostructures exhibited a broad (absorption) band at ∼264 nm; this band corresponded to the typical inter-band transition of a metallic system and resulted possibly from the absorbance of the ionic Pd 2+ . The catalytic properties of the Pd and Pd@C core–shell nanostructures were investigated using the reduction of nitrobenzene to aniline by an excess amount of NaBH 4 in an aqueous solution at room temperature, as a model reaction. Owing to the graphitized carbon-layered structure and the high specific surface area, the resulting Pd@C nanostructures exhibited higher conversion efficiencies than their bare Pd counterparts. In fact, the layered structure provided access to the surface of the Pd nanostructures for the hydrogenation reaction, owing to the synergistic effect between graphitized carbon and the nanostructures. Their unique

  19. Enantioselective catalytic syntheses of alpha-branched chiral amines

    DEFF Research Database (Denmark)

    Brase, S.; Baumann, T.; Dahmen, S.

    2007-01-01

    Chiral amines play a pivotal role in fine chemical and natural product syntheses and the design of novel materials.......Chiral amines play a pivotal role in fine chemical and natural product syntheses and the design of novel materials....

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

    NARCIS (Netherlands)

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

    2016-01-01

    α-Chiral amines are of significant importance in medicinal chemistry, asymmetric synthesis and material science, but methods for their efficient synthesis are scarce. In particular, the synthesis of α-chiral amines with the challenging tetrasubstituted carbon stereocentre is a long-standing problem

  1. Facile Fabrication of Highly Active Magnetic Aminoclay Supported Palladium Nanoparticles for the Room Temperature Catalytic Reduction of Nitrophenol and Nitroanilines

    Directory of Open Access Journals (Sweden)

    Lei Jia

    2018-06-01

    Full Text Available Magnetically recyclable nanocatalysts with excellent performance are urgent need in heterogeneous catalysis, due to their magnetic nature, which allows for convenient and efficient separation with the help of an external magnetic field. In this research, we developed a simple and rapid method to fabricate a magnetic aminoclay (AC based an AC@Fe3O4@Pd nanocatalyst by depositing palladium nanoparticles (Pd NPs on the surface of the magnetic aminoclay nanocomposite. The microstructure and the magnetic properties of as-prepared AC@Fe3O4@Pd were tested using transmission electron microscopy (TEM, energy-dispersive X-ray spectroscopy (EDS, X-ray diffraction (XRD, and vibrating sample magnetometry (VSM analyses. The resultant AC@Fe3O4@Pd nanocatalyst with the magnetic Fe-based inner shell, catalytically activate the outer noble metal shell, which when combined with ultrafine Pd NPs, synergistically enhanced the catalytic activity and recyclability in organocatalysis. As the aminoclay displayed good water dispersibility, the nanocatalyst indicated satisfactory catalytic performance in the reaction of reducing nitrophenol and nitroanilines to the corresponding aminobenzene derivatives. Meanwhile, the AC@Fe3O4@Pd nanocatalyst exhibited excellent reusability, while still maintaining good activity after several catalytic cycles.

  2. 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

  3. Enantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular Michael additions to α,β-unsaturated esters.

    Science.gov (United States)

    Gammack Yamagata, Adam D; Datta, Swarup; Jackson, Kelvin E; Stegbauer, Linus; Paton, Robert S; Dixon, Darren J

    2015-04-13

    A new catalytic asymmetric desymmetrization reaction for the synthesis of enantioenriched derivatives of 2-azabicyclo[3.3.1]nonane, a key motif common to many alkaloids, has been developed. Employing a cyclohexanediamine-derived primary amine organocatalyst, a range of prochiral cyclohexanone derivatives possessing an α,β-unsaturated ester moiety linked to the 4-position afforded the bicyclic products, which possess three stereogenic centers, as single diastereoisomers in high enantioselectivity (83-99% ee) and in good yields (60-90%). Calculations revealed that stepwise C-C bond formation and proton transfer via a chair-shaped transition state dictate the exclusive endo selectivity and enabled the development of a highly enantioselective primary amine catalyst. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Ultrasound-Assisted Enantioselective Esterification of Ibuprofen Catalyzed by a Flower-Like Nanobioreactor

    Directory of Open Access Journals (Sweden)

    Baiyi An

    2016-04-01

    Full Text Available A flower-like nanobioreactor was prepared for resolution of ibuprofen in organic solvents. Ultrasound irradiation has been used to improve the enzyme performance of APE1547 (a thermophilic esterase from the archaeon Aeropyrum pernix K1 in the enantioselective esterification. Under optimum reaction conditions (ultrasound power, 225 W; temperature, 45 °C; water activity, 0.21, the immobilized APE1547 showed an excellent catalytic performance (enzyme activity, 13.26 μmol/h/mg; E value, 147.1. After ten repeated reaction batches, the nanobioreactor retained almost 100% of its initial enzyme activity and enantioselectivity. These results indicated that the combination of the immobilization method and ultrasound irradiation can enhance the enzyme performance dramatically.

  5. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    KAUST Repository

    Zhao, Changgui

    2018-02-05

    Axially chiral molecules are among the most valuable substrates in organic synthesis. They are typically used as chiral ligands or catalysts in asymmetric reactions. Recent progress for the construction of these chiral molecules is mainly focused on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a catalytic C–C bond formation occurs, providing axially chiral α-pyrone−aryls in moderate to good yields and with high enantioselectivities. Control experiments indicated that alkynyl acyl azoliums, acting as active intermediates, are employed to atroposelectively assemble chiral biaryls and such a methodology may be creatively applied to other useful NHC-catalyzed asymmetric transformations.

  6. 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.

  7. 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.

  8. 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

  9. Mathematical optimization techniques for managing selective catalytic reduction for a fleet of coal-fired power plants

    Science.gov (United States)

    Alanis Pena, Antonio Alejandro

    Major commercial electricity generation is done by burning fossil fuels out of which coal-fired power plants produce a substantial quantity of electricity worldwide. The United States has large reserves of coal, and it is cheaply available, making it a good choice for the generation of electricity on a large scale. However, one major problem associated with using coal for combustion is that it produces a group of pollutants known as nitrogen oxides (NO x). NOx are strong oxidizers and contribute to ozone formation and respiratory illness. The Environmental Protection Agency (EPA) regulates the quantity of NOx emitted to the atmosphere in the United States. One technique coal-fired power plants use to reduce NOx emissions is Selective Catalytic Reduction (SCR). SCR uses layers of catalyst that need to be added or changed to maintain the required performance. Power plants do add or change catalyst layers during temporary shutdowns, but it is expensive. However, many companies do not have only one power plant, but instead they can have a fleet of coal-fired power plants. A fleet of power plants can use EPA cap and trade programs to have an outlet NOx emission below the allowances for the fleet. For that reason, the main aim of this research is to develop an SCR management mathematical optimization methods that, with a given set of scheduled outages for a fleet of power plants, minimizes the total cost of the entire fleet of power plants and also maintain outlet NO x below the desired target for the entire fleet. We use a multi commodity network flow problem (MCFP) that creates edges that represent all the SCR catalyst layers for each plant. This MCFP is relaxed because it does not consider average daily NOx constraint, and it is solved by a binary integer program. After that, we add the average daily NOx constraint to the model with a schedule elimination constraint (MCFPwSEC). The MCFPwSEC eliminates, one by one, the solutions that do not satisfy the average daily

  10. EMISSION REDUCTION FROM A DIESEL ENGINE FUELED BY CERIUM OXIDE NANO-ADDITIVES USING SCR WITH DIFFERENT METAL OXIDES COATED CATALYTIC CONVERTER

    Directory of Open Access Journals (Sweden)

    B. JOTHI THIRUMAL

    2015-11-01

    Full Text Available This paper reports the results of experimental investigations on the influence of the addition of cerium oxide in nanoparticle form on the major physiochemical properties and the performance of diesel. The fuel is modified by dispersing the catalytic nanoparticle by ultrasonic agitation. The physiochemical properties of sole diesel fuel and modified fuel are tested with ASTM standard procedures. The effects of the additive nanoparticles on the individual fuel properties, the engine performance, and emissions are studied, and the dosing level of the additive is optimized. Cerium oxide acts as an oxygen-donating catalyst and provides oxygen for the oxidation of CO during combustion. The active energy of cerium oxide acts to burn off carbon deposits within the engine cylinder at the wall temperature and prevents the deposition of non-polar compounds on the cylinder wall which results in reduction in HC emission by 56.5%. Furthermore, a low-cost metal oxide coated SCR (selective catalyst reduction, using urea as a reducing agent, along with different types of CC (catalytic converter, has been implemented in the exhaust pipe to reduce NOx. It was observed that a reduction in NOx emission is 50–60%. The tests revealed that cerium oxide nanoparticles can be used as an additive in diesel to improve complete combustion of the fuel and reduce the exhaust emissions significantly.

  11. The Poisoning Effect of Na Doping over Mn-Ce/TiO2 Catalyst for Low-Temperature Selective Catalytic Reduction of NO by NH3

    Directory of Open Access Journals (Sweden)

    Liu Yang

    2014-01-01

    Full Text Available Sodium carbonate (Na2CO3, sodium nitrate (NaNO3, and sodium chloride (NaCl were chosen as the precursors to prepare the Na salts deposited Mn-Ce/TiO2 catalysts through an impregnation method. The influence of Na on the performance of the Mn-Ce/TiO2 catalyst for low-temperature selective catalytic reduction of NOx by NH3 was investigated. Experimental results showed that Na salts had negative effects on the activity of Mn-Ce/TiO2 and the precursors of Na salts also affected the catalytic activity. The precursor Na2CO3 had a greater impact on the catalytic activity, while NaNO3 had minimal effect. The characterization results indicated that the significant changes in physical and chemical properties of Mn-Ce/TiO2 were observed after Na was doped on the catalysts. The significant decreases in surface areas and NH3 adsorption amounts were observed after Na was doped on the catalysts, which could be considered as the main reasons for the deactivation of Na deposited Mn-Ce/TiO2.

  12. Fabrication of magnetically recyclable Fe3O4@Cu nanocomposites with high catalytic performance for the reduction of organic dyes and 4-nitrophenol

    International Nuclear Information System (INIS)

    Tang, Mingyi; Zhang, Sai; Li, Xianxian; Pang, Xiaobo; Qiu, Haixia

    2014-01-01

    A facile and efficient approach to synthesize Fe 3 O 4 @Cu nanocomposites using L-Lysine as a linker was developed. The morphology, composition and crystallinity of the Fe 3 O 4 @Cu nanocomposites were characterized by Fourier Transform infrared spectroscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and powder X-ray diffraction. In addition, the magnetic properties were determined with vibrating sample magnetometer. The surface of the Fe 3 O 4 contained many small Cu nanoparticles with sizes of about 3 nm. It was found that the Fe 3 O 4 @Cu nanocomposites could catalyze the degradation of organic dyes. The catalytic activities of the Fe 3 O 4 @Cu nanocomposites for the reduction of nitrophenol were also studied. The Fe 3 O 4 @Cu nanocomposites are more efficient catalysts compared with Cu nanoparticles and can easily be recovered from the reaction mixture with magnet. The cost effective and recyclable Fe 3 O 4 @Cu nanocomposites provide an exciting new material for environmental protection applications. - Highlights: • Cu nanoparticles as small as 3 nm are synthesized. • Low cost Fe 3 O 4 @Cu magnetical nanoparticles show catalytic activity for organic dyes and 4-nitrophenol. • The Fe 3 O 4 @Cu display high catalytic activity after 13 cycles

  13. Fabrication of magnetically recyclable Fe{sub 3}O{sub 4}@Cu nanocomposites with high catalytic performance for the reduction of organic dyes and 4-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Mingyi, E-mail: mingyitjucu@163.com [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Zhang, Sai; Li, Xianxian; Pang, Xiaobo [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Qiu, Haixia [School of Science, Tianjin University, Tianjin 300072 (China)

    2014-12-15

    A facile and efficient approach to synthesize Fe{sub 3}O{sub 4}@Cu nanocomposites using L-Lysine as a linker was developed. The morphology, composition and crystallinity of the Fe{sub 3}O{sub 4}@Cu nanocomposites were characterized by Fourier Transform infrared spectroscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and powder X-ray diffraction. In addition, the magnetic properties were determined with vibrating sample magnetometer. The surface of the Fe{sub 3}O{sub 4} contained many small Cu nanoparticles with sizes of about 3 nm. It was found that the Fe{sub 3}O{sub 4}@Cu nanocomposites could catalyze the degradation of organic dyes. The catalytic activities of the Fe{sub 3}O{sub 4}@Cu nanocomposites for the reduction of nitrophenol were also studied. The Fe{sub 3}O{sub 4}@Cu nanocomposites are more efficient catalysts compared with Cu nanoparticles and can easily be recovered from the reaction mixture with magnet. The cost effective and recyclable Fe{sub 3}O{sub 4}@Cu nanocomposites provide an exciting new material for environmental protection applications. - Highlights: • Cu nanoparticles as small as 3 nm are synthesized. • Low cost Fe{sub 3}O{sub 4}@Cu magnetical nanoparticles show catalytic activity for organic dyes and 4-nitrophenol. • The Fe{sub 3}O{sub 4}@Cu display high catalytic activity after 13 cycles.

  14. Selective catalytic reduction of NO{sub x} to nitrogen over Co-Pt/ZSM-5: Part A. Characterization and kinetic studies

    Energy Technology Data Exchange (ETDEWEB)

    Maisuls, S.E.; Seshan, K.; Feast, S.; Lercher, J.A. [Laboratory for Catalytic Processes and Materials, Faculty of Chemical Technology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands)

    2001-01-01

    The selective catalytic reduction of NO by propene in the presence of excess oxygen has been studied over catalysts based on Co-Pt supported on ZSM-5. Pure Pt based catalysts are highly active, but produce large amounts of N{sub 2}O. Bimetallic Co-Pt/ZSM-5 catalysts with low Pt contents (0.1wt.%) show a synergistic effect by combining high stability and activity of Pt catalysts with the high N{sub 2} selectivity of Co catalysts. The lower selectivity to N{sub 2}O is attributed to its selective conversion over Co. The catalysts also showed high water and sulfur tolerance above 350C.

  15. The Catalytic Bias of 2-Oxoacid:ferredoxin Oxidoreductase in CO_2: evolution and reduction through a ferredoxin-mediated electrocatalytic assay

    International Nuclear Information System (INIS)

    Li, Bin; Elliott, Sean J.

    2016-01-01

    Enzymes from the 2-oxoacid: ferredoxin oxidoreductase (OFOR) family engage in both CO_2 evolution and reduction in nature, depending on their physiological roles. Two enzymes and their redox partner ferredoxins (Fds) from Hydrogenobacter thermophilus and Desulfovibrio africanus were examined to investigate the basis of the catalytic bias. The Fd1 from H. thermophilus demonstrated a potential of ∼ −485 mV at room temperature, the lowest for known single [4Fe-4S] cluster Fds. It suggests a low potential electron donor may be the key factor in overcoming the large thermodynamic barrier of CO_2 reduction. The Fd-mediated electrocatalytic experiments further demonstrated the impact of Fd’s potential on the direction of the OFOR reaction: as OFOR enzymes could essentially catalyze both CO_2 evolution and reduction in vitro, the difference in their physiological roles is associated with the reduction potential of the redox partner Fd. The electrocatalytic assay could study both CO_2 evolution and reduction in one setup and is a good tool to probe Fds’ reactivity that arise from their reduction potentials.

  16. A Simple Primary Amine Catalyst for Enantioselective α-Hydroxylations and α-Fluorinations of Branched Aldehydes

    OpenAIRE

    Witten, Michael R.; Jacobsen, Eric N.

    2015-01-01

    A new primary amine catalyst for the asymmetric α-hydroxylation and α-fluorination of α-branched aldehydes is described. The products of the title transformations are generated in excellent yields and with high enantioselectivities. Both processes can be performed within short reaction times and on gram scale. The similarity in the results obtained in both reactions, combined with computational evidence, implies a common basis for stereoinduction and the possibility of a general catalytic mec...

  17. Enantioselective Direct α-Amination of Aldehydes via a Photoredox Mechanism: A Strategy for Asymmetric Amine Fragment Coupling

    OpenAIRE

    Cecere, Giuseppe; Koenig, Christian M.; Alleva, Jennifer L.; MacMillan, David W. C.

    2013-01-01

    The direct, asymmetric α-amination of aldehydes has been accomplished via a combination of photoredox and organocatalysis. Photon-generated, nitrogen-centered radicals undergo enantioselective α-addition to catalytically formed chiral enamines to directly produce stable α-amino aldehyde adducts bearing synthetically useful amine substitution patterns. Incorporation of a photolabile group on the amine precursor obviates the need to employ a photoredox catalyst in this transformation. Important...

  18. Continuous-flow enantioselective α-aminoxylation of aldehydes catalyzed by a polystyrene-immobilized hydroxyproline

    Directory of Open Access Journals (Sweden)

    Xacobe C. Cambeiro

    2011-10-01

    Full Text Available The application of polystyrene-immobilized proline-based catalysts in packed-bed reactors for the continuous-flow, direct, enantioselective α-aminoxylation of aldehydes is described. The system allows the easy preparation of a series of β-aminoxy alcohols (after a reductive workup with excellent optical purity and with an effective catalyst loading of ca. 2.5% (four-fold reduction compared to the batch process working at residence times of ca. 5 min.

  19. A microwave assisted one-pot route synthesis of bimetallic PtPd alloy cubic nanocomposites and their catalytic reduction for 4-nitrophenol

    Science.gov (United States)

    Zhang, Jian; Gan, Wei; Fu, Xucheng; Hao, Hequn

    2017-10-01

    We herein report a simple, rapid, and eco-friendly chemical route to the one-pot synthesis of bimetallic PtPd alloy cubic nanocomposites under microwave irradiation. During this process, water was employed as an environmentally benign solvent, while dimethylformamide served as a mild reducing agent, and polyvinylpyrrolidone was used as both a dispersant and a stabilizer. The structure, morphology, and composition of the resulting alloy nanocomposites were examined by x-ray diffraction, transmission electron microscopy, and energy dispersive x-ray spectroscopy. A detailed study was then carried out into the catalytic activity of the PtPd nanocomposites with a Pt:Pd molar ratio of 50:50 in the reduction of 4-nitrophenol (4-NP) by sodium borohydride as a model reaction. Compared with pristine Pt and Pd monometallic nanoparticles (PtNPs and PdNPs), the bimetallic PtPd alloy nanocomposites exhibited enhanced catalytic activities and were readily recyclable in the reduction of 4-NP due to synergistic effects.

  20. Preparation of FeO(OH Modified with Polyethylene Glycol and Its Catalytic Activity on the Reduction of Nitrobenzene with Hydrazine Hydrate

    Directory of Open Access Journals (Sweden)

    Ke Ying Cai

    2016-10-01

    Full Text Available Iron oxyhydroxide was prepared by dropping ammonia water to Fe(NO33.9H2O dispersed in polyethylene glycol (PEG 1000. The catalyst was characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy and laser particle size analyzer. The results showed the catalyst modified with polyethylene glycol was amorphous. The addition of PEG during the preparation make the particle size of the catalyst was smaller and more uniform. The catalytic performance was tested in the reduction of nitroarenes to corresponding amines with hydrazine hydrate, and the catalyst showed excellent activity and stability. Copyright © 2016 BCREC GROUP. All rights reserved Received: 2nd February 2016; Revised: 26th April 2016; Accepted: 7th June 2016 How to Cite: Cai, K.Y., Liu, Y.S., Song, M., Zhou, Y.M., Liu, Q., Wang, X.H. (2016. Preparation of FeO(OH Modified with Polyethylene Glycol and Its Catalytic Activity on the Reduction of Nitrobenzene with Hydrazine Hydrate. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (3: 363-368 (doi:10.9767/bcrec.11.3.576.363-368 Permalink/DOI: http://doi.org/10.9767/bcrec.11.3.576.363-368

  1. Enhanced hydrothermal stability of Cu-ZSM-5 catalyst via surface modification in the selective catalytic reduction of NO with NH_3

    International Nuclear Information System (INIS)

    Zhang, Tao; Shi, Juan; Liu, Jian; Wang, Daxi; Zhao, Zhen; Cheng, Kai; Li, Jianmei

    2016-01-01

    Highlights: • The hydrothermal stability of Cu-ZSM-5 catalyst was enhanced after surface modification. • An inert silica layer was deposited on the surface of Cu-ZSM-5 and formed a protective layer. • The contact between Si and Cu and Al atoms could form Si-O-Al and Si- O−Cu bonds. • The redox and acidity properties of Cu-ZSM-5-CLD-Aged catalyst were largely retained. • The adsorption and activation of NO and NH_3 was almost unchanged over Cu-ZSM-5-CLD catalyst before and after hydrothermal treatment. - Abstract: The surface of Cu-ZSM-5 catalyst was modified by chemical liquid deposition (CLD) of tetraethoxysilane (TEOS) for enhancing its hydrothermal stability in the selective catalytic reduction of NO with NH_3. After hydrothermal aging at 750 °C for 13 h, the catalytic performance of Cu-ZSM-5-Aged catalyst was significantly reduced for NO reduction in the entire temperature range, while that of Cu-ZSM-5-CLD-Aged catalyst was affected very little. The characterization results indicated that an inert silica layer was deposited on the surface of Cu-ZSM-5 and formed a protective layer, which prevents the detachment of Cu"2"+ from ZSM-5 ion-exchange positions and the dealumination of zeolite during the hydrothermal aging process. Based on the data it is hypothesized to be the primary reason for the high hydrothermal stability of Cu-ZSM-5-CLD catalyst.

  2. Highly recyclable and ultra-rapid catalytic reduction of organic pollutants on Ag-Cu@ZnO bimetal nanocomposite synthesized via green technology

    Science.gov (United States)

    Gangarapu, Manjari; Sarangapany, Saran; Suja, Devipriya P.; Arava, Vijaya Bhaskara Rao

    2018-04-01

    In this study, synthesis of Ag-Cu alloy bimetal nanoparticles anchored on high surface and porous ZnO using a facile, greener and low-cost aqeous bark extract of Aglaia roxburghiana for highly active, ultra-rapid and stable catalyst is performed. The nanocomposite was scrupulously characterized using UV-Vis spectrophotometer, X-ray diffraction, Raman spectrophotometer, high-resolution transmission electron microscope, selected area (electron) diffraction, scanning electron microscope with energy dispersive X-ray spectroscopy, and Fourier-transform infrared spectroscopy. The catalytic activity of the green synthesized Ag-Cu bimetal nanocomposite was evaluated in the reduction of 4-nitrophenol (4-NP), methylene blue (MB) and rhodamine B (Rh B) dyes. The different types of dye exhibited very high and effective catalytic activity within few seconds. The theoretical investigations reveal that the unique synergistic effect of Ag-Cu nanoparticles and immobilization over ZnO assists in the reduction of 4-NP, MB and Rh B. Loading and leaching of metal nanoparticles were obtained using inductively coupled plasma atomic emission spectroscopy. Moreover, the stable and efficient recyclability of nanocomposite by centrifugation after completion of the reaction was demonstrated. The results lead to the design different possible bimetal on ZnO with boosting and an effective catalyst for the environmental applications.

  3. Remarkable promoting effect of rhodium on the catalytic performance of Ag/Al2O3 for the selective reduction of NO with decane

    International Nuclear Information System (INIS)

    Sato, Kazuhito; Yoshinari, Tomohiro; Kintaichi, Yoshiaki; Haneda, Masaaki; Hamada, Hideaki

    2003-01-01

    The addition of small amounts of rhodium enhanced the activity of Ag/Al 2 O 3 catalyst for the selective reduction of NO with decane at low temperatures. The Rh-promoted Ag/Al 2 O 3 showed its high performance even in the presence of low concentrations of SO 2 . Based on the catalytic activity for elementary reactions, it was suggested that the role of added rhodium is to enhance the reaction between NO x and decane-derived species, leading to NO reduction. Catalyst characterization by UV-Vis spectroscopy indicated that the major silver species on Rh-promoted Ag/Al 2 O 3 is Ag nn δ+ clusters, which would be responsible for the high activity. FT-IR measurements revealed that the formation rate of isocyanate species, which is a major reaction intermediate, is higher on Rh-promoted Ag/Al 2 O 3

  4. Advanced byproduct recovery: Direct catalytic reduction of sulfur dioxide to elemental sulfur. Quarterly report, April 1--June 30, 1997

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-31

    The team of Arthur D. Little, Tufts University and Engelhard Corporation are conducting Phase 1 of a four and a half year, two-phase effort to develop and scale-up an advanced byproduct recovery technology that is a direct, single-stage, catalytic process for converting sulfur dioxide to elemental sulfur. This catalytic process reduces SO{sub 2} over a fluorite-type oxide (such as ceria and zirconia). The catalytic activity can be significantly promoted by active transition metals, such as copper. More than 95% elemental sulfur yield, corresponding to almost complete sulfur dioxide conversion, was obtained over a Cu-Ce-O oxide catalyst as part of an on-going DOE-sponsored, University Coal Research Program. This type of mixed metal oxide catalyst has stable activity, high selectivity for sulfur production, and is resistant to water and carbon dioxide poisoning. Tests with CO and CH{sub 4} reducing gases indicate that the catalyst has the potential for flexibility with regard to the composition of the reducing gas, making it attractive for utility use. The performance of the catalyst is consistently good over a range of SO{sub 2} inlet concentration (0.1 to 10%) indicating its flexibility in treating SO{sub 2} tail gases as well as high concentration streams. The principal objective of the Phase 1 program is to identify and evaluate the performance of a catalyst which is robust and flexible with regard to choice of reducing gas. In order to achieve this goal, the authors have planned a structured program including: Market/process/cost/evaluation; Lab-scale catalyst preparation/optimization studies; Lab-scale, bulk/supported catalyst kinetic studies; Bench-scale catalyst/process studies; and Utility review. Progress is reported from all three organizations.

  5. Catalytic reduction of NO{sub x}. Final report; Katalytisk Reduktion av NO{sub x}. Slutrapport

    Energy Technology Data Exchange (ETDEWEB)

    Khodayari, Raziyeh; Odenbrand, Ingemar [Lund Univ. (Sweden). Chemical Engineering II

    2002-02-01

    This report is intended to show the work regarding the SCR technique performed at Chemical Engineering II, Lund Inst. of Tech. since the start in 1982. The emphasis is on work performed the last 7 years which deals with deactivation and regeneration of SCR catalysts. In chapter 1 a short general introduction to the SCR technique is given. Chapter 2 describes the work performed up to 1995. It shows the kinetics for the reaction between NO and NH{sub 3}, reactions between NO{sub 2} and NH{sub 3} as well as patents for a new process for cleaning flue gases based on our research results. Later work on using zeolites as catalysts for the reduction and for the oxidation of NO was presented. Then a series of characterisations were performed on model catalysts consisting of 2-30 wt.% V{sub 2}O{sub 5} on a coprecipitated silica-titania support. The formation of nitrous oxide was studied and found to be noticeable when water is not present in the gas and on a catalyst which contains large amounts of crystallites of V{sub 2}O{sub 5}. Chapter 3 deals with international research in the area of deactivation of SCR catalysts in i.e. biofuelled applications. Material from a literature search from December 2001 is presented. It contains general material on the deactivation with alkali metals and SO{sub 2}. Chapter 4 deals with our studies of deactivated SCR catalysts. During 1995-2001 we have studied the deactivation of catalysts in a number of Swedish plants. The sensitivity of zeolites to poisoning in waste combustion (GRAAB) was tested by artificial poisoning with 2 wt.% metal of the elements; Na, K, Mg, Fe, Zn, Cu, Al, Ni and Cr. The combustion of waste at SYSAV gave high contents of Na, Y, Ca, Pb and Zn on the catalyst after 2000 hours on stream. Activity measurements showed that low concentrations of ammonium sulphate, 1-5 vol.%, promotes the SCR reaction. A maximal activity is obtained at around 5 vol.%. There exists an optimal content of ammonium sulphate on the catalyst

  6. Simple one-pot synthesis of platinum-palladium nanoflowers with enhanced catalytic activity and methanol-tolerance for oxygen reduction in acid media

    International Nuclear Information System (INIS)

    Zheng, Jie-Ning; He, Li-Li; Chen, Fang-Yi; Wang, Ai-Jun; Xue, Meng-Wei; Feng, Jiu-Ju

    2014-01-01

    Graphical abstract: PtPd nanoflowers were fabricated by one-pot solvothermal co-reduction method in oleylamine system, which exhibited the improved electrocatalytic activity and higher methanol tolerance for oxygen reduction, compared with commercial Pt and Pd black catalysts. - Highlights: • Bimetallic alloyed PtPd nanoflowers are prepared by a simple one-pot solvothermal co-reduction method. • PtPd nanoflowers display high catalytic performance for ORR dominated by a four-electron pathway. • PtPd nanoflowers show good methanol tolerance for ORR. - Abstract: In this work, bimetallic alloyed platinum-palladium (PtPd) nanoflowers are fabricated by one-pot solvothermal co-reduction of Pt (II) acetylacetonate and Pd (II) acetylacetonate in oleylamine system. The as-prepared nanostructures show the enhanced electrocatalytic activity for oxygen reduction reaction (ORR), dominated by a four-electron pathway based on the Koutecky-Levich plots, mainly owing to the inhibition of the formation of Pt–OH ad via the downshift of d-band center for Pt. Meanwhile, PtPd nanoflowers display good methanol tolerance and improved stability for ORR. The chronoamperometry test reveals that the current of PtPd nanoflowers remains 45.9% of its original value within 6000 s, much higher than those of commercial Pt (36.7%) and Pd (32.2%) black catalysts. Therefore, PtPd nanoflowers with unique interconnected structures can be used as a promising cathode catalyst in direct methanol fuel cells

  7. Direct, enantioselective α-alkylation of aldehydes using simple olefins.

    Science.gov (United States)

    Capacci, Andrew G; Malinowski, Justin T; McAlpine, Neil J; Kuhne, Jerome; MacMillan, David W C

    2017-11-01

    Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes-photoredox, enamine and hydrogen-atom transfer (HAT) catalysis-enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

  8. Enantioselective Biotransformation of Chiral Persistent Organic Pollutants.

    Science.gov (United States)

    Zhang, Ying; Ye, Jing; Liu, Min

    2017-01-01

    Enantiomers of chiral compounds commonly undergo enantioselective transformation in most biologically mediated processes. As chiral persistent organic pollutants (POPs) are extensively distributed in the environment, differences between enantiomers in biotransformation should be carefully considered to obtain exact enrichment and specific health risks. This review provides an overview of in vivo biotransformation of chiral POPs currently indicated in the Stockholm Convention and their chiral metabolites. Peer-reviewed journal articles focused on the research question were thoroughly searched. A set of inclusion and exclusion criteria were developed to identify relevant studies. We mainly compared the results from different animal models under controlled laboratory conditions to show the difference between enantiomers in terms of distinct transformation potential. Interactions with enzymes involved in enantioselective biotransformation, especially cytochrome P450 (CYP), were discussed. Further research areas regarding this issue were proposed. Limited evidence for a few POPs has been found in 30 studies. Enantioselective biotransformation of α-hexachlorocyclohexane (α-HCH), chlordane, dichlorodiphenyltrichloroethane (DDT), heptachlor, hexabromocyclododecane (HBCD), polychlorinated biphenyls (PCBs), and toxaphene, has been investigated using laboratory mammal, fish, bird, and worm models. Tissue and excreta distributions, as well as bioaccumulation and elimination kinetics after administration of racemate and pure enantiomers, have been analyzed in these studies. Changes in enantiomeric fractions have been considered as an indicator of enantioselective biotransformation of chiral POPs in most studies. Results of different laboratory animal models revealed that chiral POP biotransformation is seriously affected by chirality. Pronounced results of species-, tissue-, gender-, and individual-dependent differences are observed in in vivo biotransformation of chiral POPs

  9. Effect of metal ions doping (M = Ti4+, Sn4+) on the catalytic performance of MnOx/CeO2 catalyst for low temperature selective catalytic reduction of NO with NH3

    Science.gov (United States)

    Xiong, Yan; Tang, Changjin; Dong, Lin

    2015-04-01

    Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, PR China The abatement of nitrogen oxides (NOx) emission from exhaust gases of diesel and stationary sources is a significant challenge for economic and social development. Ceria-based solid solutions were synthesized and used as supports to prepare MnOx/Ce0.8Ti0.2O2 and MnOx/Ce0.8Sn0.2O2 catalysts (Mn/CeTi and Mn/CeSn) for low temperature selective catalytic reduction of NO by NH3 (NH3-SCR). The effects of Ti or Sn doping on the catalytic performance of MnOx/CeO2 catalyst were investigated. Experimental results show that doping of Ti or Sn increases the NO removal efficiency of MnOx/CeO2. The NO conversion of Mn/CeTi catalyst is more than 90 % at temperature window of 175 ~ 300 °C under a gas hour space velocity of 60,000 mL.g-1.h-1. Modified catalysts are also found to exhibit greatly improved resistance to sulfur-poisoning. NH3-TPD results suggest that NH3 desorption on the catalysts is observed over a wide temperature range, due to the variability of adsorbed NH3 species with different thermal stabilities. Doping of Ti and Sn into Mn/CeO2 greatly increased the NH3 adsorption ability of the composites which could promote the SCR reaction. Characterization results also indicate that doping of Ti or Sn brings about catalysts with higher BET surface area, enhanced oxygen storage capacity and increased surface acidity.

  10. Modelling substrate specificity and enantioselectivity for lipases and esterases by substrate-imprinted docking

    Directory of Open Access Journals (Sweden)

    Tyagi Sadhna

    2009-06-01

    Full Text Available Abstract Background Previously, ways to adapt docking programs that were developed for modelling inhibitor-receptor interaction have been explored. Two main issues were discussed. First, when trying to model catalysis a reaction intermediate of the substrate is expected to provide more valid information than the ground state of the substrate. Second, the incorporation of protein flexibility is essential for reliable predictions. Results Here we present a predictive and robust method to model substrate specificity and enantioselectivity of lipases and esterases that uses reaction intermediates and incorporates protein flexibility. Substrate-imprinted docking starts with covalent docking of reaction intermediates, followed by geometry optimisation of the resulting enzyme-substrate complex. After a second round of docking the same substrate into the geometry-optimised structures, productive poses are identified by geometric filter criteria and ranked by their docking scores. Substrate-imprinted docking was applied in order to model (i enantioselectivity of Candida antarctica lipase B and a W104A mutant, (ii enantioselectivity and substrate specificity of Candida rugosa lipase and Burkholderia cepacia lipase, and (iii substrate specificity of an acetyl- and a butyrylcholine esterase toward the substrates acetyl- and butyrylcholine. Conclusion The experimentally observed differences in selectivity and specificity of the enzymes were reproduced with an accuracy of 81%. The method was robust toward small differences in initial structures (different crystallisation conditions or a co-crystallised ligand, although large displacements of catalytic residues often resulted in substrate poses that did not pass the geometric filter criteria.

  11. Catalytic role of Cu(II) in the reduction of Cr(VI) by citric acid under an irradiation of simulated solar light.

    Science.gov (United States)

    Li, Ying; Chen, Cheng; Zhang, Jing; Lan, Yeqing

    2015-05-01

    The catalytic role of Cu(II) in the reduction of Cr(VI) by citric acid with simulated solar light was investigated. The results demonstrated that Cu(II) could significantly accelerate Cr(VI) reduction and the reaction obeyed to pseudo zero-order kinetics with respect to Cr(VI). The removal of Cr(VI) was related to the initial concentrations of Cu(II), citric acid, and the types of organic acids. The optimal removal of Cr(VI) was achieved at pH 4, and the rates of Cu(II) photocatalytic reduction of Cr(VI) by organic acids were in the order: tartaric acid (two α-OH groups, two -COOH groups)>citric acid (one α-OH group, three -COOH groups)>malic acid (one α-OH group, two -COOH groups)>lactic acid (one α-OH group, one -COOH group)≫succinic acid (two -COOH groups), suggesting that the number of α-OH was the key factor for the reaction, followed by the number of -COOH. The formation of Cu(II)-citric acid complex could generate Cu(I) and radicals through a pathway of metal-ligand-electron transfer, promoting the reduction of Cr(VI). This study is helpful to fully understanding the conversion of Cr(VI) in the existence of both organic acids and Cu(II) with solar light in aquatic environments. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. The selective catalytic reduction of NO with NH3 over a novel Ce-Sn-Ti mixed oxides catalyst: Promotional effect of SnO2

    Science.gov (United States)

    Yu, Ming'e.; Li, Caiting; Zeng, Guangming; Zhou, Yang; Zhang, Xunan; Xie, Yin'e.

    2015-07-01

    A series of novel catalysts (CexSny) for the selective catalytic reduction of NO by NH3 were prepared by the inverse co-precipitation method. The aim of this novel design was to improve the NO removal efficiency of CeTi by the introduction of SnO2. It was found that the Ce-Sn-Ti catalyst was much more active than Ce-Ti and the best Ce:Sn molar ratio was 2:1. Ce2Sn1 possessed a satisfied NO removal efficiency at low temperature (160-280 °C), while over 90% NO removal efficiency maintained in the temperature range of 280-400 °C at the gas hourly space velocity (GHSV) of 50,000 h-1. Besides, Ce2Sn1 kept a stable NO removal efficiency within a wide range of GHSV and a long period of reacting time. Meanwhile, Ce2Sn1 exhibited remarkable resistance to both respectively and simultaneously H2O and SO2 poisoning due to the introduction of SnO2. The promotional effect of SnO2 was studied by N2 adsorption-desorption, X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectroscopy (XPS) and H2 temperature programmed reduction (H2-TPR) for detail information. The characterization results revealed that the excellent catalytic performance of Ce2Sn1 was associated with the higher specific surface area, larger pore volume and poorer crystallization. Besides, the introduction of SnO2 could result in not only greater conversion of Ce4+ to Ce3+ but also the increase amount of chemisorbed oxygen, which are beneficial to improve the SCR activity. More importantly, a novel peak appearing at lower temperatures through the new redox equilibrium of 2Ce4+ + Sn2+ ↔ 2Ce3+ + Sn4+ and higher total H2 consumption can be obtained by the addition of SnO2. Finally, the possible reaction mechanism of the selective catalytic reduction over Ce2Sn1 was also proposed.

  13. Exploiting nanospace for asymmetric catalysis: confinement of immobilized, single-site chiral catalysts enhances enantioselectivity.

    Science.gov (United States)

    Thomas, John Meurig; Raja, Robert

    2008-06-01

    In the mid-1990s, it became possible to prepare high-area silicas having pore diameters controllably adjustable in the range ca. 20-200 Å. Moreover, the inner walls of these nanoporous solids could be functionalized to yield single-site, chiral, catalytically active organometallic centers, the precise structures of which could be determined using in situ X-ray absorption and FTIR and multinuclear magic angle spinning (MAS) NMR spectroscopy. This approach opened up the prospect of performing heterogeneous enantioselective conversions in a novel manner, under the spatial restrictions imposed by the nanocavities within which the reactions occur. In particular, it suggested an alternative method for preparing pharmaceutically and agrochemically useful asymmetric products by capitalizing on the notion, initially tentatively perceived, that spatial confinement of prochiral reactants (and transition states formed at the chiral active center) would provide an altogether new method of boosting the enantioselectivity of the anchored chiral catalyst. Initially, we anchored chiral single-site heterogeneous catalysts to nanopores covalently via a ligand attached to Pd(II) or Rh(I) centers. Later, we employed a more convenient and cheaper electrostatic method, relying in part on strong hydrogen bonding. This Account provides many examples of these processes, encompassing hydrogenations, oxidations, and aminations. Of particular note is the facile synthesis from methyl benzoylformate of methyl mandelate, which is a precursor in the synthesis of pemoline, a stimulant of the central nervous system; our procedure offers several viable methods for reducing ketocarboxylic acids. In addition to relying on earlier (synchrotron-based) in situ techniques for characterizing catalysts, we have constructed experimental procedures involving robotically controlled catalytic reactors that allow the kinetics of conversion and enantioselectivity to be monitored continually, and we have access to

  14. Microwave-irradiated preparation of reduced graphene oxide-Ni nanostructures and their enhanced performance for catalytic reduction of 4-nitrophenol

    International Nuclear Information System (INIS)

    Qiu, Hanxun; Qiu, Feilong; Han, Xuebin; Li, Jing; Yang, Junhe

    2017-01-01

    Highlights: • Nickel nanoparticle-decorated reduced graphene-oxide nanostructures were prepared by an environmentally friendly, one-pot strategy via an efficient microwave irradiation approach. • Upon microwave irradiation, the composites could be prepared within only a few hundred seconds, much faster than using the widely used traditional hydrothermal methods that may take tens of hours generally. • The nanostructure exhibits superior catalytic activity and selectivity towards transforming the highly toxic nitroaromatic compounds to industrially useful intermediates • The corresponding kinetic reaction rate constant (κ) is even four-fold compared to pure Ni nanoparticles. - Abstract: Here we report an environmentally friendly, one-pot strategy toward preparation of nickel nanoparticle-decorated reduced graphene-oxide (Ni-RGO) nanostructures, by employing Ni(AC) 2 as nickel source and ethylene glycol as both solvent and reducing agent via a facile microwave irradiation heating approach. The results show that Ni nanoparticles with an average diameter of around 40 nm are homogeneously anchored onto the surface of RGO sheets. As compared to the pure Ni nanoparticles and RGO sheets, Ni-RGO composites with over 64 wt% loading of Ni nanoparticles possess superior catalytic activities and selectivity toward the reduction of 4-nitrophenol. The corresponding kinetic reaction rate constant (defined as κ) is even four-fold compared to pure Ni nanoparticles. Such promising composites show great potential for friendly treatment of industrial waste containing nitrophenol in a simple, sustainable and green way.

  15. Liquid-phase pulsed laser ablation synthesis of graphitized carbon-encapsulated palladium core-shell nanospheres for catalytic reduction of nitrobenzene to aniline

    Science.gov (United States)

    Kim, Yu-jin; Ma, Rory; Reddy, D. Amaranatha; Kim, Tae Kyu

    2015-12-01

    Graphitized carbon-encapsulated palladium (Pd) core-shell nanospheres were produced via pulsed laser ablation of a solid Pd foil target submerged in acetonitrile. The microstructural features and optical properties of these nanospheres were characterized via high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy. Microstructural analysis indicated that the core-shell nanostructures consisted of single-crystalline cubic metallic Pd spheres that serve as the core material, over which graphitized carbon was anchored as a heterogeneous shell. The absorbance spectrum of the synthesized nanostructures exhibited a broad (absorption) band at ∼264 nm; this band corresponded to the typical inter-band transition of a metallic system and resulted possibly from the absorbance of the ionic Pd2+. The catalytic properties of the Pd and Pd@C core-shell nanostructures were investigated using the reduction of nitrobenzene to aniline by an excess amount of NaBH4 in an aqueous solution at room temperature, as a model reaction. Owing to the graphitized carbon-layered structure and the high specific surface area, the resulting Pd@C nanostructures exhibited higher conversion efficiencies than their bare Pd counterparts. In fact, the layered structure provided access to the surface of the Pd nanostructures for the hydrogenation reaction, owing to the synergistic effect between graphitized carbon and the nanostructures. Their unique structure and excellent catalytic performance render Pd@C core-shell nanostructures highly promising candidates for catalysis applications.

  16. Microwave-irradiated preparation of reduced graphene oxide-Ni nanostructures and their enhanced performance for catalytic reduction of 4-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, Hanxun, E-mail: hxqiu@usst.edu.cn; Qiu, Feilong; Han, Xuebin; Li, Jing; Yang, Junhe, E-mail: jhyang@usst.edu.cn

    2017-06-15

    Highlights: • Nickel nanoparticle-decorated reduced graphene-oxide nanostructures were prepared by an environmentally friendly, one-pot strategy via an efficient microwave irradiation approach. • Upon microwave irradiation, the composites could be prepared within only a few hundred seconds, much faster than using the widely used traditional hydrothermal methods that may take tens of hours generally. • The nanostructure exhibits superior catalytic activity and selectivity towards transforming the highly toxic nitroaromatic compounds to industrially useful intermediates • The corresponding kinetic reaction rate constant (κ) is even four-fold compared to pure Ni nanoparticles. - Abstract: Here we report an environmentally friendly, one-pot strategy toward preparation of nickel nanoparticle-decorated reduced graphene-oxide (Ni-RGO) nanostructures, by employing Ni(AC){sub 2} as nickel source and ethylene glycol as both solvent and reducing agent via a facile microwave irradiation heating approach. The results show that Ni nanoparticles with an average diameter of around 40 nm are homogeneously anchored onto the surface of RGO sheets. As compared to the pure Ni nanoparticles and RGO sheets, Ni-RGO composites with over 64 wt% loading of Ni nanoparticles possess superior catalytic activities and selectivity toward the reduction of 4-nitrophenol. The corresponding kinetic reaction rate constant (defined as κ) is even four-fold compared to pure Ni nanoparticles. Such promising composites show great potential for friendly treatment of industrial waste containing nitrophenol in a simple, sustainable and green way.

  17. Enantioselective properties of induced lipases from Geotrichum

    Czech Academy of Sciences Publication Activity Database

    Zarevúcka, Marie; Kejík, Z.; Šaman, David; Wimmer, Zdeněk; Demnerová, K.

    2005-01-01

    Roč. 37, - (2005), s. 481-486 ISSN 0141-0229 R&D Projects: GA MŠk(CZ) OC D30.001; GA MŠk(CZ) OC D13.10 Institutional research plan: CEZ:AV0Z40550506 Keywords : Geotrichum * lipase * enantioselectivity Subject RIV: CC - Organic Chemistry Impact factor: 1.705, year: 2005

  18. Enantioselective pharmacokinetics of sibutramine in rat.

    Science.gov (United States)

    Noh, Keumhan; Bae, Kyoungjin; Min, Bokyoung; Kim, Eunyoung; Kwon, Kwang-il; Jeong, Taecheon; Kang, Wonku

    2010-02-01

    Racemic sibutramine is widely used to treat obesity owing to its inhibition of serotonin and noradrenaline reuptake in synapses. Although the enantioselective effects of sibutramine and its two active desmethyl-metabolites, monodesmethylsibutramine (MDS) and didesmethylsibutramine (DDS), on anorexia and energy expenditure have been elucidated, the enantioselective pharmacokinetics of sibutramine are still unclear. Therefore, we aimed to characterize the enantioselective pharmacokinetics of sibutramine and its metabolites in plasma and urine following an intravenous and a single oral administration of sibutramine in rats. The absolute bioavailability of sibutramine was only about 7%. The pharmacologically less effective S-isomer of DDS was predominant in the plasma: the C ( max ) and the AUC ( inf ) were 28 and 30 times higher than those of the R-isomer, respectively (psibutramine metabolites MDS and DDS were present at lower concentrations, owing to their rapid biotransformation to hydroxylated and/or carbamoylglucuronized forms and their faster excretion in the urine. The present study is the first to elucidate the enantioselective pharmacokinetics of sibutramine in rats.

  19. Microwave-irradiated preparation of reduced graphene oxide-Ni nanostructures and their enhanced performance for catalytic reduction of 4-nitrophenol

    Science.gov (United States)

    Qiu, Hanxun; Qiu, Feilong; Han, Xuebin; Li, Jing; Yang, Junhe

    2017-06-01

    Here we report an environmentally friendly, one-pot strategy toward preparation of nickel nanoparticle-decorated reduced graphene-oxide (Ni-RGO) nanostructures, by employing Ni(AC)2 as nickel source and ethylene glycol as both solvent and reducing agent via a facile microwave irradiation heating approach. The results show that Ni nanoparticles with an average diameter of around 40 nm are homogeneously anchored onto the surface of RGO sheets. As compared to the pure Ni nanoparticles and RGO sheets, Ni-RGO composites with over 64 wt% loading of Ni nanoparticles possess superior catalytic activities and selectivity toward the reduction of 4-nitrophenol. The corresponding kinetic reaction rate constant (defined as κ) is even four-fold compared to pure Ni nanoparticles. Such promising composites show great potential for friendly treatment of industrial waste containing nitrophenol in a simple, sustainable and green way.

  20. Metal-Carbon-CNF Composites Obtained by Catalytic Pyrolysis of Urban Plastic Residues as Electro-Catalysts for the Reduction of CO2

    Directory of Open Access Journals (Sweden)

    Jesica Castelo-Quibén

    2018-05-01

    Full Text Available Metal–carbon–carbon nanofibers composites obtained by catalytic pyrolysis of urban plastic residues have been prepared using Fe, Co or Ni as pyrolitic catalysts. The composite materials have been fully characterized from a textural and chemical point of view. The proportion of carbon nanofibers and the final content of carbon phases depend on the used pyrolitic metal with Ni being the most active pyrolitic catalysts. The composites show the electro-catalyst activity in the CO2 reduction to hydrocarbons, favoring all the formation of C1 to C4 hydrocarbons. The tendency of this activity is in accordance with the apparent faradaic efficiencies and the linear sweep voltammetries. The cobalt-based composite shows high selectivity to C3 hydrocarbons within this group of compounds.

  1. Life cycle assessment of selective non-catalytic reduction (SNCR) of nitrous oxides in a full-scale municipal solid waste incinerator

    DEFF Research Database (Denmark)

    Møller, Jacob; Munk, Bjarne; Crillesen, Kim

    2011-01-01

    Selective non-catalytic reduction (SNCR) of nitrous oxides in a full-scale municipal solid waste incinerator was investigated using LCA. The relationship between NOx-cleaning and ammonia dosage was measured at the plant. Un-reacted ammonia – the ammonia slip – leaving the flue-gas cleaning system......-cleaning efficiency, the fate of the ammonia slip as well as the environmental impact from ammonia production, the potential acidification and nutrient enrichment from NOx-cleaning was calculated as a function of ammonia dosage. Since the exact fate of the ammonia slip could not be measured directly, a number...... of scenarios were set up ranging from “best case” with no ammonia from the slip ending up in the environment to “worst case” where all the ammonia slip eventually ended up in the environment and contributed to environmental pollution. In the “best case” scenario the highest ammonia dosage was most beneficial...

  2. Macrodynamic study and catalytic reduction of NO by ammonia under mild conditions over Pt-La-Ce-O/Al2O3 catalysts

    International Nuclear Information System (INIS)

    Wang, Yanhui; Zhu, Jingli; Ma, Runyu

    2007-01-01

    Catalytic reduction of NO using ammonia upon series prepared catalysts under 423-573 K in a fixed bed reactor was investigated. Results showed that the performance of supported platinum catalyst could be improved by addition of La and Ce to it. Experimental studies indicated that the suitable molar ratio of Pt:La:Ce would be 1.0:3.78:3.56, Pt-La-Ce (c). Results also found Pt-La-Ce (c) catalyst had good stability and tolerance to certain amounts of sulfur compounds under the used experimental conditions. Characterization for the fresh and used catalysts showed the Pt-La-Ce (c) catalyst had a stable structure. In addition, based on experimental data and using a nonlinear regression algorithm method, an empirical macrodynamic equation was obtained in this study

  3. Green synthesis of gold and silver nanoparticles using gallic acid: catalytic activity and conversion yield toward the 4-nitrophenol reduction reaction

    Science.gov (United States)

    Park, Jisu; Cha, Song-Hyun; Cho, Seonho; Park, Youmie

    2016-06-01

    In the present report, gallic acid was used as both a reducing and stabilizing agent to synthesize gold and silver nanoparticles. The synthesized gold and silver nanoparticles exhibited characteristic surface plasmon resonance bands at 536 and 392 nm, respectively. Nanoparticles that were approximately spherical in shape were observed in high-resolution transmission electron microscopy and atomic force microscopy images. The hydrodynamic radius was determined to be 54.4 nm for gold nanoparticles and 33.7 nm for silver nanoparticles in aqueous medium. X-ray diffraction analyses confirmed that the synthesized nanoparticles possessed a face-centered cubic structure. FT-IR spectra demonstrated that the carboxylic acid functional groups of gallic acid contributed to the electrostatic binding onto the surface of the nanoparticles. Zeta potential values of -41.98 mV for the gold nanoparticles and -53.47 mV for the silver nanoparticles indicated that the synthesized nanoparticles possess excellent stability. On-the-shelf stability for 4 weeks also confirmed that the synthesized nanoparticles were quite stable without significant changes in their UV-visible spectra. The synthesized nanoparticles exhibited catalytic activity toward the reduction reaction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride. The rate constant of the silver nanoparticles was higher than that of the gold nanoparticles in the catalytic reaction. Furthermore, the conversion yield (%) of 4-nitrophenol to 4-aminophenol was determined using reversed-phase high-performance liquid chromatography with UV detection at 254 nm. The silver nanoparticles exhibited an excellent conversion yield (96.7-99.9 %), suggesting that the synthesized silver nanoparticles are highly efficient catalysts for the 4-nitrophenol reduction reaction.

  4. Electronic coupling induced high performance of N, S-codoped graphene supported CoS2 nanoparticles for catalytic reduction and evolution of oxygen

    Science.gov (United States)

    Chen, Bohong; Jiang, Zhongqing; Zhou, Lingshan; Deng, Binglu; Jiang, Zhong-Jie; Huang, Jianlin; Liu, Meilin

    2018-06-01

    A simple synthetic method is developed for the synthesis of CoS2/N, S-codoped graphene. The result shows the existence of a strong electronic coupling between CoS2 and N, S-codoped graphene. The pyrrolic and pyridinic type nitrogen and S in the form of C-S-C in N, S-codoped graphene are found to be the anchoring sites of the CoS2 nanoparticles. As a bifunctional catalyst, the CoS2/N, S-codoped graphene exhibits an oxygen reduction onset potential of 0.963 V vs. RHE and delivers an oxygen evolution overpotential of 393 mV at the current density of 10 mA cm-2. Its oxygen reduction and evolution catalytic activities are comparable to those of the Pt/C and the state-of-art RuO2/C, respectively. Most impressively, the CoS2/N, S-codoped graphene exhibits a potential gap of 771 mV. This value is lower than those of most bifuntional catalysts reported, clearly indicating its potential use as the bifunctional catalyst to replace the noble-metal based catalysts for practical applications. Additionally, our results also suggest a great importance to prepare a single pure phase CoS2 in improving the catalytic bifunctionality of the CoS2/N, S-codoped graphene. The primary Zn-air battery with CoS2/N, S-codoped graphene shows a higher discharge peak power density than that with Pt/C.

  5. Green synthesis of gold and silver nanoparticles using gallic acid: catalytic activity and conversion yield toward the 4-nitrophenol reduction reaction

    International Nuclear Information System (INIS)

    Park, Jisu; Cha, Song-Hyun; Cho, Seonho; Park, Youmie

    2016-01-01

    In the present report, gallic acid was used as both a reducing and stabilizing agent to synthesize gold and silver nanoparticles. The synthesized gold and silver nanoparticles exhibited characteristic surface plasmon resonance bands at 536 and 392 nm, respectively. Nanoparticles that were approximately spherical in shape were observed in high-resolution transmission electron microscopy and atomic force microscopy images. The hydrodynamic radius was determined to be 54.4 nm for gold nanoparticles and 33.7 nm for silver nanoparticles in aqueous medium. X-ray diffraction analyses confirmed that the synthesized nanoparticles possessed a face-centered cubic structure. FT-IR spectra demonstrated that the carboxylic acid functional groups of gallic acid contributed to the electrostatic binding onto the surface of the nanoparticles. Zeta potential values of −41.98 mV for the gold nanoparticles and −53.47 mV for the silver nanoparticles indicated that the synthesized nanoparticles possess excellent stability. On-the-shelf stability for 4 weeks also confirmed that the synthesized nanoparticles were quite stable without significant changes in their UV–visible spectra. The synthesized nanoparticles exhibited catalytic activity toward the reduction reaction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride. The rate constant of the silver nanoparticles was higher than that of the gold nanoparticles in the catalytic reaction. Furthermore, the conversion yield (%) of 4-nitrophenol to 4-aminophenol was determined using reversed-phase high-performance liquid chromatography with UV detection at 254 nm. The silver nanoparticles exhibited an excellent conversion yield (96.7–99.9 %), suggesting that the synthesized silver nanoparticles are highly efficient catalysts for the 4-nitrophenol reduction reaction.

  6. Green synthesis of gold and silver nanoparticles using gallic acid: catalytic activity and conversion yield toward the 4-nitrophenol reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jisu [Inje University, College of Pharmacy (Korea, Republic of); Cha, Song-Hyun; Cho, Seonho [Seoul National University, Department of Naval Architecture and Ocean Engineering (Korea, Republic of); Park, Youmie, E-mail: youmiep@inje.ac.kr [Inje University, College of Pharmacy (Korea, Republic of)

    2016-06-15

    In the present report, gallic acid was used as both a reducing and stabilizing agent to synthesize gold and silver nanoparticles. The synthesized gold and silver nanoparticles exhibited characteristic surface plasmon resonance bands at 536 and 392 nm, respectively. Nanoparticles that were approximately spherical in shape were observed in high-resolution transmission electron microscopy and atomic force microscopy images. The hydrodynamic radius was determined to be 54.4 nm for gold nanoparticles and 33.7 nm for silver nanoparticles in aqueous medium. X-ray diffraction analyses confirmed that the synthesized nanoparticles possessed a face-centered cubic structure. FT-IR spectra demonstrated that the carboxylic acid functional groups of gallic acid contributed to the electrostatic binding onto the surface of the nanoparticles. Zeta potential values of −41.98 mV for the gold nanoparticles and −53.47 mV for the silver nanoparticles indicated that the synthesized nanoparticles possess excellent stability. On-the-shelf stability for 4 weeks also confirmed that the synthesized nanoparticles were quite stable without significant changes in their UV–visible spectra. The synthesized nanoparticles exhibited catalytic activity toward the reduction reaction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride. The rate constant of the silver nanoparticles was higher than that of the gold nanoparticles in the catalytic reaction. Furthermore, the conversion yield (%) of 4-nitrophenol to 4-aminophenol was determined using reversed-phase high-performance liquid chromatography with UV detection at 254 nm. The silver nanoparticles exhibited an excellent conversion yield (96.7–99.9 %), suggesting that the synthesized silver nanoparticles are highly efficient catalysts for the 4-nitrophenol reduction reaction.

  7. Enhanced hydrothermal stability of Cu-ZSM-5 catalyst via surface modification in the selective catalytic reduction of NO with NH{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Tao; Shi, Juan; Liu, Jian, E-mail: liujian@cup.edu.cn; Wang, Daxi; Zhao, Zhen, E-mail: zhenzhao@cup.edu.cn; Cheng, Kai; Li, Jianmei

    2016-07-01

    Highlights: • The hydrothermal stability of Cu-ZSM-5 catalyst was enhanced after surface modification. • An inert silica layer was deposited on the surface of Cu-ZSM-5 and formed a protective layer. • The contact between Si and Cu and Al atoms could form Si-O-Al and Si- O−Cu bonds. • The redox and acidity properties of Cu-ZSM-5-CLD-Aged catalyst were largely retained. • The adsorption and activation of NO and NH{sub 3} was almost unchanged over Cu-ZSM-5-CLD catalyst before and after hydrothermal treatment. - Abstract: The surface of Cu-ZSM-5 catalyst was modified by chemical liquid deposition (CLD) of tetraethoxysilane (TEOS) for enhancing its hydrothermal stability in the selective catalytic reduction of NO with NH{sub 3}. After hydrothermal aging at 750 °C for 13 h, the catalytic performance of Cu-ZSM-5-Aged catalyst was significantly reduced for NO reduction in the entire temperature range, while that of Cu-ZSM-5-CLD-Aged catalyst was affected very little. The characterization results indicated that an inert silica layer was deposited on the surface of Cu-ZSM-5 and formed a protective layer, which prevents the detachment of Cu{sup 2+} from ZSM-5 ion-exchange positions and the dealumination of zeolite during the hydrothermal aging process. Based on the data it is hypothesized to be the primary reason for the high hydrothermal stability of Cu-ZSM-5-CLD catalyst.

  8. 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.

  9. Charge transfer-resistance in nitrogen-doped/undoped graphene: Its influence on the electro-catalytic reduction of H2O2

    International Nuclear Information System (INIS)

    Magerusan, Lidia; Pogacean, Florina; Socaci, Crina; Coros, Maria; Rosu, Marcela-Corina; Pruneanu, Stela

    2016-01-01

    Nitrogen doped (N-Gr) and undoped (TRGO) graphene were chemically synthesized and characterized by TEM, STEM-EDX and XPS. The electrochemical reduction of H 2 O 2 was investigated with bare glassy carbon (GC) electrode and with GC modified with each graphene sample. The active area of TRGO/GC and N-Gr/GC modified electrodes were found to be 0.75 and 0.295 cm 2 , respectively. Both were considerably larger than that of bare GC (0.07 cm 2 ). We carefully looked at the kinetic of interfacial electron transfer process and found that the charge-transfer resistance (R ct ) of TRGO/GC electrode (7.83 × 10 6 Ω) was significantly lower than that of N-Gr/GC electrode (4.81 × 10 7 Ω) or bare GC (1.74 × 10 9 Ω). Interestingly, although TRGO/GC electrode had the largest active area and the smallest charge transfer resistance, it did not promote the H 2 O 2 electrochemical reduction. In contrast, N-Gr/GC modified electrode exhibited an enhanced electro-catalytic activity towards H 2 O 2 reduction, which was related to the presence of heterogeneous atoms into the sp 2 carbon network.

  10. Simulated solarlight catalytic reduction of Cr(VI) on microwave–ultrasonication synthesized flower-like CuO in the presence of tartaric acid

    International Nuclear Information System (INIS)

    Xu, Zhihui; Yu, Yaqun; Fang, Di; Liang, Jianru; Zhou, Lixiang

    2016-01-01

    In this study, flower-like CuO was successfully synthesized by a microwave–ultrasound assisted method and well characterized by X-ray diffractions, Fourier transform infrared spectrum, scanning electron microscopy, transmission electron microscopy, specific surface area, UV–vis diffused reflection spectra, X-ray photoelectron spectroscopy and point of zero charge. The photocatalytic performance of the as-prepared CuO was examined on the Cr(VI) reduction in the presence of tartaric acid under simulated solarlight irradiation. The results show that the developed CuO catalyst exhibited good photocatalytic activity with 100% reduction of Cr(VI) after irradiation of 30 min under the test condition of c(Cr(VI)) = 100 μM, catalyst loading = 400 mg/L, c(tartaric acid) = 4 mM and initial pH = 3. The reaction mechanism was proposed. The effects of test parameters, such as catalyst loading, tartaric acid concentration and initial pH, on Cr(VI) reduction efficiency were also investigated. It is worth mentioning that the developed catalyst can work at a relatively wide range of pH with quite high catalytic performance. - Highlights: • Flower-like CuO microstructure was prepared by MW-US assisted method. • The prepared CuO can catalyze the reduction Cr(VI) by tartaric acid under simulated solarlight. • The formation of ≡Cu(II)-tartaric acid complex play a key role in the reduction of Cr(VI). • The catalyst can operate effectively at a relatively wide range of pH.

  11. Structure Investigation of Ti(IV)BODOLates Involved in the Catalytic Asymmetric Reduction of Ketones Using Catecholborane

    DEFF Research Database (Denmark)

    Sarvary, Ian; Norrby, Per-Ola; Frejd, Torbjörn

    2004-01-01

    The complexes formed on mixing Ti(OiPr)4 and bicyclo-octanediols (BODOLs) 1 and 2 (1:1) are useful as chiral catalysts in asymmetric reductions and were investigated by 1HNMR-spectroscopy and by computational methods. A consistent picture emerged of head-to-tail dimers being kept together via a T...

  12. Enantioselectivity in environmental risk assessment of modern chiral pesticides

    International Nuclear Information System (INIS)

    Ye Jing; Zhao Meirong; Liu Jing; Liu Weiping

    2010-01-01

    Chiral pesticides comprise a new and important class of environmental pollutants nowadays. With the development of industry, more and more chiral pesticides will be introduced into the market. But their enantioselective ecotoxicology is not clear. Currently used synthetic pyrethroids, organophosphates, acylanilides, phenoxypropanoic acids and imidazolinones often behave enantioselectively in agriculture use and they always pose unpredictable enantioselective ecological risks on non-target organisms or human. It is necessary to explore the enantioselective toxicology and ecological fate of these chiral pesticides in environmental risk assessment. The enantioselective toxicology and the fate of these currently widely used pesticides have been discussed in this review article. - Chiral pesticides could pose unpredictable enantioselective toxicity on non-target organisms.

  13. Reduction of light cycle oil in catalytic cracking of bitumen-derived crude HGOs through catalyst selection

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Fuchen; Xu, Chunming [State Key Laboratory of Heavy Oil Processing, China University of Petroleum Beijing, 102200 (China); Ng, Siauw H. [National Centre for Upgrading Technology, 1 Oil Patch Drive, Suite A202, Devon, Alberta (Canada); Yui, Sok [Syncrude Research Centre, 9421-17 Avenue, Edmonton, Alberta (Canada)

    2007-09-15

    In an attempt to reduce the production of light cycle oil (LCO), a non-premium fluid catalytic cracking (FCC) product in North America, a large-pore catalyst containing rare-earth-exchanged Y (REY) zeolite, was used to crack two Canadian bitumen-derived crude heavy gas oils (HGOs) hydrotreated to different extents. For comparison, a regular equilibrium FCC catalyst with ultra-stable Y (USY) zeolite and a conventional western Canadian crude HGO were also included in the study. Cracking experiments were conducted in a fixed-bed microactivity test (MAT) reactor at 510 C, 30 s oil injection time, and varying catalyst-to-oil ratios for different conversions. The results show that pre-cracking of heavy molecules with wide-pore matrix, followed by zeolite cracking, enhanced conversion at the expense of light and heavy cycle oils at a constant catalyst-to-oil ratio, giving improved product selectivities (e.g., higher gasoline and lower dry gas, LCO, and coke yields, in general, at a given conversion). To systematically assess the benefits of employing the specialty catalyst over the regular catalyst in cracking Canadian HGOs, individual product yields were compared at common bases, including constant catalyst-to-oil ratios, conversions, and coke yields for three feeds, and at maximum gasoline yield for one feed. In most cases, the preferred choice of large-pore zeolite-rich catalyst over its counterpart was evident. The observed cracking phenomena were explained based on properties of catalysts and characterization data of feedstocks, including their hydrocarbon type analyses by gas chromatograph with a mass-selective detector (GC-MSD). (author)

  14. 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

  15. In-line localized monitoring of catalyst activity in selective catalytic NO.sub.x reduction systems

    Science.gov (United States)

    Muzio, Lawrence J [Laguna Niguel, CA; Smith, Randall A [Huntington Beach, CA

    2009-12-22

    Localized catalyst activity in an SCR unit for controlling emissions from a boiler, power plant, or any facility that generates NO.sub.x-containing flue gases is monitored by one or more modules that operate on-line without disrupting the normal operation of the facility. Each module is positioned over a designated lateral area of one of the catalyst beds in the SCR unit, and supplies ammonia, urea, or other suitable reductant to the catalyst in the designated area at a rate that produces an excess of the reductant over NO.sub.x on a molar basis through the designated area. Sampling probes upstream and downstream of the designated area draw samples of the gas stream for NO.sub.x analysis, and the catalyst activity is determined from the difference in NO.sub.x levels between the two probes.

  16. Catalytic Activity Enhancement for Oxygen Reduction on Epitaxial Perovskite Thin Films for Solid-Oxide Fuel Cells

    KAUST Repository

    la O', Gerardo Jose; Ahn, Sung-Jin; Crumlin, Ethan; Orikasa, Yuki; Biegalski, Michael D.; Christen, Hans M.; Shao-Horn, Yang

    2010-01-01

    Figure Presented The active ingredient: La0.8Sr 0.2CoO3-δ (LSC) epitaxial thin films are prepared on (001 )-oriented yttria-stabilized zirconia (YSZ) single crystals with a gadolinium-doped ceria (GDC) buffer layer (see picture). The LSC epitaxial films exhibit better oxygen reduction kinetics than bulk LSC. The enhanced activity is attributed in part to higher oxygen nonstoichiometry. © 2010 Wiley-VCH Verlag GmbH & Co. KCaA, Weinheim.

  17. Catalytic Activity Enhancement for Oxygen Reduction on Epitaxial Perovskite Thin Films for Solid-Oxide Fuel Cells

    KAUST Repository

    la O', Gerardo Jose

    2010-06-22

    Figure Presented The active ingredient: La0.8Sr 0.2CoO3-δ (LSC) epitaxial thin films are prepared on (001 )-oriented yttria-stabilized zirconia (YSZ) single crystals with a gadolinium-doped ceria (GDC) buffer layer (see picture). The LSC epitaxial films exhibit better oxygen reduction kinetics than bulk LSC. The enhanced activity is attributed in part to higher oxygen nonstoichiometry. © 2010 Wiley-VCH Verlag GmbH & Co. KCaA, Weinheim.

  18. A general enantioselective route to the chamigrene natural product family

    KAUST Repository

    White, David E.

    2010-06-01

    Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

  19. A general enantioselective route to the chamigrene natural product family

    KAUST Repository

    White, David E.; Stewart, Ian C.; Seashore-Ludlow, Brinton A.; Grubbs, Robert H.; Stoltz, Brian M.

    2010-01-01

    Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

  20. Combustion, performance, and selective catalytic reduction of NOx for a diesel engine operated with combined tri fuel (H_2, CH_4, and conventional diesel)

    International Nuclear Information System (INIS)

    Abu-Jrai, Ahmad M.; Al-Muhtaseb, Ala'a H.; Hasan, Ahmad O.

    2017-01-01

    In this study, the effect of tri fuel (ULSD, H_2, and CH_4) operation under real exhaust gas conditions with different gaseous fuel compositions on the combustion characteristics, engine emissions, and selective catalytic reduction (SCR) after treatment was examined at low, medium, and high engine loads. Pt/Al_2O_3-SCR reactor was used and operated at different exhaust gas temperatures. Results revealed that at low load, the two gaseous fuels (H_2 and CH_4) have the same trend on combustion proccess, where both reduce the in-cylinder pressure and rate of heat release. At the high engine load there was a considerable influence appeared as an increase of the premixed combustion phase and a significant decrease of the total combustion duration. In terms of emissions, it was observed that at high engine load, fuels with high CH_4 content tend to reduce NOx formation, whereas, fuels with high H_2 content tend to reduce PM formation, moreover, combustion of tri fuel with 50:50 fuel mixture resulted in lower BSFC compared to the other ratios and hence, the best engine efficiency. The hydrocarbon-SCR catalyst has shown satisfactory performance in NOx reduction under real diesel exhaust gas in a temperature window of 180–280 °C for all engine loads. - Highlights: • Effect of tri fuel (ULSD, H_2, CH_4) on combustion and engine emissions was examined. • Fuel with high CH_4 content (H50-M50 and H25-M75) tend to reduce NOx formation. • Fuel with high H_2 content (H75-M25 and H50-M50) tend to reduce PM formation. • Increasing the percentage of H_2 in the feed gas improved the NO_x reduction. • The hydrocarbon-SCR catalyst has shown satisfactory performance in NO_x reduction.

  1. Catalytic N2O decomposition and reduction by NH3 over Fe/Beta and Fe/SSZ-13 catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Aiyong; Wang, Yilin; Walter, Eric D.; Kukkadapu, Ravi K.; Guo, Yanglong; Lu, Guanzhong; Weber, Robert S.; Wang, Yong; Peden, Charles H. F.; Gao, Feng

    2018-02-01

    Fe/zeolites are important N2O abatement catalysts, efficient in direct N2O decomposition and (selective) catalytic N2O reduction. In this study, Fe/Beta and Fe/SSZ-13 were synthesized via solution ion-exchange and used to catalyze these two reactions. Nature of the Fe species was probed with UV-vis, Mössbauer and EPR spectroscopies and H2-TPR. The characterizations collectively indicate that isolated and dinuclear Fe sites dominate in Fe/SSZ-13, whereas Fe/Beta contains higher concentrations of oligomeric FexOy species. H2-TPR results suggest that Fe-O interactions are weaker in Fe/SSZ-13, as evidenced by the lower reduction temperatures and higher extents of autoreduction during high-temperature pretreatments in inert gas. Kinetic measurements show that Fe/SSZ-13 has higher activity in catalytic N2O decomposition, thus demonstrating a positive correlation between activity and Fe-O binding, consistent with O2 desorption being rate-limiting for this reaction. However, Fe/Beta was found to be more active in catalyzing N2O reduction by NH3. This indicates that larger active ensembles (i.e., oligomers) are more active for this reaction, consistent with the fact that both N2O and NH3 need to be activated in this case. The authors from PNNL gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle. Aiyong Wang gratefully acknowledges the China Scholarship Council for the Joint-Training Scholarship Program with the Pacific

  2. Combined experimental and theoretical study of the mechanism and enantioselectivity of palladium-catalyzed intermolecular Heck coupling

    DEFF Research Database (Denmark)

    Henriksen, Signe Teuber; Norrby, Per-Ola; Kaukoranta, Päivi

    2008-01-01

    . The steric interactions in this transition state fully account for the enantioselectivity observed with the ligands studied. The calculations also predict relative reactivity and nonlinear mixing effects for the investigated ligands; these predictions are fully validated by experimental testing. Finally......The asymmetric Heck reaction using P,N-ligands has been studied by a combination of theoretical and experimental methods. The reaction follows Halpern-style selectivity; that is, the major isomer is produced from the least favored form of the pre-insertion intermediate. The initially formed Ph......, the low conversion observed with some catalysts was found to be caused by inactivation due to weak binding of the ligand to Pd(0). Adding monodentate PPh3 alleviated the precipitation problem without deteriorating the enantioselectivity and led to one of the most effective catalytic systems to date....

  3. A Catalytic Path for Electrolyte Reduction in Lithium-Ion Cells Revealed by in Situ Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy

    KAUST Repository

    Shi, Feifei; Ross, Philip N.; Zhao, Hui; Liu, Gao; Somorjai, Gabor A.; Komvopoulos, Kyriakos

    2015-01-01

    © 2015 American Chemical Society. Although controlling the interfacial chemistry of electrodes in Li-ion batteries (LIBs) is crucial for maintaining the reversibility, electrolyte decomposition has not been fully understood. In this study, electrolyte decomposition on model electrode surfaces (Au and Sn) was investigated by in situ attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. Simultaneously obtained ATR-FTIR spectra and cyclic voltammetry measurements show that lithium ethylene dicarbonate and lithium propionate form on the Au electrode at 0.6 V, whereas diethyl 2,5-dioxahexane dicarboxylate and lithium propionate form on the Sn electrode surface at 1.25 V. A noncatalytic reduction path on the Au surface and a catalytic reduction path on the Sn surface are introduced to explain the surface dependence of the overpotential and product selectivity. This represents a new concept for explaining electrolyte reactions on the anode of LIBs. The present investigation shows that catalysis plays a dominant role in the electrolyte decomposition process and has important implications in electrode surface modification and electrolyte recipe selection, which are critical factors for enhancing the efficiency, durability, and reliability of LIBs.

  4. A Catalytic Path for Electrolyte Reduction in Lithium-Ion Cells Revealed by in Situ Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy

    KAUST Repository

    Shi, Feifei

    2015-03-11

    © 2015 American Chemical Society. Although controlling the interfacial chemistry of electrodes in Li-ion batteries (LIBs) is crucial for maintaining the reversibility, electrolyte decomposition has not been fully understood. In this study, electrolyte decomposition on model electrode surfaces (Au and Sn) was investigated by in situ attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. Simultaneously obtained ATR-FTIR spectra and cyclic voltammetry measurements show that lithium ethylene dicarbonate and lithium propionate form on the Au electrode at 0.6 V, whereas diethyl 2,5-dioxahexane dicarboxylate and lithium propionate form on the Sn electrode surface at 1.25 V. A noncatalytic reduction path on the Au surface and a catalytic reduction path on the Sn surface are introduced to explain the surface dependence of the overpotential and product selectivity. This represents a new concept for explaining electrolyte reactions on the anode of LIBs. The present investigation shows that catalysis plays a dominant role in the electrolyte decomposition process and has important implications in electrode surface modification and electrolyte recipe selection, which are critical factors for enhancing the efficiency, durability, and reliability of LIBs.

  5. Integrated Removal of NOx with Carbon Monoxide as Reductant, and Capture of Mercury in a Low Temperature Selective Catalytic and Adsorptive Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Neville Pinto; Panagiotis Smirniotis; Stephen Thiel

    2010-08-31

    Coal will likely continue to be a dominant component of power generation in the foreseeable future. This project addresses the issue of environmental compliance for two important pollutants: NO{sub x} and mercury. Integration of emission control units is in principle possible through a Low Temperature Selective Catalytic and Adsorptive Reactor (LTSCAR) in which NO{sub x} removal is achieved in a traditional SCR mode but at low temperature, and, uniquely, using carbon monoxide as a reductant. The capture of mercury is integrated into the same process unit. Such an arrangement would reduce mercury removal costs significantly, and provide improved control for the ultimate disposal of mercury. The work completed in this project demonstrates that the use of CO as a reductant in LTSCR is technically feasible using supported manganese oxide catalysts, that the simultaneous warm-gas capture of elemental and oxidized mercury is technically feasible using both nanostructured chelating adsorbents and ceria-titania-based materials, and that integrated removal of mercury and NO{sub x} is technically feasible using ceria-titania-based materials.

  6. Artificial neural networks study of the catalytic reduction of resazurin: stopped-flow injection kinetic-spectrophotometric determination of Cu(II) and Ni(II)

    International Nuclear Information System (INIS)

    Magni, Diana M.; Olivieri, Alejandro C.; Bonivardi, Adrian L.

    2005-01-01

    An artificial neural network (ANN) procedure was used in the development of a catalytic spectrophotometric method for the determination of Cu(II) and Ni(II) employing a stopped-flow injection system. The method is based on the catalytic action of these ions on the reduction of resazurin by sulfide. ANNs trained by back-propagation of errors allowed us to model the systems in a concentration range of 0.5-6 and 1-15 mg l -1 for Cu(II) and Ni(II), respectively, with a low relative error of prediction (REP) for each cation: REP Cu(II) = 0.85% and REP Ni(II) = 0.79%. The standard deviations of the repeatability (s r ) and of the within-laboratory reproducibility (s w ) were measured using standard solutions of Cu(II) and Ni(II) equal to 2.75 and 3.5 mg l -1 , respectively: s r [Cu(II)] = 0.039 mg l -1 , s r [Ni(II)] = 0.044 mg l -1 , s w [Ni(II)] = 0.045 mg l -1 and s w [Ni(II)] = 0.050 mg l -1 . The ANNs-kinetic method has been applied to the determination of Cu(II) and Ni(II) in electroplating solutions and provided satisfactory results as compared with flame atomic absorption spectrophotometry method. The effect of resazurin, NaOH and Na 2 S concentrations and the reaction temperature on the analytical sensitivity is discussed

  7. Mixture of fuels approach for the synthesis of SrFeO(3-δ) nanocatalyst and its impact on the catalytic reduction of nitrobenzene.

    Science.gov (United States)

    Naveenkumar, Akula; Kuruva, Praveena; Shivakumara, Chikkadasappa; Srilakshmi, Chilukoti

    2014-11-17

    A modified solution combustion approach was applied in the synthesis of nanosize SrFeO(3-δ) (SFO) using single as well as mixture of citric acid, oxalic acid, and glycine as fuels with corresponding metal nitrates as precursors. The synthesized and calcined powders were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis and derivative thermogravimetric analysis (TG-DTG), scanning electron microscopy, transmission electron microscopy, N2 physisorption methods, and acidic strength by n-butyl amine titration methods. The FT-IR spectra show the lower-frequency band at 599 cm(-1) corresponds to metal-oxygen bond (possible Fe-O stretching frequencies) vibrations for the perovskite-structure compound. TG-DTG confirms the formation temperature of SFO ranging between 850-900 °C. XRD results reveal that the use of mixture of fuels in the preparation has effect on the crystallite size of the resultant compound. The average particle size of the samples prepared from single fuels as determined from XRD was ∼50-35 nm, whereas for samples obtained from mixture of fuels, particles with a size of 30-25 nm were obtained. Specifically, the combination of mixture of fuels for the synthesis of SFO catalysts prevents agglomeration of the particles, which in turn leads to decrease in crystallite size and increase in the surface area of the catalysts. It was also observed that the present approach also impacted the catalytic activity of the SFO in the catalytic reduction of nitrobenzene to azoxybenzene.

  8. Program to reduce NOx emissions of HNO{sub 3} plants with selective catalytic reduction; Programme visant a reduire les emissions de NOx d'ateliers d'HNO{sub 3} par reduction catalytique selective

    Energy Technology Data Exchange (ETDEWEB)

    Gry, Ph. [Grande Paroisse SA, Group ATOFINA, 92 - Paris la Defense (France)

    2001-07-01

    Grande Paroisse well known as G.P. has been created in 1919. Nowadays, it is an affiliated company of ATOFINA. The Company is the first French producer of fertilizers and the third West European. In its sites G.P. controls 1.3 millions metric tons per year of nitric acid, on 13 units. Continuous improvement of its technology together with productivity development make G.P. one of the most competitive fertilizer manufacturer. A technical team achieves this objective and maintains a world wide reputable technology. For the past 15 years, industry has tried to reduce NO{sub x} atmospheric pollution. The SCR (Selective Catalytic Reduction) is most used with ammonia for nitric acid units and described here under. (author)

  9. Vancomycin Molecular Interactions: Antibiotic and Enantioselective Mechanisms

    Science.gov (United States)

    Ward, Timothy J.; Gilmore, Aprile; Ward, Karen; Vowell, Courtney

    Medical studies established that vancomycin and other related macrocyclic antibiotics have an enhanced antimicrobial activity when they are associated as dimers. The carbohydrate units attached to the vancomycin basket have an essential role in the dimerization reaction. Covalently synthesized dimers were found active against vancomycin-resistant bacterial strains. A great similarity between antibiotic potential and enantioselectivity was established. A covalent vancomycin dimer was studied in capillary electrophoresis producing excellent chiral separation of dansyl amino acids. Balhimycin is a macrocyclic glycopeptide structurally similar to vancomycin. The small differences are, however, responsible for drastic differences in enantioselectivity in the same experimental conditions. Contributions from studies examining vancomycin's mechanism for antimicrobial activity have substantially aided our understanding of its mechanism in chiral recognition.

  10. A Mild and Convenient Method for the Reduction of Carbonyl Compounds with NaBH{sub 4} in the Presence of Catalytic Amounts of MoCl{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Zeynizadeh, Behzad; Yahyaei, Saiedeh [Urmia University, Urmia (Iran, Islamic Republic of)

    2003-11-15

    NaBH{sub 4} with catalytic amounts of MoCl{sub 5} can readily reduce a variety of carbonyl compounds such as aldehydes, ketones, acyloins, α-diketones and conjugated enones to their corresponding alcohols in good to excellent yields. Reduction reactions were performed under aprotic condition in CH{sub 3}CN at room temperature or reflux. In addition, the chemoselective reduction of aldehydes over ketones was accomplished successfully with this reducing system.

  11. Synthesis of honeycomb-like palladium nanostructures by using cucurbit[7]uril and their catalytic activities for reduction of 4-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Premkumar, Thathan [Department of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), 1 Oryong-dong, Buk-gu, Gwangju 500-712 (Korea, Republic of); The University College/Department of Chemistry, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Geckeler, Kurt E., E-mail: keg@gist.ac.kr [Department of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), 1 Oryong-dong, Buk-gu, Gwangju 500-712 (Korea, Republic of); Department of Nanobio Materials and Electronics (WCU), Gwangju Institute of Science and Technology (GIST), 1 Oryong-dong, Buk-gu, Gwangju 500-712 (Korea, Republic of)

    2014-12-15

    An eco-friendly one-pot method to synthesize self-assembled palladium nanoclusters using a macrocycle, namely cucurbit[7]uril, in the alkaline medium without employing any special reducing or capping agents and/or external energy at room temperature is described. This greener approach, which utilizes water as a benign solvent and biocompatible cucurbit[7]uril as both reducing and protecting agents, can be applied to synthesize other noble metal nanoparticles such as gold, silver, and platinum. Owing to unique structural arrangement of cucurbit[7]uril, it was possible to prepare palladium nanoclusters of honeycomb-like structure irrespective of the reaction conditions. The honeycomb-like palladium nanoclusters were characterized using transmission electron microscopy (TEM), higher-resolution TEM (HR-TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), UV–vis, and FT-IR spectroscopy. Significantly, the synthesized palladium nanoclusters exhibited catalytic activity for the reduction reaction of 4-nitrophenol at room temperature. The approach launched here is easy, green, and user-friendly in contrast to the conventional techniques using polymers or surfactants and harsh reductants. - Highlights: • A simple and one-pot method to synthesis palladium nanostructures with honey-comb like structure. • The strategy established here does not require any harsh and toxic reducing agents. • It has a potential to be a general method for the synthesis of metal nanoparticles in water medium. • Palladium nanoclusters can be used as catalyst for the reduction reaction of 4-nitrophenol. • This system makes a novel platform for industrial and biomedical applications.

  12. A novel bio-degradable polymer stabilized Ag/TiO2 nanocomposites and their catalytic activity on reduction of methylene blue under natural sun light.

    Science.gov (United States)

    Geetha, D; Kavitha, S; Ramesh, P S

    2015-11-01

    In the present work we defined a novel method of TiO2 doped silver nanocomposite synthesis and stabilization using bio-degradable polymers viz., chitosan (Cts) and polyethylene glycol (PEG). These polymers are used as reducing agents. The instant formation of AgNPs was analyzed by visual observation and UV-visible spectrophotometer. TiO2 nanoparticles doped at different concentrations viz., 0.03, 0.06 and 0.09mM on PEG/Cts stabilized silver (0.04wt%) were successfully synthesized. This study presents a simple route for the in situ synthesis of both metal and polymer confined within the nanomaterial, producing ternary hybrid inorganic-organic nanomaterials. The results reveal that they have higher photocatalytic efficiencies under natural sun light. The synthesized TiO2 doped Ag nanocomposites (NCs) were characterized by SEM/EDS, TEM, XRD, FTIR and DLS with zeta potential. The stability of Ag/TiO2 nanocomposite is due to the high negative values of zeta potential and capping of constituents present in the biodegradable polymer which is evident from zeta potential and FT-IR studies. The XRD and EDS pattern of synthesized Ag/TiO2 NCs showed their crystalline structure, with face centered cubic geometry oriented in (111) plane. AFM and DLS studies revealed that the diameter of stable Ag/TiO2 NCs was approximately 35nm. Moreover the catalytic activity of synthesize Ag/TiO2 NCs in the reduction of methylene blue was studied by UV-visible spectrophotometer. The synthesized Ag/TiO2 NCs are observed to have a good catalytic activity on the reduction of methylene blue by bio-degradable which is confirmed by the decrease in absorbance maximum value of methylene blue with respect to time using UV-vis spectrophotometer. The significant enhancement in the photocatalytic activity of Ag/TiO2 nanocomposites under sun light irradiation can be ascribed to the effect of noble metal Ag by acting as electron traps in TiO2 band gap. Copyright © 2015. Published by Elsevier Inc.

  13. Selective catalytic reduction of NOx in lean-burn engine exhaust over a Pt/V/MCM-41 catalyst

    International Nuclear Information System (INIS)

    Jeon, Jong Yeol; Kim, Hee Young; Woo, Seong Ihl

    2003-01-01

    The activities of Pt supported on various metal-substituted MCM-41 (V-, Ti-, Fe-, Al-, Ga-, La-, Co-, Mo-, Ce-, and Zr-MCM-41) and V-impregnated MCM-41 were investigated for the reduction of NO by C 3 H 6 . Among these catalysts, Pt supported on V-impregnated MCM-41 showed the best activity. The maximum conversion of NO into N 2 +N 2 O over this Pt/V/MCM-41 catalyst (Pt=1wt.%, V=3.8wt.%) was 73%, and this maximum conversion was sustained over a temperature range of 70C from 270 to 340C. The high activity of Pt/V/MCM-41 over a broad temperature range resulted from two additional reactions besides the reaction occurring on usual supported Pt, the reaction of NO with surface carbonaceous materials, and the reaction of NO occurring on support V-impregnated MCM-41. The former additional reaction showed an oscillation characteristic, a phenomenon in which the concentrations of parts of reactant and product gases oscillate continuously. At low temperature, some water vapor injected into the reactant gas mixture promoted the reaction occurring on usual supported Pt, whereas at high temperature, it suppressed the additional reaction related to carbonaceous materials. Five-hundred parts per million of SO 2 added to the reactant gas mixture only slightly decreased the NO conversion of Pt/V/MCM-41

  14. Preparation of zeolite supported TiO{sub 2}, ZnO and ZrO{sub 2} and the study on their catalytic activity in NO{sub x} reduction and 1-pentanol dehydration

    Energy Technology Data Exchange (ETDEWEB)

    Fatimah, Is [Chemistry Department, Islamic University of Indonesia Kampus Terpadu UII, Jl. Kaliurang Km 14, Sleman, Yogyakarta (Indonesia)

    2016-03-29

    Preparation of zeolite supported TiO{sub 2}, ZnO and ZrO{sub 2} and their catalytic activity was studied. Activated natural zeolite from Indonesia was utilized for the preparation and catalytic activity test on NO{sub x} reduction by NH{sub 3} and also 1-pentanol dehydration were examined. Physicochemical characterization of materials was studied by x-ray diffraction (XRD) measurement, scanning electron microscope, solid acidity determination and also gas sorption analysis. The results confirmed that the preparation gives some improvements on physicochemical characters suitable for catalysis mechanism in those reactions. Solid acidity and specific surface area contributed significantly to the activity.

  15. Fluxional additives: a second generation control in enantioselective catalysis.

    Science.gov (United States)

    Sibi, Mukund P; Manyem, Shankar; Palencia, Hector

    2006-10-25

    The concept of "fluxional additives", additives that can adopt enantiomeric conformations depending on the chiral information in the ligand, is demonstrated in enantioselective Diels-Alder and nitrone cycloaddition reactions. The additive design is modular, and diverse structures are accessible in three steps. Chiral Lewis acids from main group and transition metals show enhancements in enantioselectivity in the presence of these additives.

  16. Tin-free enantioselective radical reactions using silanes.

    Science.gov (United States)

    Sibi, Mukund P; Yang, Yong-Hua; Lee, Sunggi

    2008-12-04

    Readily available hexyl silane is an excellent choice as a H-atom donor and a chain carrier in Lewis acid mediated enantioselective radical reactions. Conjugate radical additions to alpha,beta-unsaturated imides at room temperature proceed in good yields and excellent enantioselectivities.

  17. Chiral amides via copper-catalysed enantioselective conjugate addition

    NARCIS (Netherlands)

    Schoonen, Anne K.; Fernández-Ibáñez, M. Ángeles; Fañanás-Mastral, Martín; Teichert, Johannes F.; Feringa, Bernard

    2014-01-01

    A highly enantioselective one pot procedure for the synthesis of beta-substituted amides was developed starting from the corresponding alpha,beta-unsaturated esters. This new methodology is based on the copper-catalysed enantioselective conjugate addition of Grignard reagents to

  18. Selective catalytic reduction of NO{sub x} with NH{sub 3} over iron-cerium-tungsten mixed oxide catalyst prepared by different methods

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, Zhi-bo, E-mail: xzb328@163.com [School of Energy and Power Engineering, University of Shanghai for Science & Technology, Shanghai 200093 (China); Collaborative Innovation Research Institute, University of Shanghai for Science & Technology, Shanghai 200093 (China); Shanghai Power Equipment Research Institute, Shanghai 200240 (China); Liu, Jing; Zhou, Fei; Liu, Dun-yu; Lu, Wei [School of Energy and Power Engineering, University of Shanghai for Science & Technology, Shanghai 200093 (China); Jin, Jing [School of Energy and Power Engineering, University of Shanghai for Science & Technology, Shanghai 200093 (China); Collaborative Innovation Research Institute, University of Shanghai for Science & Technology, Shanghai 200093 (China); Ding, Shi-fa [Shanghai Power Equipment Research Institute, Shanghai 200240 (China)

    2017-06-01

    Highlights: • Iron-cerium-tungsten mixed oxide catalysts were prepared through three different methods. • The effect of preparation methods on the NH{sub 3}-SCR activity and the surface structure properties of catalyst were investigated. • Iron-cerium-tungsten mixed oxide prepared through microwave irradiation assistant critic acid sol-gel shows higher NH{sub 3}-SCR activity. - Abstract: A series of magnetic Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z} catalysts were synthesized by three different methods(Co-precipitation(Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-CP), Hydrothermal treatment assistant critic acid sol-gel method(Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-HT) and Microwave irradiation assistant critic acid sol-gel method(Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-MW)), and the catalytic activity was evaluated for selective catalytic reduction of NO with NH{sub 3}. The catalyst was characterized by XRD, N{sub 2} adsorption-desorption, XPS, H{sub 2}-TPR and NH{sub 3}-TPD. Among the tested catalysts, Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-MW shows the highest NO{sub x} conversion over per gram in unit time with NO{sub x} conversion of 60.8% at 350 °C under a high gas hourly space velocity of 1,200,000 ml/(g h). Different from Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-CP catalyst, there exists a large of iron oxide crystallite(γ-Fe{sub 2}O{sub 3} and α-Fe{sub 2}O{sub 3}) scattered in Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z} catalysts prepared through hydrothermal treatment or microwave irradiation assistant critic acid sol-gel method, and higher iron atomic concentration on their surface. And Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-MW shows higher surface absorbed oxygen concentration and better dispersion compared with Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-HT catalyst. These features were favorable for the high catalytic performance of NO reduction with NH{sub 3} over Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-MW catalyst.

  19. Optimization of the fluid catalytic cracking unit performance by application of a high motor Octane catalyst and reduction of gasoline vapour pressure

    International Nuclear Information System (INIS)

    Chavdarov, I.; Stratiev, D.; Shishkova, I.; Dinkov, R.; Petkov, P.

    2013-01-01

    Full text: The fluid catalytic cracking (FCC) gasoline is the main contributor to the refinery gasoline pool in the LUKOIL Neftohim Burgas (LNB) refinery. Next in quantity contributor in the refinery gasoline pool is the reformate. The FCC gasoline sensitivity (MON-RON) is about 12 points. The reformer gasoline sensitivity is 11 points. The high sensitivity of the main contributors to the LNB refinery gasoline pool leads to a shortage in the motor octane number. For that reason a selection of an FCC catalyst that is capable of increasing the motor octane number of the FCC gasoline was performed. The application of this catalyst in the LNB FCC unit has led to an increase of the motor octane number of the FCC gasoline by 0.5 points, which enabled the refinery to increase the production of automotive gasolines by 1.3 % and to increase the share of premium automotive gasoline by 5 %. This had an effect of improvement of the refinery economics by a six figure number of US $ per year. The optimization of the FCC gasoline Reid Vapor Pressure (RVP) during the winter season, consisting in a reduction of the RVP from 60 to 50 kPa and an increase of the FCC C 4 olefins yield, has led to an augmentation of high motor octane number alkylate production. As a result the refinery economics was improved by a five figure number of US $ per year. key words: FCC gasoline motor octane number, gasoline RVP, FCC operation profitability

  20. Influence of flue gas desulfurization (FGD) installations on emission characteristics of PM2.5 from coal-fired power plants equipped with selective catalytic reduction (SCR).

    Science.gov (United States)

    Li, Zhen; Jiang, Jingkun; Ma, Zizhen; Fajardo, Oscar A; Deng, Jianguo; Duan, Lei

    2017-11-01

    Flue gas desulfurization (FGD) and selective catalytic reduction (SCR) technologies have been widely used to control the emissions of sulphur dioxide (SO 2 ) and nitrogen oxides (NO X ) from coal-fired power plants (CFPPs). Field measurements of emission characteristics of four conventional CFPPs indicated a significant increase in particulate ionic species, increasing PM 2.5 emission with FGD and SCR installations. The mean concentrations of PM 2.5 from all CFPPs tested were 3.79 ± 1.37 mg/m 3 and 5.02 ± 1.73 mg/m 3 at the FGD inlet and outlet, respectively, and the corresponding contributions of ionic species were 19.1 ± 7.7% and 38.2 ± 7.8%, respectively. The FGD was found to enhance the conversion of NH 3 slip from the SCR to NH 4 + in the PM 2.5 , together with the conversion of SO 2 to SO 4 2- , and increased the primary NH 4 + and SO 4 2- aerosol emissions by approximately 18.9 and 4.2 times, respectively. This adverse effect should be considered when updating the emission inventory of CFPPs and should draw the attention of policy-makers for future air pollution control. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Facile approach to synthesize uniform Au@mesoporous SnO{sub 2} yolk–shell nanoparticles and their excellent catalytic activity in 4-nitrophenol reduction

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ya [Changchun University of Science and Technology, School of Chemistry & Environmental Engineering (China); Li, Lu; Wang, Chungang, E-mail: wangcg925@nenu.edu.cn [Northeast Normal University, Faculty of Chemistry (China); Wang, Tingting, E-mail: wangtt@cust.edu.cn [Changchun University of Science and Technology, School of Chemistry & Environmental Engineering (China)

    2016-01-15

    Monodispersed and uniform Au@mesoporous SnO{sub 2} yolk–shell nanoparticles (Au@mSnO{sub 2} yolk–shell NPs) composed of the moveable Au NP cores and mSnO{sub 2} shells have been successfully fabricated via a facile and reproducible approach. The outside mSnO{sub 2} shells of Au@mSnO{sub 2} yolk–shell NPs not only prevent Au NPs from aggregating and corroding by the reaction solution but also allow the Au NPs to contact with reactant molecules easily through the mesoporous channels. The obtained Au@mSnO{sub 2} yolk–shell NPs are characterized by means of transmission electron microscope, scanning electron microscopy, X-ray powder diffraction, X-ray photoelectron spectrum, and UV–vis absorption spectroscopy. The synthesized materials exhibit excellent catalytic performance and high stability towards the reduction of 4-nitrophenol with NaBH{sub 4} as a reducing agent, which may be ascribed to their high specific surface area and unique mesoporous structure. Moreover, the synthetic strategy reported in this paper can be extended to fabricate a series of multifunctional noble metal@metal oxide yolk–shell nanocomposite materials with unique properties for various applications.

  2. Promoted V2O5/TiO2 catalysts for selective catalytic reduction of NO with NH3 at low temperatures

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Schill, Leonhard; Godiksen, Anita

    2016-01-01

    characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR, Raman, FTIR and EPR spectroscopy to investigate the properties of the catalysts. XRPD, Raman and FTIR showed that promotion with 15 wt.% HPA does not cause V2O5 to be present in crystalline form, also at a loading of 5 wt.% V2O5. Hence, use of HPAs does......The influence of varying the V2O5 content (3–6 wt.%) was studied for the selective catalytic reduction (SCR) of nitrogen oxides by ammonia on heteropoly acid (HPA)- and tungsten oxide (WO3)-promoted V2O5/TiO2 catalysts. The SCR activity and alkali deactivation resistance of HPA-promoted V2O5/TiO2...... catalysts was found to be much higher than for WO3-promoted catalysts. By increasing the vanadium content from 3 to 5 wt.% the catalysts displayed a two fold increase in activity at 225 °C and retained their initial activity after alkali doping at a molar K/V ratio of 0.181. Furthermore, the catalysts were...

  3. Reducing NO(x) emissions from a nitric acid plant of domestic petrochemical complex: enhanced conversion in conventional radial-flow reactor of selective catalytic reduction process.

    Science.gov (United States)

    Abbasfard, Hamed; Hashemi, Seyed Hamid; Rahimpour, Mohammad Reza; Jokar, Seyyed Mohammad; Ghader, Sattar

    2013-01-01

    The nitric acid plant of a domestic petrochemical complex is designed to annually produce 56,400 metric tons (based on 100% nitric acid). In the present work, radial-flow spherical bed reactor (RFSBR) for selective catalytic reduction of nitric oxides (NO(x)) from the stack of this plant was modelled and compared with the conventional radial-flow reactor (CRFR). Moreover, the proficiency of a radial-flow (water or nitrogen) membrane reactor was also compared with the CRFR which was found to be inefficient at identical process conditions. In the RFSBR, the space between the two concentric spheres is filled by a catalyst. A mathematical model, including conservation of mass has been developed to investigate the performance of the configurations. The model was checked against the CRFR in a nitric acid plant located at the domestic petrochemical complex. A good agreement was observed between the modelling results and the plant data. The effects of some important parameters such as pressure and temperature on NO(x) conversion were analysed. Results show 14% decrease in NO(x) emission annually in RFSBR compared with the CRFR, which is beneficial for the prevention of NO(x) emission, global warming and acid rain.

  4. 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.

  5. Deactivation of La-Fe-ZSM-5 catalyst for selective catalytic reduction of NO with NH{sup 3}. Field study results

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Gongshin; Yang, Ralph T. [Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109 (United States); Chang, Ramsay; Cardoso, Sylvio [Air Pollution Control, Power Generation, Electric Power Research Institute, Palo Alto, CA 94304-1395 (United States); Smith, Randall A. [Fossil Energy Research Corporation, Laguna Hills, CA 92653 (United States)

    2004-11-08

    Results are summarized for a study on the effects of poisons on the La-Fe-ZSM-5 catalyst activity for the selective catalytic reduction of NO by ammonia. The deactivation of La-Fe-ZSM-5 honeycombs was studied in field tests. A honeycomb catalyst containing 25%La-Fe-ZSM-5 had an overall activity similar to that of a commercial vanadia honeycomb catalyst. Long-term activity test results show that the 25%La-Fe-ZSM-5 catalyst activity decreased to 50% after 300h and 25% after 1769h of on-stream flue gas exposure. The deactivation is correlated to the amounts of poisons deposited on the catalyst. Poisons include alkali and alkaline earth metals, As and Hg. Hg was found to be ion-exchanged from HgCl{sup 2} to form Hg-ZSM-5, and Hg was found to be among the strongest poisons. The poisoning effects of these elements appeared to be additive. Thus, from the chemical analysis of the deactivated catalyst, the deactivation of Fe-ZSM-5 can be predicted.

  6. Ethanol-selective catalytic reduction of NO by Ag/Al2O3 catalysts: Activity and deactivation by alkali salts

    DEFF Research Database (Denmark)

    Schill, Leonhard; Putluru, Siva Sankar Reddy; Jacobsen, Casper Funk

    2012-01-01

    Ag/Al2O3 catalysts with and without potassium doping were prepared by incipient wetness impregnation and characterized by N2 physisorption, XRPD, NH3-TPD and SEM. The influence of the Ag content from 1 to 5 wt.% was investigated for the selective catalytic reduction (SCR) of NO with ethanol. The 3...... wt.% Ag/Al2O3 catalyst was found to be the most active and CO2 selective over a wide temperature window (300–500 ◦C). Addition of 500 ppm of H2 has a mild promotional effect on the activity while SO2 has a strong negative influence on the SCR activity. Furthermore, the Ag/Al2O3 ethanol-SCR catalyst......3 ethanol-SCR catalyst compared to the conventional NH3-SCR catalyst. The still low potassium resistance, in combination with the high sensitivity to SO2, seems not to make these catalysts a real option for biomass fired boilers....

  7. Fe-N-C electrocatalysts for oxygen reduction reaction synthesized by using aniline salt and Fe3+/H2O2 catalytic system

    KAUST Repository

    Bukola, Saheed; Merzougui, Belabbes A.; Akinpelu, Akeem; Laoui, Tahar; Hedhili, Mohamed N.; Swain, Greg M.; Shao, Minhua

    2014-01-01

    Non-precious metal (NPM) catalysts are synthesized by polymerizing aniline salt using an aqueous Fe3+/H2O2 coupled catalytic system on a carbon matrix with a porous creating agent. The sulfur containing compunds such as ammonium peroxydisulfate, are eliminated in this method resulting in a much simpler process. The catalysts' porous structures are enhanced with ammonium carbonate as a sacrificial material that yields voids when decomposed during the heat treatment at 900 °C in N2 atmosphere. Two catalysts Fe-N-C/Vu and Fe-N-C/KB (Vu = Vulcan and KB = Ketjen black) were synthesized and characterized. Their oxygen reduction reaction (ORR) activities were investigated using a rotating ring-disk electrode (RRDE) in both 0.1 M KOH and 0.1 M HClO4. The catalysts show improved ORR activities close to that of Pt-based catalysts, low H2O2 formation and also demonstrated a remarkable tolerance towards methanol oxidation.

  8. Synthesis and kinetics investigation of meso-microporous Cu-SAPO-34 catalysts for the selective catalytic reduction of NO with ammonia.

    Science.gov (United States)

    Liu, Jixing; Yu, Fuhong; Liu, Jian; Cui, Lifeng; Zhao, Zhen; Wei, Yuechang; Sun, Qianyao

    2016-10-01

    A series of meso-microporous Cu-SAPO-34 catalysts were successfully synthesized by a one-pot hydrothermal crystallization method, and these catalysts exhibited excellent NH 3 -SCR performance at low temperature. Their structure and physic chemical properties were characterized by means of X-ray diffraction patterns (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), N 2 sorption-desorption, nuclear magnetic resonance (NMR), Inductively Coupled Plasma-Atomic Emission spectrometer (ICP-AES), X-ray absorption spectroscopy (XPS), Temperature-programmed desorption of ammonia (NH 3 -TPD), Ultraviolet visible diffuse reflectance spectroscopy (UV-Vis DRS) and Temperature programmed reduction (TPR). The analysis results indicate that the high activities of Cu-SAPO-34 catalysts could be attributed to the enhancement of redox property, the formation of mesopores and the more acid sites. Furthermore, the kinetic results verify that the formation of mesopores remarkably reduces diffusion resistance and then improves the accessibility of reactants to catalytically active sites. The 1.0-Cu-SAPO-34 catalyst exhibited the high NO conversion (>90%) among the wide activity temperature window in the range of 150-425°C. Copyright © 2016. Published by Elsevier B.V.

  9. Fe-N-C electrocatalysts for oxygen reduction reaction synthesized by using aniline salt and Fe3+/H2O2 catalytic system

    KAUST Repository

    Bukola, Saheed

    2014-11-01

    Non-precious metal (NPM) catalysts are synthesized by polymerizing aniline salt using an aqueous Fe3+/H2O2 coupled catalytic system on a carbon matrix with a porous creating agent. The sulfur containing compunds such as ammonium peroxydisulfate, are eliminated in this method resulting in a much simpler process. The catalysts\\' porous structures are enhanced with ammonium carbonate as a sacrificial material that yields voids when decomposed during the heat treatment at 900 °C in N2 atmosphere. Two catalysts Fe-N-C/Vu and Fe-N-C/KB (Vu = Vulcan and KB = Ketjen black) were synthesized and characterized. Their oxygen reduction reaction (ORR) activities were investigated using a rotating ring-disk electrode (RRDE) in both 0.1 M KOH and 0.1 M HClO4. The catalysts show improved ORR activities close to that of Pt-based catalysts, low H2O2 formation and also demonstrated a remarkable tolerance towards methanol oxidation.

  10. Synergy of CuO and CeO2 combination for mercury oxidation under low-temperature selective catalytic reduction atmosphere

    KAUST Repository

    Li, Hailong

    2016-07-19

    Synergy for low temperature Hg0 oxidation under selective catalytic reduction (SCR) atmosphere was achieved when copper oxides and cerium oxides were combined in a CuO-CeO2/TiO2 (CuCeTi) catalyst. Hg0 oxidation efficiency as high as 99.0% was observed on the CuCeTi catalyst at 200 °C, even the gas hourly space velocity was extremely high. To analyze the synergistic effect, comparisons of catalyst performance in the presence of different SCR reaction gases were systematically conducted over CuO/TiO2 (CuTi), CeO2/TiO2 (CeTi) and CuCeTi catalysts prepared by sol-gel method. The interactions between copper oxides and cerium oxides in CuCeTi catalyst yielded more surface chemisorbed oxygen, and facilitated the conversion of gas-phase O2 to surface oxygen, which are favorable for Hg0 oxidation. Copper oxides in the combination interacted with NO forming more chemisorbed oxygen for Hg0 oxidation in the absence of gas-phase O2. Cerium oxides in the combination promoted Hg0 oxidation through enhancing the transformations of NO to NO2. In the absence of NO, NH3 exhibited no inhibitive effect on Hg0 oxidation, because enough Lewis acid sites due to the combination of copper oxides and cerium oxides scavenged the competitive adsorption between NH3 and Hg0. In the presence of NO, although NH3 lowered Hg0 oxidation rate through inducing reduction of oxidized mercury, complete recovery of Hg0 oxidation activity over the CuCeTi catalyst was quickly achieved after cutting off NH3. This study revealed the synergistic effect of the combination of copper oxides and cerium oxides on Hg0 oxidation, and explored the involved mechanisms. Such knowledge would help obtaining maximum Hg0 oxidation co-benefit from SCR units in coal-fired power plants.

  11. Adaptation of HepG2 cells to a steady-state reduction in the content of protein phosphatase 6 (PP6) catalytic subunit

    Energy Technology Data Exchange (ETDEWEB)

    Boylan, Joan M. [Department of Pediatrics, Brown University and Rhode Island Hospital, Providence, RI (United States); Salomon, Arthur R. [Department of Molecular Biology, Cell Biology and Biochemistry, Brown University, Providence, RI (United States); Department of Chemistry, Brown University, Providence, RI (United States); Tantravahi, Umadevi [Division of Genetics, Department of Pathology, Brown University and Women and Infants Hospital, Providence, RI (United States); Gruppuso, Philip A., E-mail: philip_gruppuso@brown.edu [Department of Pediatrics, Brown University and Rhode Island Hospital, Providence, RI (United States); Department of Molecular Biology, Cell Biology and Biochemistry, Brown University, Providence, RI (United States)

    2015-07-15

    Protein phosphatase 6 (PP6) is a ubiquitous Ser/Thr phosphatase involved in an array of cellular processes. To assess the potential of PP6 as a therapeutic target in liver disorders, we attenuated expression of the PP6 catalytic subunit in HepG2 cells using lentiviral-transduced shRNA. Two PP6 knock-down (PP6KD) cell lines (90% reduction of PP6-C protein content) were studied in depth. Both proliferated at a rate similar to control cells. However, flow cytometry indicated G2/M cell cycle arrest that was accounted for by a shift of the cells from a diploid to tetraploid state. PP6KD cells did not show an increase in apoptosis, nor did they exhibit reduced viability in the presence of bleomycin or taxol. Gene expression analysis by microarray showed attenuated anti-inflammatory signaling. Genes associated with DNA replication were downregulated. Mass spectrometry-based phosphoproteomic analysis yielded 80 phosphopeptides representing 56 proteins that were significantly affected by a stable reduction in PP6-C. Proteins involved in DNA replication, DNA damage repair and pre-mRNA splicing were overrepresented among these. PP6KD cells showed intact mTOR signaling. Our studies demonstrated involvement of PP6 in a diverse set of biological pathways and an adaptive response that may limit the effectiveness of targeting PP6 in liver disorders. - Highlights: • Lentiviral-transduced shRNA was used to generate a stable knockdown of PP6 in HepG2 cells. • Cells adapted to reduced PP6; cell proliferation was unaffected, and cell survival was normal. • However, PP6 knockdown was associated with a transition to a tetraploid state. • Genomic profiling showed downregulated anti-inflammatory signaling and DNA replication. • Phosphoproteomic profiling showed changes in proteins associated with DNA replication and repair.

  12. Adaptation of HepG2 cells to a steady-state reduction in the content of protein phosphatase 6 (PP6) catalytic subunit

    International Nuclear Information System (INIS)

    Boylan, Joan M.; Salomon, Arthur R.; Tantravahi, Umadevi; Gruppuso, Philip A.

    2015-01-01

    Protein phosphatase 6 (PP6) is a ubiquitous Ser/Thr phosphatase involved in an array of cellular processes. To assess the potential of PP6 as a therapeutic target in liver disorders, we attenuated expression of the PP6 catalytic subunit in HepG2 cells using lentiviral-transduced shRNA. Two PP6 knock-down (PP6KD) cell lines (90% reduction of PP6-C protein content) were studied in depth. Both proliferated at a rate similar to control cells. However, flow cytometry indicated G2/M cell cycle arrest that was accounted for by a shift of the cells from a diploid to tetraploid state. PP6KD cells did not show an increase in apoptosis, nor did they exhibit reduced viability in the presence of bleomycin or taxol. Gene expression analysis by microarray showed attenuated anti-inflammatory signaling. Genes associated with DNA replication were downregulated. Mass spectrometry-based phosphoproteomic analysis yielded 80 phosphopeptides representing 56 proteins that were significantly affected by a stable reduction in PP6-C. Proteins involved in DNA replication, DNA damage repair and pre-mRNA splicing were overrepresented among these. PP6KD cells showed intact mTOR signaling. Our studies demonstrated involvement of PP6 in a diverse set of biological pathways and an adaptive response that may limit the effectiveness of targeting PP6 in liver disorders. - Highlights: • Lentiviral-transduced shRNA was used to generate a stable knockdown of PP6 in HepG2 cells. • Cells adapted to reduced PP6; cell proliferation was unaffected, and cell survival was normal. • However, PP6 knockdown was associated with a transition to a tetraploid state. • Genomic profiling showed downregulated anti-inflammatory signaling and DNA replication. • Phosphoproteomic profiling showed changes in proteins associated with DNA replication and repair

  13. Hybrid selective noncatalytic reduction (SNCR)/selective catalytic reduction (SCR) for NOx removal using low-temperature SCR with Mn-V2O5/TiO2 catalyst.

    Science.gov (United States)

    Choi, Sung-Woo; Choi, Sang-Ki; Bae, Hun-Kyun

    2015-04-01

    A hybrid selective noncatalytic reduction/selective catalytic reduction (SNCR/SCR) system that uses two types of technology, low-temperature SCR process and SNCR process, was designed to develop nitrogen oxide (NOx) reduction technology. SCR was conducted with space velocity (SV)=2400 hr(-1) and hybrid SNCR/SCR with SV=6000 hr(-1), since the study focused on reducing the amount of catalyst and both achieved 98% NOx reduction efficiency. Characteristics of NOx reduction by NH3 were studied for low-temperature SCR system at 150 °C using Mn-V2O5/TiO2 catalyst. Mn-added V2O5/TiO2 catalyst was produced, and selective catalyst reduction of NOx by NH3 was experimented. NOx reduction rate according to added Mn content in Mn-V2O5/TiO2 catalyst was studied with varying conditions of reaction temperature, normalized stoichiometric ratio (NSR), SV, and O2 concentration. In the catalyst experiment according to V2O5 concentration, 1 wt.% V2O5 catalyst showed the highest NOx reduction rate: 98% reduction at temperature window of 200~250 °C. As a promoter of the V2O5 catalyst, 5 wt.% Mn was added, and the catalyst showed 47~90% higher efficiency even with low temperatures, 100~200 °C. Mn-V2O5/TiO2 catalyst, prepared by adding 5 wt.% Mn in V2O5/TiO2 catalyst, showed increments of catalyst activation at 150 °C as well as NOx reduction. Mn-V2O5/TiO2 catalyst showed 8% higher rate for NOx reduction compared with V2O5/TiO2 catalyst in 150 °C SCR. Thus, (5 wt.%)Mn-(1 wt.%)V2O5/TiO2 catalyst was applied in SCR of hybrid SNCR/SCR system of low temperature at 150 °C. Low-temperature SCR hybrid SNCR/SCR (150 °C) system and hybrid SNCR/SCR (350 °C) showed 91~95% total reduction rate with conditions of SV=2400~6000 hr(-1) SCR and 850~1050 °C SNCR, NSR=1.5~2.0, and 5% O2. Hybrid SNCR/SCR (150 °C) system proved to be more effective than the hybrid SNCR/SCR (350 °C) system at low temperature. NOx control is very important, since they are the part of greenhouse gases as well as the

  14. The influence of a silica pillar in lamellar tetratitanate for selective catalytic reduction of NO{sub x} using NH{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Nogueira da Cunha, Beatriz; Gonçalves, Alécia Maria; Gomes da Silveira, Rafael [Institute of Chemistry, Federal University of Goiás, C. Postal 131, CEP 74001-970 Goiânia, GO (Brazil); Urquieta-González, Ernesto A. [Laboratory of Applied Catalysis, Department of Chemical Engineering, Federal University of Sao Carlos, Rodovia Washington Luis Km 235, C. Postal 676, CEP 13565-905 São Carlos, SP (Brazil); Magalhães Nunes, Liliane, E-mail: lilianemnunes@gmail.com [Institute of Chemistry, Federal University of Goiás, C. Postal 131, CEP 74001-970 Goiânia, GO (Brazil)

    2015-01-15

    Highlights: • Potassium ions significantly affected the SCR. • The introduction of silica in the catalyst promotes the NH{sub 3}-SCR reaction. • The catalysts activities were not significantly influenced by SO{sub 2} addition. - Abstract: Silica-pillared layered titanate (SiO{sub 2}–Ti{sub 4}O{sub 9}) was prepared by intercalating organosilanes into the interlayers of a layered K{sub 2}Ti{sub 4}O{sub 9} followed by calcination at 500 °C. The lamellar titanates produced were used as a support to prepare vanadium catalysts (1 and 2 wt%) through wet impregnation for selective catalytic reduction (SCR) of NO. The catalysts were characterized using nitrogen adsorption (BET), X-ray diffraction (XRD), temperature programmed reduction (H{sub 2}-TPR), nuclear magnetic resonance ({sup 29}Si NMR), and infrared spectroscopy (FT-IR). Reduction of NO by NH{sub 3} was studied in a fixed-bed reactor packed with the catalysts and fed a mixture comprising 1% NH{sub 3}, 1% NO, 10% O{sub 2}, and 34 ppm SO{sub 2} (when used) in helium. The results demonstrate that activity is correlated with the support, i.e., with acidic strength of catalysts. The potassium in the support, K{sub 2}Ti{sub 4}O{sub 9}, significantly affected the reaction and level of vanadium species reduction. The catalyst (1VSiT) with 1 wt% vanadium impregnated on the SiO{sub 2}–Ti{sub 4}O{sub 9} support reduced ∼80% of the NO. Approximately the same conversion rate was generated on the catalyst (2VSiT) with 2 wt% vanadium using the same support. The increased NH{sub 3} adsorption demonstrate that introduction of silica in the catalyst promotes the NH{sub 3}-SCR reaction. More importantly, 2VSiT and 1VSiT were strongly resistant to SO{sub 2} poisoning.

  15. The effect of soot on ammonium nitrate species and NO2 selective catalytic reduction over Cu-zeolite catalyst-coated particulate filter.

    Science.gov (United States)

    Mihai, Oana; Tamm, Stefanie; Stenfeldt, Marie; Olsson, Louise

    2016-02-28

    A selective catalytic reduction (SCR)-coated particulate filter was evaluated by means of dynamic tests performed using NH3, NO2, O2 and H2O. The reactions were examined both prior to and after soot removal in order to study the effect of soot on ammonium nitrate formation and decomposition, ammonia storage and NO2 SCR. A slightly larger ammonia storage capacity was observed when soot was present in the sample, which indicated that small amounts of ammonia can adsorb on the soot. Feeding of NO2 and NH3 in the presence of O2 and H2O at low temperature (150, 175 and 200°C) leads to a large formation of ammonium nitrate species and during the subsequent temperature ramp using H2O and argon, a production of nitrous oxides was observed. The N2O formation is often related to ammonium nitrate decomposition, and our results showed that the N2O formation was clearly decreased by the presence of soot. We therefore propose that in the presence of soot, there are fewer ammonium nitrate species on the surface due to the interactions with the soot. Indeed, we do observe CO2 production during the reaction conditions also at 150°C, which shows that there is a reaction with these species and soot. In addition, the conversion of NOx due to NO2 SCR was significantly enhanced in the presence of soot; we attribute this to the smaller amount of ammonium nitrate species present in the experiments where soot is available since it is well known that ammonium nitrate formation is a major problem at low temperature due to the blocking of the catalytic sites. Further, a scanning electron microscopy analysis of the soot particles shows that they are about 30-40 nm and are therefore too large to enter the pores of the zeolites. There are likely CuxOy or other copper species available on the outside of the zeolite crystallites, which could have been enhanced due to the hydrothermal treatment at 850°C of the SCR-coated filter prior to the soot loading. We therefore propose that soot is

  16. Synthesis of Superparamagnetic Core-Shell Structure Supported Pd Nanocatalysts for Catalytic Nitrite Reduction with Enhanced Activity, No Detection of Undesirable Product of Ammonium, and Easy Magnetic Separation Capability.

    Science.gov (United States)

    Sun, Wuzhu; Yang, Weiyi; Xu, Zhengchao; Li, Qi; Shang, Jian Ku

    2016-01-27

    Superparamagnetic nanocatalysts could minimize both the external and internal mass transport limitations and neutralize OH(-) produced in the reaction more effectively to enhance the catalytic nitrite reduction efficiency with the depressed product selectivity to undesirable ammonium, while possess an easy magnetic separation capability. However, commonly used qusi-monodispersed superparamagnetic Fe3O4 nanosphere is not suitable as catalyst support for nitrite reduction because it could reduce the catalytic reaction efficiency and the product selectivity to N2, and the iron leakage could bring secondary contamination to the treated water. In this study, protective shells of SiO2, polymethylacrylic acid, and carbon were introduced to synthesize Fe3O4@SiO2/Pd, Fe3O4@PMAA/Pd, and Fe3O4@C/Pd catalysts for catalytic nitrite reduction. It was found that SiO2 shell could provide the complete protection to Fe3O4 nanosphere core among these shells. Because of its good dispersion, dense structure, and complete protection to Fe3O4, the Fe3O4@SiO2/Pd catalyst demonstrated the highest catalytic nitrite reduction activity without the detection of NH4(+) produced. Due to this unique structure, the activity of Fe3O4@SiO2/Pd catalysts for nitrite reduction was found to be independent of the Pd nanoparticle size or shape, and their product selectivity was independent of the Pd nanoparticle size, shape, and content. Furthermore, their superparamagnetic nature and high saturation magnetization allowed their easy magnetic separation from treated water, and they also demonstrated a good stability during the subsequent recycling experiment.

  17. The Effect of Acidic and Redox Properties of V2O5/CeO2-ZrO2 Catalysts in Selective Catalytic Reduction of NO by NH3

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Riisager, Anders; Fehrmann, Rasmus

    2009-01-01

    V2O5 supported ZrO2 and CeO2–ZrO2 catalysts were prepared and characterized by N2 physisorption, XRPD, TPR, and NH3-TPD methods. The influence of calcination temperature from 400 to 600 °C on crystallinity, acidic and redox properties were studied and compared with the catalytic activity...... in the selective catalytic reduction (SCR) of NO with ammonia. The surface area of the catalysts decreased gradually with increasing calcination temperature. The SCR activity of V2O5/ZrO2 catalysts was found to be related with the support crystallinity, whereas V2O5/CeO2–ZrO2 catalysts were also dependent...... on acidic and redox properties of the catalyst. The V2O5/CeO2–ZrO2 catalysts showed high activity and selectivity for reduction of NO with NH3....

  18. 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.

  19. Influence on the oxidative potential of a heavy-duty engine particle emission due to selective catalytic reduction system and biodiesel blend.

    Science.gov (United States)

    Godoi, Ricardo H M; Polezer, Gabriela; Borillo, Guilherme C; Brown, Andrew; Valebona, Fabio B; Silva, Thiago O B; Ingberman, Aline B G; Nalin, Marcelo; Yamamoto, Carlos I; Potgieter-Vermaak, Sanja; Penteado Neto, Renato A; de Marchi, Mary Rosa R; Saldiva, Paulo H N; Pauliquevis, Theotonio; Godoi, Ana Flavia L

    2016-08-01

    Although the particulate matter (PM) emissions from biodiesel fuelled engines are acknowledged to be lower than those of fossil diesel, there is a concern on the impact of PM produced by biodiesel to human health. As the oxidative potential of PM has been suggested as trigger for adverse health effects, it was measured using the Electron Spin Resonance (OP(ESR)) technique. Additionally, Energy Dispersive X-ray Fluorescence Spectroscopy (EDXRF) was employed to determine elemental concentration, and Raman Spectroscopy was used to describe the amorphous carbon character of the soot collected on exhaust PM from biodiesel blends fuelled test-bed engine, with and without Selective Catalytic Reduction (SCR). OP(ESR) results showed higher oxidative potential per kWh of PM produced from a blend of 20% soybean biodiesel and 80% ULSD (B20) engine compared with a blend of 5% soybean biodiesel and 95% ULSD (B5), whereas the SCR was able to reduce oxidative potential for each fuel. EDXRF data indicates a correlation of 0.99 between concentration of copper and oxidative potential. Raman Spectroscopy centered on the expected carbon peaks between 1100cm(-1) and 1600cm(-1) indicate lower molecular disorder for the B20 particulate matter, an indicative of a more graphitic carbon structure. The analytical techniques used in this study highlight the link between biodiesel engine exhaust and increased oxidative potential relative to biodiesel addition on fossil diesel combustion. The EDXRF analysis confirmed the prominent role of metals on free radical production. As a whole, these results suggest that 20% of biodiesel blends run without SCR may pose an increased health risk due to an increase in OH radical generation. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Fabrication of Bi-Fe{sub 3}O{sub 4}@RGO hybrids and their catalytic performance for the reduction of 4-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xuefang; Xia, Fengling; Li, Xichuan; Xu, Xiaoyang; Wang, Huan; Yang, Nian; Gao, Jianping, E-mail: jianpinggaols@126.com [Tianjin University, School of Science (China)

    2015-11-15

    Nanocatalysts are frequently connected to magnetic nanoparticles. These composites are easy to be retrieved from the reaction system under a magnetic field because of their magnetic properties. Magnetic separation is particularly promising in industry since it can solve many issues present in filtration, centrifugation, or gravitation separation. Herein, a facile method to prepare bismuth and Fe{sub 3}O{sub 4} nanoparticles loaded on reduced graphene oxide magnetic hybrids (Bi-Fe{sub 3}O{sub 4}@RGO) using soluble starch as a dispersant is demonstrated. The magnetic Fe{sub 3}O{sub 4} nanoparticles were synthesized by the co-precipitation of Fe{sup 2+} and Fe{sup 3+} ions, and Bi nanoparticles were fabricated by the redox reactions between sodium borohydride and ammonium bismuth citrate in the presence of soluble starch. Transmission electron microscopy images demonstrate that the average diameter of the Fe{sub 3}O{sub 4} nanoparticles is about 5 nm and the diameters of Bi nanoparticles range from 10 to 20 nm. The magnetic Bi-Fe{sub 3}O{sub 4}@RGO hybrids exhibit high catalytic activity in the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by NaBH{sub 4} with a first-order rate constant (K) of 0.00808 s{sup −1} and is magnetically recyclable for at least five cycles. This strategy provides an efficient and recyclable catalyst for the use in environmental protection applications.

  1. Assessment of Malawi's success in child mortality reduction through the lens of the Catalytic Initiative Integrated Health Systems Strengthening programme: Retrospective evaluation.

    Science.gov (United States)

    Doherty, Tanya; Zembe, Wanga; Ngandu, Nobubelo; Kinney, Mary; Manda, Samuel; Besada, Donela; Jackson, Debra; Daniels, Karen; Rohde, Sarah; van Damme, Wim; Kerber, Kate; Daviaud, Emmanuelle; Rudan, Igor; Muniz, Maria; Oliphant, Nicholas P; Zamasiya, Texas; Rohde, Jon; Sanders, David

    2015-12-01

    Malawi is estimated to have achieved its Millennium Development Goal (MDG) 4 target. This paper explores factors influencing progress in child survival in Malawi including coverage of interventions and the role of key national policies. We performed a retrospective evaluation of the Catalytic Initiative (CI) programme of support (2007-2013). We developed estimates of child mortality using four population household surveys undertaken between 2000 and 2010. We recalculated coverage indicators for high impact child health interventions and documented child health programmes and policies. The Lives Saved Tool (LiST) was used to estimate child lives saved in 2013. The mortality rate in children under 5 years decreased rapidly in the 10 CI districts from 219 deaths per 1000 live births (95% confidence interval (CI) 189 to 249) in the period 1991-1995 to 119 deaths (95% CI 105 to 132) in the period 2006-2010. Coverage for all indicators except vitamin A supplementation increased in the 10 CI districts across the time period 2000 to 2013. The LiST analysis estimates that there were 10 800 child deaths averted in the 10 CI districts in 2013, primarily attributable to the introduction of the pneumococcal vaccine (24%) and increased household coverage of insecticide-treated bednets (19%). These improvements have taken place within a context of investment in child health policies and scale up of integrated community case management of childhood illnesses. Malawi provides a strong example for countries in sub-Saharan Africa of how high impact child health interventions implemented within a decentralised health system with an established community-based delivery platform, can lead to significant reductions in child mortality.

  2. Assessment of Malawi’s success in child mortality reduction through the lens of the Catalytic Initiative Integrated Health Systems Strengthening programme: Retrospective evaluation

    Directory of Open Access Journals (Sweden)

    Tanya Doherty

    2015-12-01

    Full Text Available Malawi is estimated to have achieved its Millennium Development Goal (MDG 4 target. This paper explores factors influencing progress in child survival in Malawi including coverage of interventions and the role of key national policies. We performed a retrospective evaluation of the Catalytic Initiative (CI programme of support (2007–2013. We developed estimates of child mortality using four population household surveys undertaken between 2000 and 2010. We recalculated coverage indicators for high impact child health interventions and documented child health programmes and policies. The Lives Saved Tool (LiST was used to estimate child lives saved in 2013. The mortality rate in children under 5 years decreased rapidly in the 10 CI districts from 219 deaths per 1000 live births (95% confidence interval (CI 189 to 249 in the period 1991–1995 to 119 deaths (95% CI 105 to 132 in the period 2006–2010. Coverage for all indicators except vitamin A supplementation increased in the 10 CI districts across the time period 2000 to 2013. The LiST analysis estimates that there were 10 800 child deaths averted in the 10 CI districts in 2013, primarily attributable to the introduction of the pneumococcal vaccine (24% and increased household coverage of insecticide–treated bednets (19%. These improvements have taken place within a context of investment in child health policies and scale up of integrated community case management of childhood illnesses. Malawi provides a strong example for countries in sub–Saharan Africa of how high impact child health interventions implemented within a decentralised health system with an established community–based delivery platform, can lead to significant reductions in child mortality.

  3. Unique catalytic properties of a butoxy chain-containing ruthenated porphyrin towards oxidation of uric acid and reduction of dioxygen for visible light-enhanced fuel cells

    International Nuclear Information System (INIS)

    Liu, Junchen; Wang, Yi; Deng, Qiang; Zhu, Licai; Chao, Hui; Li, Hong

    2016-01-01

    Highlights: • Ru(II)PTPP/CdS shows two Ru(II)-based oxidation peaks at 0.296 V and 0.830 V. • Photoelectrocatalytic oxidation of UA exhibits good linear responses. • The butoxy chain endows Ru(II)PTPP with multifunctional catalytic properties. • Ru(II)PTPP on CF electrode can remarkably promote the reduction of oxygen. • The assembled cell has I_S_C of 0.136 mA cm"−"2 and P_m_a_x of 31.50 μW cm"−"2. - Abstract: This paper reports the photoelectrocatalytic activities of a ruthenated porphyrin [Ru(phen)_2(IP-C_4O-TPP)]"2"+ (denoted as Ru(II)PTPP, phen = 1,10-phenanthroline, IP = imidazo[4,5-f][1,10]phenanthroline and TPP = 5,10,15,20-tetraphenylporphyrin) containing a covalently-linked butoxy chain (-C_4O-) between IP and TPP moieties by means of various electrochemical techniques in combination with absorption spectroscopy and scanning electronic microscopy. Ru(II)PTPP is assembled on the surface of CdS nanoparticles, showing two Ru(II)-based peaks at 0.296 V and 0.830 V, where uric acid (UA) can be photoelectrocatalytically oxidized in a linear range of 0.01-10.0 mmol L"−"1. The −C_4O- chain endows the Ru(II)PTPP/carbon felt (CF) electrode with favorable dioxygen (O_2) binding sites to achieve a couple of new redox peaks at −0.213 V, where O_2 involves electrocatalytic reduction reactions. While employing 5.0 mmol L"−"1 UA as fuel, and 60 mL min"−"1 O_2 as oxidant, the proposed photoelectrochemical fuel cell shows open-circuit photovoltage of 0.656 V, short-circuit photocurrent density of 0.136 mA cm"−"2, and maximum power density of 31.50 μW cm"−"2 at 0.497 V under visible-light illumination of 0.18 mW cm"−"2. The present study provides an interesting platform for the utilization of renewable energy sources.

  4. An unsaturated metal site-promoted approach to construct strongly coupled noble metal/HNb3O8 nanosheets for efficient thermo/photo-catalytic reduction.

    Science.gov (United States)

    Shen, Lijuan; Xia, Yuzhou; Lin, Sen; Liang, Shijing; Wu, Ling

    2017-10-05

    Creating two-dimensional (2D) crystal-metal heterostructures with an ultrathin thickness has spurred increasing research endeavors in catalysis because of its fascinating opportunities in tuning the electronic state at the surface and enhancing the chemical reactivity. Here we report a novel and facile Nb 4+ -assisted strategy for the in situ growth of highly dispersed Pd nanoparticles (NPs) on monolayer HNb 3 O 8 nanosheets (HNb 3 O 8 NS) constituting a 2D Pd/HNb 3 O 8 NS heterostructure composite without using extra reducing agents and stabilizing agents. The Pd NP formation is directed via a redox reaction between an oxidative Pd salt precursor (H 2 PdCl 4 ) and reductive unsaturated surface metal (Nb 4+ ) sites induced by light irradiation on monolayer HNb 3 O 8 NS. The periodic arrangement of metal Nb nodes on HNb 3 O 8 NS leads to a homogeneous distribution of Pd NPs. Density functional theory (DFT) calculations reveal that the direct redox reaction between the Nb 4+ and Pd 2+ ions leads to a strong chemical interaction between the formed Pd metal NPs and the monolayer HNb 3 O 8 support. Consequently, the as-obtained Pd/HNb 3 O 8 composite serves as a highly efficient bifunctional catalyst in both heterogeneous thermocatalytic and photocatalytic selective reduction of aromatic nitro compounds in water under ambient conditions. The achieved high activity originates from the unique 2D nanosheet configuration and in situ Pd incorporation, which leads to a large active surface area, strong metal-support interaction and enhanced charge transport capability. Moreover, this facile Nb 4+ -assisted synthetic route has demonstrated to be general, which can be applied to load other metals such as Au and Pt on monolayer HNb 3 O 8 NS. It is anticipated that this work can extend the facile preparation of noble metal/nanosheet 2D heterostructures, as well as promote the simultaneous capture of duple renewable thermal and photon energy sources to drive an energy efficient

  5. Catalytically supported reduction of emissions from small-scale biomass furnace systems; Katalytisch unterstuetzte Minderung von Emissionen aus Biomasse-Kleinfeuerungsanlagen

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, Ingo; Lenz, Volker; Schenker, Marian; Thiel, Christian [DBFZ Deutsches Biomasseforschungszentrum gemeinnuetzige GmbH, Leipzig (Germany); Kraus, Markus; Matthes, Mirjam; Roland, Ulf [Helmholtz-Zentrum fuer Umweltforschung GmbH - UFZ, Leipzig (Germany); Bindig, Rene; Einicke, Wolf-Dietrich [Leipzig Univ. (Germany)

    2011-06-29

    The increased use of solid biomass in small combustion for generating heat from renewable energy sources is unfortunately associated with increased emissions of airborne pollutants. The reduction is possible on the one hand by the use of high-quality modern furnaces to the latest state of the art. On the other hand, several promising approaches method for retrofitting small-scale furnaces are currently being developed that will allow an effective emission reduction by the subsequent treatment of the exhaust gas. The overview of current available emission control technologies for small-scale biomass combustion plants shows that there is still considerable need for research on the sustainable production of heat from solid biofuels. The amendment to the 1st BImSchV provides a necessary drastic reduction of discharged pollutants from small-scale biomass furnaces. When using the fuel wood in modern central heating boilers the required limits can be met at full load. However, dynamic load changes can cause brief dramatic emission increases even with wood central heating boilers. Firebox and control optimization must contribute in the future to a further reduction of emissions. The typical simple single-room fireplaces like hand-fed wood stoves are suitable under type test conditions to comply the limit values. By contrast, in practical operation, the harmful gas emissions be exceeded without secondary measures normally. The performed experimental investigations show that a reduction of both CO and of organic compounds by catalytic combustion is possible. In addition to developing specially adapted catalysts, it is necessary to provide additional dust separation by combined processes, since conventional catalysts are not suitable for deposition and retention of particulate matter or would lose their activity due to dust accumulation on the active surface, when the catalyst would act as a filter at the same time. To enable sufficiently high reaction temperatures and thus a

  6. Catalytically supported reduction of emissions from small-scale biomass furnace systems; Katalytisch unterstuetzte Minderung von Emissionen aus Biomasse-Kleinfeuerungsanlagen

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, Ingo; Lenz, Volker; Schenker, Marian; Thiel, Christian [DBFZ Deutsches Biomasseforschungszentrum gemeinnuetzige GmbH, Leipzig (Germany); Kraus, Markus; Matthes, Mirjam; Roland, Ulf [Helmholtz-Zentrum fuer Umweltforschung GmbH - UFZ, Leipzig (Germany); Bindig, Rene; Einicke, Wolf-Dietrich [Leipzig Univ. (Germany)

    2011-06-29

    The increased use of solid biomass in small combustion for generating heat from renewable energy sources is unfortunately associated with increased emissions of airborne pollutants. The reduction is possible on the one hand by the use of high-quality modern furnaces to the latest state of the art. On the other hand, several promising approaches method for retrofitting small-scale furnaces are currently being developed that will allow an effective emission reduction by the subsequent treatment of the exhaust gas. The overview of current available emission control technologies for small-scale biomass combustion plants shows that there is still considerable need for research on the sustainable production of heat from solid biofuels. The amendment to the 1st BImSchV provides a necessary drastic reduction of discharged pollutants from small-scale biomass furnaces. When using the fuel wood in modern central heating boilers the required limits can be met at full load. However, dynamic load changes can cause brief dramatic emission increases even with wood central heating boilers. Firebox and control optimization must contribute in the future to a further reduction of emissions. The typical simple single-room fireplaces like hand-fed wood stoves are suitable under type test conditions to comply the limit values. By contrast, in practical operation, the harmful gas emissions be exceeded without secondary measures normally. The performed experimental investigations show that a reduction of both CO and of organic compounds by catalytic combustion is possible. In addition to developing specially adapted catalysts, it is necessary to provide additional dust separation by combined processes, since conventional catalysts are not suitable for deposition and retention of particulate matter or would lose their activity due to dust accumulation on the active surface, when the catalyst would act as a filter at the same time. To enable sufficiently high reaction temperatures and thus a

  7. Catalytic silica particles via template-directed molecular imprinting

    Energy Technology Data Exchange (ETDEWEB)

    Markowitz, M.A.; Kust, P.R.; Deng, G.; Schoen, P.E.; Dordick, J.S.; Clark, D.S.; Gaber, B.P.

    2000-02-22

    The surfaces of silica particle were molecularly imprinted with an {alpha}-chymotrypsin transition-state analogue (TSA) by utilizing the technique of template-directed synthesis of mineralized materials. The resulting catalytic particles hydrolyzed amides in an enantioselective manner. A mixture of a nonionic surfactant and the acylated chymotrysin TSA, with the TSA acting as the headgroup at the surfactant-water interface, was used to form a microemulsion for silica particle formation. Incorporation of amine-, dihydroimidazole-, and carboxylate-terminated trialkoxysilanes into the particles during imprinting resulted in enhancement of the rates of amide hydrolysis. Acylated imprint molecules formed more effective imprints in the presence of the functionalized silanes than nonacylated imprint molecules. Particles surface-imprinted with the chymotrypsin TSA were selective for the trypsin substrate, and particles surface-imprinted with the L-isomer of the enzyme TSA were enantioselective for the D-isomer of the substrate.

  8. Spin-Center Shift-Enabled Direct Enantioselective α-Benzylation of Aldehydes with Alcohols.

    Science.gov (United States)

    Nacsa, Eric D; MacMillan, David W C

    2018-03-07

    Nature routinely engages alcohols as leaving groups, as DNA biosynthesis relies on the removal of water from ribonucleoside diphosphates by a radical-mediated "spin-center shift" (SCS) mechanism. Alcohols, however, remain underused as alkylating agents in synthetic chemistry due to their low reactivity in two-electron pathways. We report herein an enantioselective α-benzylation of aldehydes using alcohols as alkylating agents based on the mechanistic principle of spin-center shift. This strategy harnesses the dual activation modes of photoredox and organocatalysis, engaging the alcohol by SCS and capturing the resulting benzylic radical with a catalytically generated enamine. Mechanistic studies provide evidence for SCS as a key elementary step, identify the origins of competing reactions, and enable improvements in chemoselectivity by rational photocatalyst design.

  9. Kinetic mechanism and enantioselectivity of halohydrin dehalogenase from Agrobacterium radiobacter

    NARCIS (Netherlands)

    Tang, Lixia; Lutje Spelberg, Jeffrey H.; Fraaije, Marco W.; Janssen, DB

    2003-01-01

    Halohydrin dehalogenase (HheC) from Agrobacterium radiobacter AD1 catalyzes the reversible intramolecular nucleophilic displacement of a halogen by a hydroxyl group in vicinal haloalcohols, producing the corresponding epoxides. The enzyme displays high enantioselectivity toward some aromatic

  10. Enantioselective cyclizations and cyclization cascades of samarium ketyl radicals

    Science.gov (United States)

    Kern, Nicolas; Plesniak, Mateusz P.; McDouall, Joseph J. W.; Procter, David J.

    2017-12-01

    The rapid generation of molecular complexity from simple starting materials is a key challenge in synthesis. Enantioselective radical cyclization cascades have the potential to deliver complex, densely packed, polycyclic architectures, with control of three-dimensional shape, in one step. Unfortunately, carrying out reactions with radicals in an enantiocontrolled fashion remains challenging due to their high reactivity. This is particularly the case for reactions of radicals generated using the classical reagent, SmI2. Here, we demonstrate that enantioselective SmI2-mediated radical cyclizations and cascades that exploit a simple, recyclable chiral ligand can convert symmetrical ketoesters to complex carbocyclic products bearing multiple stereocentres with high enantio- and diastereocontrol. A computational study has been used to probe the origin of the enantioselectivity. Our studies suggest that many processes that rely on SmI2 can be rendered enantioselective by the design of suitable ligands.

  11. Rhodium(II)-catalyzed enantioselective synthesis of troponoids.

    Science.gov (United States)

    Murarka, Sandip; Jia, Zhi-Jun; Merten, Christian; Daniliuc, Constantin-G; Antonchick, Andrey P; Waldmann, Herbert

    2015-06-22

    We report a rhodium(II)-catalyzed highly enantioselective 1,3-dipolar cycloaddition reaction between the carbonyl moiety of tropone and carbonyl ylides to afford troponoids in good to high yields with excellent enantioselectivity. We demonstrate that α-diazoketone-derived carbonyl ylides, in contrast to carbonyl ylides derived from diazodiketoesters, undergo [6+3] cycloaddition reactions with tropone to yield the corresponding bridged heterocycles with excellent stereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Asymmetric Reduction of Substituted 2-Tetralones by Thermoanaerobacter pseudoethanolicus Secondary Alcohol Dehydrogenase

    KAUST Repository

    Bsharat, Odey

    2017-01-30

    Ketones bearing two bulky substituents, named bulky-bulky ketones, were successfully reduced to their corresponding optically enriched alcohols by using various mutants of Thermoanaerobacter pseudoethanolicus secondary alcohol dehydrogenase (TeSADH). Substituted 2-tetralones, in particular, were reduced to 2-tetralols with high conversion and high enantioselectivity. The pharmacological importance of substituted 2-tetralols as key drug-building blocks makes our biocatalytic reduction method a highly essential tool. We showed that changing the position of the substituent on the aromatic ring of 2-tetralones impacts their binding affinity and the reaction maximum catalytic rate. Docking studies with several TeSADH mutants explain how the position of the substituent on the tetralone influences the binding orientation of substituted 2-tetralones and their reaction stereoselectivity.

  13. Asymmetric Reduction of Substituted 2-Tetralones by Thermoanaerobacter pseudoethanolicus Secondary Alcohol Dehydrogenase

    KAUST Repository

    Bsharat, Odey; Musa, Musa M.; Vieille, Claire; Oladepo, Sulayman; Takahashi, Masateru; Hamdan, Samir

    2017-01-01

    Ketones bearing two bulky substituents, named bulky-bulky ketones, were successfully reduced to their corresponding optically enriched alcohols by using various mutants of Thermoanaerobacter pseudoethanolicus secondary alcohol dehydrogenase (TeSADH). Substituted 2-tetralones, in particular, were reduced to 2-tetralols with high conversion and high enantioselectivity. The pharmacological importance of substituted 2-tetralols as key drug-building blocks makes our biocatalytic reduction method a highly essential tool. We showed that changing the position of the substituent on the aromatic ring of 2-tetralones impacts their binding affinity and the reaction maximum catalytic rate. Docking studies with several TeSADH mutants explain how the position of the substituent on the tetralone influences the binding orientation of substituted 2-tetralones and their reaction stereoselectivity.

  14. Influence on the oxidative potential of a heavy-duty engine particle emission due to selective catalytic reduction system and biodiesel blend

    International Nuclear Information System (INIS)

    Godoi, Ricardo H.M.; Polezer, Gabriela; Borillo, Guilherme C.; Brown, Andrew; Valebona, Fabio B.; Silva, Thiago O.B.; Ingberman, Aline B.G.; Nalin, Marcelo; Yamamoto, Carlos I.; Potgieter-Vermaak, Sanja; Penteado Neto, Renato A.; Marchi, Mary Rosa R. de; Saldiva, Paulo H.N.; Pauliquevis, Theotonio; Godoi, Ana Flavia L.

    2016-01-01

    Although the particulate matter (PM) emissions from biodiesel fuelled engines are acknowledged to be lower than those of fossil diesel, there is a concern on the impact of PM produced by biodiesel to human health. As the oxidative potential of PM has been suggested as trigger for adverse health effects, it was measured using the Electron Spin Resonance (OP"E"S"R) technique. Additionally, Energy Dispersive X-ray Fluorescence Spectroscopy (EDXRF) was employed to determine elemental concentration, and Raman Spectroscopy was used to describe the amorphous carbon character of the soot collected on exhaust PM from biodiesel blends fuelled test-bed engine, with and without Selective Catalytic Reduction (SCR). OP"E"S"R results showed higher oxidative potential per kWh of PM produced from a blend of 20% soybean biodiesel and 80% ULSD (B20) engine compared with a blend of 5% soybean biodiesel and 95% ULSD (B5), whereas the SCR was able to reduce oxidative potential for each fuel. EDXRF data indicates a correlation of 0.99 between concentration of copper and oxidative potential. Raman Spectroscopy centered on the expected carbon peaks between 1100 cm"−"1 and 1600 cm"−"1 indicate lower molecular disorder for the B20 particulate matter, an indicative of a more graphitic carbon structure. The analytical techniques used in this study highlight the link between biodiesel engine exhaust and increased oxidative potential relative to biodiesel addition on fossil diesel combustion. The EDXRF analysis confirmed the prominent role of metals on free radical production. As a whole, these results suggest that 20% of biodiesel blends run without SCR may pose an increased health risk due to an increase in OH radical generation. - Highlights: • PM emission from biodiesel burning may be more harmful to human health than diesel. • Euro V (SCR) engine fuelled with B5 and B20 tested in a bench dynamometer • Electron Spin Resonance (ESR) to access the oxidative potential of PM emission

  15. Influence on the oxidative potential of a heavy-duty engine particle emission due to selective catalytic reduction system and biodiesel blend

    Energy Technology Data Exchange (ETDEWEB)

    Godoi, Ricardo H.M., E-mail: rhmgodoi@ufpr.br [Environmental Engineering Department, Federal University of Parana, Curitiba, PR (Brazil); Polezer, Gabriela; Borillo, Guilherme C. [Environmental Engineering Department, Federal University of Parana, Curitiba, PR (Brazil); Brown, Andrew [Division of Chemistry and Environmental Science, School of Science and the Environment, Manchester Metropolitan University, Manchester (United Kingdom); Valebona, Fabio B.; Silva, Thiago O.B.; Ingberman, Aline B.G. [Environmental Engineering Department, Federal University of Parana, Curitiba, PR (Brazil); Nalin, Marcelo [LAVIE - Institute of Chemistry, São Paulo State University - UNESP, Araraquara (Brazil); Yamamoto, Carlos I. [Chemical Engineering Department, Federal University of Parana, Curitiba, PR (Brazil); Potgieter-Vermaak, Sanja [Division of Chemistry and Environmental Science, School of Science and the Environment, Manchester Metropolitan University, Manchester (United Kingdom); Penteado Neto, Renato A. [Vehicle Emissions Laboratory, Institute of Technology for Development (LACTEC), Curitiba, PR (Brazil); Marchi, Mary Rosa R. de [Analytical Chemistry Department, Institute of Chemistry, São Paulo State University - UNESP, Araraquara (Brazil); Saldiva, Paulo H.N. [Laboratory of Experimental Air Pollution, Department of Pathology, School of Medicine, University of São Paulo, São Paulo (Brazil); Pauliquevis, Theotonio [Department of Natural and Earth Sciences, Federal University of São Paulo, Diadema (Brazil); Godoi, Ana Flavia L. [Environmental Engineering Department, Federal University of Parana, Curitiba, PR (Brazil)

    2016-08-01

    Although the particulate matter (PM) emissions from biodiesel fuelled engines are acknowledged to be lower than those of fossil diesel, there is a concern on the impact of PM produced by biodiesel to human health. As the oxidative potential of PM has been suggested as trigger for adverse health effects, it was measured using the Electron Spin Resonance (OP{sup ESR}) technique. Additionally, Energy Dispersive X-ray Fluorescence Spectroscopy (EDXRF) was employed to determine elemental concentration, and Raman Spectroscopy was used to describe the amorphous carbon character of the soot collected on exhaust PM from biodiesel blends fuelled test-bed engine, with and without Selective Catalytic Reduction (SCR). OP{sup ESR} results showed higher oxidative potential per kWh of PM produced from a blend of 20% soybean biodiesel and 80% ULSD (B20) engine compared with a blend of 5% soybean biodiesel and 95% ULSD (B5), whereas the SCR was able to reduce oxidative potential for each fuel. EDXRF data indicates a correlation of 0.99 between concentration of copper and oxidative potential. Raman Spectroscopy centered on the expected carbon peaks between 1100 cm{sup −1} and 1600 cm{sup −1} indicate lower molecular disorder for the B20 particulate matter, an indicative of a more graphitic carbon structure. The analytical techniques used in this study highlight the link between biodiesel engine exhaust and increased oxidative potential relative to biodiesel addition on fossil diesel combustion. The EDXRF analysis confirmed the prominent role of metals on free radical production. As a whole, these results suggest that 20% of biodiesel blends run without SCR may pose an increased health risk due to an increase in OH radical generation. - Highlights: • PM emission from biodiesel burning may be more harmful to human health than diesel. • Euro V (SCR) engine fuelled with B5 and B20 tested in a bench dynamometer • Electron Spin Resonance (ESR) to access the oxidative potential of

  16. Demonstration of Selective Catalytic Reduction Technology to Control Nitrogen Oxide Emissions From High-Sulfur, Coal-Fired Boilers: A DOE Assessment

    International Nuclear Information System (INIS)

    Federal Energy Technology Center

    1999-01-01

    The goal of the U.S. Department of Energy (DOE) Clean Coal Technology (CCT) program is to furnish the energy marketplace with a number of advanced, more efficient, and environmentally responsible coal utilization technologies through demonstration projects. These projects seek to establish the commercial feasibility of the most promising advanced coal technologies that have developed beyond the proof-of-concept stage. This document serves as a DOE post-project assessment of a project selected in CCT Round 2. The project is described in the report ''Demonstration of Selective Catalytic Reduction (SCR) Technology for the Control of Nitrogen Oxide (NO(sub x)) Emissions from High-Sulfur, Coal-Fired Boilers'' (Southern Company Services 1990). In June 1990, Southern Company Services (Southern) entered into a cooperative agreement to conduct the study. Southern was a cofunder and served as the host at Gulf Power Company's Plant Crist. Other participants and cofunders were EPRI (formerly the Electric Power Research Institute) and Ontario Hydro. DOE provided 40 percent of the total project cost of$23 million. The long-term operation phase of the demonstration was started in July 1993 and was completed in July 1995. This independent evaluation is based primarily on information from Southern's Final Report (Southern Company Services 1996). The SCR process consists of injecting ammonia (NH(sub 3)) into boiler flue gas and passing the 3 flue gas through a catalyst bed where the NO(sub x) and NH(sub 3) react to form nitrogen and water vapor. The objectives of the demonstration project were to investigate: Performance of a wide variety of SCR catalyst compositions, geometries, and manufacturing methods at typical U.S. high-sulfur coal-fired utility operating conditions; Catalyst resistance to poisoning by trace metal species present in U.S. coals but not present, or present at much lower concentrations, in fuels from other countries; and Effects on the balance-of-plant equipment

  17. Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

    Science.gov (United States)

    Bayeh, Liela; Le, Phong Q.; Tambar, Uttam K.

    2017-07-01

    The stereoselective oxidation of hydrocarbons is one of the most notable advances in synthetic chemistry over the past fifty years. Inspired by nature, enantioselective dihydroxylations, epoxidations and other oxidations of unsaturated hydrocarbons have been developed. More recently, the catalytic enantioselective allylic carbon-hydrogen oxidation of alkenes has streamlined the production of pharmaceuticals, natural products, fine chemicals and other functional materials. Allylic functionalization provides a direct path to chiral building blocks with a newly formed stereocentre from petrochemical feedstocks while preserving the olefin functionality as a handle for further chemical elaboration. Various metal-based catalysts have been discovered for the enantioselective allylic carbon-hydrogen oxidation of simple alkenes with cyclic or terminal double bonds. However, a general and selective allylic oxidation using the more common internal alkenes remains elusive. Here we report the enantioselective, regioselective and E/Z-selective allylic oxidation of unactivated internal alkenes via a catalytic hetero-ene reaction with a chalcogen-based oxidant. Our method enables non-symmetric internal alkenes to be selectively converted into allylic functionalized products with high stereoselectivity and regioselectivity. Stereospecific transformations of the resulting multifunctional chiral building blocks highlight the potential for rapidly converting internal alkenes into a broad range of enantioenriched structures that can be used in the synthesis of complex target molecules.

  18. Diastereoselective and enantioselective reduction of tetralin-1,4-dione

    OpenAIRE

    Kündig, E Peter; Enriquez-Garcia, Alvaro

    2008-01-01

    Summary Background The chemistry of tetralin-1,4-dione, the stable tautomer of 1,4-dihydroxynaphthalene, has not been explored previously. It is readily accessible and offers interesting opportunities for synthesis. Results The title reactions were explored. L-Selectride reduced the diketone to give preferentially the cis-diol (d.r. 84 : 16). Red-Al gave preferentially the trans-diol (d.r. 13 : 87). NaBH4, LiAlH4, and BH3 gave lower diastereoselectivities (yields: 76–98%). Fractional crystall...

  19. 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.

  20. Enhanced catalytic four-electron dioxygen (O2) and two-electron hydrogen peroxide (H2O2) reduction with a copper(II) complex possessing a pendant ligand pivalamido group.

    Science.gov (United States)

    Kakuda, Saya; Peterson, Ryan L; Ohkubo, Kei; Karlin, Kenneth D; Fukuzumi, Shunichi

    2013-05-01

    A copper complex, [(PV-tmpa)Cu(II)](ClO4)2 (1) [PV-tmpa = bis(pyrid-2-ylmethyl){[6-(pivalamido)pyrid-2-yl]methyl}amine], acts as a more efficient catalyst for the four-electron reduction of O2 by decamethylferrocene (Fc*) in the presence of trifluoroacetic acid (CF3COOH) in acetone as compared with the corresponding copper complex without a pivalamido group, [(tmpa)Cu(II)](ClO4)2 (2) (tmpa = tris(2-pyridylmethyl)amine). The rate constant (k(obs)) of formation of decamethylferrocenium ion (Fc*(+)) in the catalytic four-electron reduction of O2 by Fc* in the presence of a large excess CF3COOH and O2 obeyed first-order kinetics. The k(obs) value was proportional to the concentration of catalyst 1 or 2, whereas the k(obs) value remained constant irrespective of the concentration of CF3COOH or O2. This indicates that electron transfer from Fc* to 1 or 2 is the rate-determining step in the catalytic cycle of the four-electron reduction of O2 by Fc* in the presence of CF3COOH. The second-order catalytic rate constant (k(cat)) for 1 is 4 times larger than the corresponding value determined for 2. With the pivalamido group in 1 compared to 2, the Cu(II)/Cu(I) potentials are -0.23 and -0.05 V vs SCE, respectively. However, during catalytic turnover, the CF3COO(-) anion present readily binds to 2 shifting the resulting complex's redox potential to -0.35 V. The pivalamido group in 1 is found to inhibit anion binding. The overall effect is to make 1 easier to reduce (relative to 2) during catalysis, accounting for the relative k(cat) values observed. 1 is also an excellent catalyst for the two-electron two-proton reduction of H2O2 to water and is also more efficient than is 2. For both complexes, reaction rates are greater than for the overall four-electron O2-reduction to water, an important asset in the design of catalysts for the latter.

  1. Evaluation of achiral templates with fluxional Brønsted basic substituents in enantioselective conjugate additions.

    Science.gov (United States)

    Adachi, Shinya; Takeda, Norihiko; Sibi, Mukund P

    2014-12-19

    Enantioselective conjugate addition of malononitrile to pyrazolidinone-derived enoates proceeds in excellent yields and high enantioselectivities. A comparison of fluxional substituents with and without a Brønsted basic site and their impact on selectivity is detailed. Molecular sieves as an additive were found to be essential to achieve high enantioselectivity.

  2. Facile synthesis of SiO{sub 2}@Cu{sub x}O@TiO{sub 2} heterostructures for catalytic reductions of 4-nitrophenol and 2-nitroaniline organic pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Zelekew, Osman Ahmed; Kuo, Dong-Hau, E-mail: dhkuo@mail.ntust.edu.tw

    2017-01-30

    Highlights: • The synthesis of SiO{sub 2}@Cu{sub x}O@TiO{sub 2}catalystwasillustrated (*). • The p-n junction between p-type Cu{sub x}O and n-type TiO{sub 2} built electric field. • The electric field results in avoiding the recombination of electron and hole. • The n-type TiO{sub 2} rich in electron outward facilitates the reduction. - Abstract: Herein, we designed the p-type Cu{sub x}O (x = 1 or 2) nanoparticles deposited on SiO{sub 2} spherical particle inside and coated with thin layered n-type TiO{sub 2} semiconductors outside for reduction purpose. The composite material, abbreviated as SiO{sub 2}@Cu{sub x}O@TiO{sub 2}, was characterized. The catalytic performance of the composite was tested for the reductions of 4-nitrophenol (4-NP) and 2-nitroaniline (2-NA). Complete reductions of 4-NP and 2-NA took, 210 and 150 s, respectively. The catalytic efficiency of the composite material may be associated with electron and hole separation resulted from the p-n junction formation between p-type Cu{sub x}O and n-type TiO{sub 2} and the built-in electric field. Moreover, the hydride ion and electrons released from NaBH{sub 4} together with outward electrons from n-type TiO{sub 2}, synergistically, are also responsible for the reduction of nitro aromatic compounds. Our design of composite material from low-priced metal oxides was successful towards reduction of nitro-aromatic compounds.

  3. TiO2/SiO2 prepared via facile sol-gel method as an ideal support for green synthesis of Ag nanoparticles using Oenothera biennis extract and their excellent catalytic performance in the reduction of 4-nitrophenol

    Directory of Open Access Journals (Sweden)

    Bahar Khodadadi

    2017-01-01

    Full Text Available In the present study, the extract of the plant of Oenothera biennis was used to green synthesis of silver nanoparticles (Ag NPs as an environmentally friendly, simple and low cost method. And Additionally, TiO2/SiO2 was prepared via facile sol-gel method using starch as an important, naturally abundant organic polymer as an ideal support. The Ag NPs/TiO2/SiO2 as an effective catalyst was prepared through reduction of Ag+ ions using Oenothera biennis extract as the reducing and stabilizing agent and Ag NPs immobilization on TiO2/SiO2 surface in the absence of any stabilizer or surfactant. Several techniques such as FT-IR spectroscopy, UV-Vis spectroscopy, X-ray Diffraction (XRD, sScanning eElectron mMicroscopy (FE-SEM, Eenergy dDispersive X-ray sSpectroscopy (EDS, and Ttransmission Eelectron Mmicroscopy (TEM were used to characterize TiO2/SiO2, silver nanoparticles (Ag NPs, and Ag NPs/TiO2/SiO2. Moreover, the catalytic activity of the Ag NPs/ TiO2/SiO2 was investigated in the reduction of 4-nitrophenol (4-NP at room temperature. On the basis of the results, the Ag NPs/TiO2/SiO2 was found to be high catalytic activity highly active catalyst according to the experimental results in this study. In addition, Ag NPs/TiO2/SiO2 can be recovered and reused several times in the reduction of 4-NP with no significant loss of catalytic activity.

  4. A Study of Different Doped Metal Cations on the Physicochemical Properties and Catalytic Activities of Ce20 M1 Ox (M=Zr, Cr, Mn, Fe, Co, Sn) Composite Oxides for Nitric Oxide Reduction by Carbon Monoxide.

    Science.gov (United States)

    Deng, Changshun; Li, Min; Qian, Junning; Hu, Qun; Huang, Meina; Lin, Qingjin; Ruan, Yongshun; Dong, Lihui; Li, Bin; Fan, Minguang

    2016-08-05

    This work is mainly focused on investigating the effects of different doped metal cations on the formation of Ce20 M1 Ox (M=Zr, Cr, Mn, Fe, Co, Sn) composite oxides and their physicochemical and catalytic properties for NO reduction by CO as a model reaction. The obtained samples were characterized by using N2 physisorption, X-ray diffraction, laser Raman spectroscopy, UV/Vis diffuse reflectance spectroscopy, inductively coupled plasma atomic emission spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction by hydrogen and by oxygen (H2 -TPR and O2 -TPD), in situ diffuse reflectance infrared Fourier transform spectroscopy, and the NO+CO model reaction. The results imply that the introduction of M(x+) into the lattice of CeO2 increases the specific surface area and pore volume, especially for variable valence metal cations, and enhances the catalytic performance to a great extent. In this regard, increases in the oxygen vacancies, reduction properties, and chemisorbed O2 (-) (and/or O(-) ) species of these Ce20 M1 Ox composite oxides (M refers to variable valence metals) play significant roles in this reaction. Among the samples, Ce20 Cr1 Ox exhibited the best catalytic performance, mainly because it has the best reducibility and more chemisorbed oxygen, and significant reasons for these attributes may be closely related to favorable synergistic interactions of the vacancies and near-surface Ce(3+) and Cr(3+) . Finally, a possible reaction mechanism was tentatively proposed to understand the reactions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

    Engelmann Pirez, M

    2004-12-15

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

  6. 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. Mn/TiO2 and Mn–Fe/TiO2 catalysts synthesized by deposition precipitation—promising for selective catalytic reduction of NO with NH3 at low temperatures

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Schill, Leonhard; Jensen, Anker Degn

    2015-01-01

    Mn/TiO2and Mn–Fe/TiO2catalysts have been prepared by impregnation (IMP) and deposition-precipitation (DP) techniques and characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR, XPS and TGA. 25 wt% Mn0.75Fe0.25Ti-DP catalyst, prepared by deposition precipitation with ammonium carbamate (AC......) as a precipitating agent, showed superior low-temperature SCR (selective catalytic reduction) of NO with NH3. The superior catalytic activity of the 25 wt% Mn0.75Fe0.25Ti-DP catalyst is probably due to the presence of amorphous phases of manganese oxide, iron oxide, high surface area, high total acidity......, acidstrength and ease of reduction of manganese oxide and iron oxide on TiO2in addition to formation of an SCR active MnOx phase with high content of chemisorbed oxygen (Oα). The optimum catalyst might beused as tail-end SCR catalysts in, e.g., biomass-fired power plants and waste incineration plants....

  8. Pentanidium-catalyzed enantioselective phase-transfer conjugate addition reactions

    KAUST Repository

    Ma, Ting

    2011-03-09

    A new chiral entity, pentanidium, has been shown to be an excellent chiral phase-transfer catalyst. The enantioselective Michael addition reactions of tert-butyl glycinate-benzophenone Schiff base with various α,β- unsaturated acceptors provide adducts with high enantioselectivities. A successful gram-scale experiment at a low catalyst loading of 0.05 mol % indicates the potential for practical applications of this methodology. Phosphoglycine ester analogues can also be utilized as the Michael donor, affording enantioenriched α-aminophosphonic acid derivatives and phosphonic analogues of (S)-proline. © 2011 American Chemical Society.

  9. Influence of gasoline inhalation on the enantioselective pharmacokinetics of fluoxetine in rats.

    Science.gov (United States)

    Cardoso, Juciane Lauren Cavalcanti; Lanchote, Vera Lucia; Pereira, Maria Paula Marques; Capela, Jorge Manuel Vieira; Lepera, José Salvador

    2013-03-01

    Fluoxetine is used clinically as a racemic mixture of (+)-(S) and (-)-(R) enantiomers for the treatment of depression. CYP2D6 catalyzes the metabolism of both fluoxetine enantiomers. We aimed to evaluate whether exposure to gasoline results in CYP2D inhibition. Male Wistar rats exposed to filtered air (n = 36; control group) or to 600 ppm of gasoline (n = 36) in a nose-only inhalation exposure chamber for 6 weeks (6 h/day, 5 days/week) received a single oral 10-mg/kg dose of racemic fluoxetine. Fluoxetine enantiomers in plasma samples were analyzed by a validated analytical method using LC-MS/MS. The separation of fluoxetine enantiomers was performed in a Chirobiotic V column using as the mobile phase a mixture of ethanol:ammonium acetate 15 mM. Higher plasma concentrations of the (+)-(S)-fluoxetine enantiomer were found in the control group (enantiomeric ratio AUC((+)-(S)/(-)-(R)) = 1.68). In animals exposed to gasoline, we observed an increase in AUC(0-∞) for both enantiomers, with a sharper increase seen for the (-)-(R)-fluoxetine enantiomer (enantiomeric ratio AUC((+)-(S)/(-)-(R)) = 1.07), resulting in a loss of enantioselectivity. Exposure to gasoline was found to result in the loss of enantioselectivity of fluoxetine, with the predominant reduction occurring in the clearance of the (-)-(R)-fluoxetine enantiomer (55% vs. 30%). Copyright © 2013 Wiley Periodicals, Inc.

  10. Molecular Design of a Chiral Brønsted Acid with Two Different Acidic Sites: Regio-, Diastereo-, and Enantioselective Hetero-Diels-Alder Reaction of Azopyridinecarboxylate with Amidodienes Catalyzed by Chiral Carboxylic Acid-Monophosphoric Acid.

    Science.gov (United States)

    Momiyama, Norie; Tabuse, Hideaki; Noda, Hirofumi; Yamanaka, Masahiro; Fujinami, Takeshi; Yamanishi, Katsunori; Izumiseki, Atsuto; Funayama, Kosuke; Egawa, Fuyuki; Okada, Shino; Adachi, Hiroaki; Terada, Masahiro

    2016-09-07

    A chiral Brønsted acid containing two different acidic sites, chiral carboxylic acid-monophosphoric acid 1a, was designed to be a new and effective concept in catalytic asymmetric hetero-Diels-Alder reactions of azopyridinecarboxylate with amidodienes. The multipoint hydrogen-bonding interactions among the carboxylic acid, monophosphoric acid, azopyridinecarboxylate, and amidodiene achieved high catalytic and chiral efficiency, producing substituted 1,2,3,6-tetrahydropyridazines with excellent stereocontrol in a single step. This constitutes the first example of regio-, diastereo-, and enantioselective azo-hetero-Diels-Alder reactions by chiral Brønsted acid catalysis.

  11. Highly Enantioselective Production of (R-Halohydrins with Whole Cells of Rhodotorula rubra KCh 82 Culture

    Directory of Open Access Journals (Sweden)

    Tomasz Janeczko

    2014-12-01

    Full Text Available Biotransformation of ten α-haloacetophenones in the growing culture of the strain Rhodotorula rubra KCh 82 has been carried out. Nine of the substrates underwent an effective enantioselective reduction to the respective (R-alcohols according to Prelog’s rule, with the exception of 2-chloro-1,2-diphenylethan-1-one that was not transformed by this strain. The expected reduction proceeded without dehalogenation, leading to the respective (R-halohydrins in high yields. The use of this biocatalyst yielded (R-2-bromo-1-phenyl-ethan-1-ol (enantiomeric excess (ee = 97% and its derivatives: 4'-Bromo- (ee = 99%; 4'-Chloro- (ee > 99%; 4'-Methoxy- (ee = 96%; 3'-Methoxy- (ee = 93%; 2'-Methoxy- (ee = 98%. There were also obtained and characterized 2,4'-dichloro-, 2,2',4'-trichloro- and 2-chloro-4'-fluoro-phenyetan-1-ol with >99% of enantiomeric excesses.

  12. Highly enantioselective production of (R)-halohydrins with whole cells of Rhodotorula rubra KCh 82 culture.

    Science.gov (United States)

    Janeczko, Tomasz; Dymarska, Monika; Kostrzewa-Susłow, Edyta

    2014-12-04

    Biotransformation of ten α-haloacetophenones in the growing culture of the strain Rhodotorula rubra KCh 82 has been carried out. Nine of the substrates underwent an effective enantioselective reduction to the respective (R)-alcohols according to Prelog's rule, with the exception of 2-chloro-1,2-diphenylethan-1-one that was not transformed by this strain. The expected reduction proceeded without dehalogenation, leading to the respective (R)-halohydrins in high yields. The use of this biocatalyst yielded (R)-2-bromo-1-phenyl-ethan-1-ol (enantiomeric excess (ee) = 97%) and its derivatives: 4'-Bromo- (ee = 99%); 4'-Chloro- (ee > 99%); 4'-Methoxy- (ee = 96%); 3'-Methoxy- (ee = 93%); 2'-Methoxy- (ee = 98%). There were also obtained and characterized 2,4'-dichloro-, 2,2',4'-trichloro- and 2-chloro-4'-fluoro-phenyetan-1-ol with >99% of enantiomeric excesses.

  13. Exmination of catalytic reduction of NO by CH4 in a Pt-polybenimidazole membrane-Pt system with and without polarization

    DEFF Research Database (Denmark)

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

    “NO reduction in the NO, CH4, Ar/Pt/C//polybenzimidazole-H3PO4//Pt/C/H2, Ar was studied at 135°C”......“NO reduction in the NO, CH4, Ar/Pt/C//polybenzimidazole-H3PO4//Pt/C/H2, Ar was studied at 135°C”...

  14. Metal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computation

    KAUST Repository

    Pluta, Roman

    2018-02-09

    A chiral iodoarene organocatalyst for the catalytic asymmetric fluorination has been developed. The catalyst was used in the asymmetric fluorination of carbonyl compounds, providing the products with a quaternary stereocenter with high enantioselectivities. Chiral hypervalent iodine difluoride intermediates were generated in situ by treatment of the catalyst with an oxidant and hydrogen fluoride as fluoride source. As such, the α-fluorination of a carbonyl compound was achieved with a nucleophilic fluorine source. A combined computational and experimental approach provided insight into the reaction mechanism and the origin of enantioselectivity.

  15. Metal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computation

    KAUST Repository

    Pluta, Roman; Krach, Patricia E.; Cavallo, Luigi; Falivene, Laura; Rueping, Magnus

    2018-01-01

    A chiral iodoarene organocatalyst for the catalytic asymmetric fluorination has been developed. The catalyst was used in the asymmetric fluorination of carbonyl compounds, providing the products with a quaternary stereocenter with high enantioselectivities. Chiral hypervalent iodine difluoride intermediates were generated in situ by treatment of the catalyst with an oxidant and hydrogen fluoride as fluoride source. As such, the α-fluorination of a carbonyl compound was achieved with a nucleophilic fluorine source. A combined computational and experimental approach provided insight into the reaction mechanism and the origin of enantioselectivity.

  16. The role of achiral pyrazolidinone templates in enantioselective Diels-Alder reactions: scope, limitations, and conformational insights.

    Science.gov (United States)

    Sibi, Mukund P; Stanley, Levi M; Nie, Xiaoping; Venkatraman, Lakshmanan; Liu, Mei; Jasperse, Craig P

    2007-01-17

    We have evaluated the role of achiral pyrazolidinone templates in conjunction with chiral Lewis acids in room temperature, enantioselective Diels-Alder cycloadditions. The role of the fluxional N(1) substituent was examined, with the bulky 1-naphthylmethyl group providing enantioselectivities up to 99% ee, while templates with smaller fluxional groups gave lower selectivities. High selectivities were also observed in reactions of 7d with chiral Lewis acids derived from relatively small chiral ligands, suggesting the pyrazolidinone templates are capable of relaying stereochemical information from the ligand to the reaction center. Lewis acids capable of adapting square planar geometries, such as Cu(OTf)2, Cu(ClO4)2, and Pd(ClO4)2, were found to be particularly effective at providing high selectivities. Additionally, substitution at the C-5 position of the pyrazolidinone templates has been shown to be critical for optimal selectivity. Reactions of the optimal pyrazolidinone appended with a number of common dienophiles and various dienes demonstrate the utility of this achiral template. Furthermore, catalytic loadings could be lowered to 2.5 mol % with essentially no loss in selectivity. Pi-Pi interactions were evaluated as a means to explain the unusually high selectivity observed at room temperature. Finally, non-C2-symmetric ligands were employed as a test to determine if chiral relay was operative.

  17. Enantioselective cycloadditions with alpha,beta-disubstituted acrylimides.

    Science.gov (United States)

    Sibi, Mukund P; Ma, Zhihua; Itoh, Kennosuke; Prabagaran, Narayanasamy; Jasperse, Craig P

    2005-06-09

    [reaction: see text] The use of N-H imide templates provides a solution to the problem of rotamer control in Lewis acid catalyzed reactions of alpha,beta-disubstituted acryloyl imides. Reactions proceed through the s-cis rotamer and with improved reactivity because A(1,3) strain is avoided. Enantioselective nitrone, nitrile oxide, and Diels-Alder cycloadditions demonstrate the principle.

  18. Pyrones to pyrans: enantioselective radical additions to acyloxy pyrones.

    Science.gov (United States)

    Sibi, Mukund P; Zimmerman, Jake

    2006-10-18

    This paper describes a highly site-, diastereo-, and enantioselective intermolecular radical addition/hydrogen atom transfer to hydroxypyrone pyromeconic and kojic acids. The methodology can be extended to the formation of chiral quaternary centers. The products obtained are densely functionalized pyran moieties. The products contain structural features amenable for the introduction of additional substituents.

  19. Lanthanide Lewis acid-mediated enantioselective conjugate radical additions.

    Science.gov (United States)

    Sibi, Mukund P; Manyem, Shankar

    2002-08-22

    [reaction: see text] Lanthanide triflates along with proline-derived ligands have been found to be efficient catalysts for enantioselective conjugate addition of nucleophilic radicals to enoates. N-Acyl oxazolidinones, when used as achiral additives, gave meaningful enhancements in the ees for the product.

  20. Guanidine-catalyzed enantioselective desymmetrization of meso-aziridines

    KAUST Repository

    Zhang, Yan

    2011-01-01

    An amino-indanol derived chiral guanidine was developed as an efficient Brønsted base catalyst for the desymmetrization of meso-aziridines with both thiols and carbamodithioic acids as nucleophiles, which provided 1,2-difunctionalized ring-opened products in high yields and enantioselectivities. © The Royal Society of Chemistry.

  1. Asymmetric Chemoenzymatic Reductive Acylation of Ketones by a Combined Iron-Catalyzed Hydrogenation-Racemization and Enzymatic Resolution Cascade

    KAUST Repository

    El-Sepelgy, Osama; Brzozowska, Aleksandra; Rueping, Magnus

    2017-01-01

    . By merging the iron-catalyzed redox reactions with enantioselective enzymatic acylations a wide range of benzylic, aliphatic and (hetero)aromatic ketones, as well as diketones, were reductively acylated. The corresponding products were isolated with high

  2. Significant Improvement of Catalytic Efficiencies in Ionic Liquids

    International Nuclear Information System (INIS)

    Song, Choong Eui; Yoon, Mi Young; Choi, Doo Seong

    2005-01-01

    The use of ionic liquids as reaction media can confer many advantages upon catalytic reactions over reactions in organic solvents. In ionic liquids, catalysts having polar or ionic character can easily be immobilized without additional structural modification and thus the ionic solutions containing the catalyst can easily be separated from the reagents and reaction products, and then, be reused. More interestingly, switching from an organic solvent to an ionic liquid often results in a significant improvement in catalytic performance (e.g., rate acceleration, (enantio)selectivity improvement and an increase in catalyst stability). In this review, some recent interesting results which can nicely demonstrate these positive 'ionic liquid effect' on catalysis are discussed

  3. Final Technical Report on Investigation of Selective Non-Catalytic Processes for In-Situ Reduction of NOx and CO Emissions from Marine Gas Turbines and Diesel Engines

    National Research Council Canada - National Science Library

    Bowman, Craig

    1997-01-01

    .... These observations suggest the possibility of utilizing SNCR for reducing NO(x) emissions from marine gas turbines and Diesel engines by direct injection of a reductant species into the combustion chamber, possibly as a fuel...

  4. Graphene-based hybrid for enantioselective sensing applications.

    Science.gov (United States)

    Zor, Erhan; Morales-Narváez, Eden; Alpaydin, Sabri; Bingol, Haluk; Ersoz, Mustafa; Merkoçi, Arben

    2017-01-15

    Chirality is a major field of research of chemical biology and is essential in pharmacology. Accordingly, approaches for distinguishing between different chiral forms of a compound are of great interest. We report on an efficient and generic enantioselective sensor that is achieved by coupling reduced graphene oxide with γ-cyclodextrin (rGO/γ-CD). The enantioselective sensing capability of the resulting structure was operated in both electrical and optical mode for of tryptophan enantiomers (D-/L-Trp). In this sense, voltammetric and photoluminescence measurements were conducted and the experimental results were compared to molecular docking method. We gain insight into the occurring recognition mechanism with selectivity toward D- and L-Trp as shown in voltammetric, photoluminescence and molecular docking responses. As an enantioselective solid phase on an electrochemical transducer, thanks to the different dimensional interaction of enantiomers with hybrid material, a discrepancy occurs in the Gibbs free energy leading to a difference in oxidation peak potential as observed in electrochemical measurements. The optical sensing principle is based on the energy transfer phenomenon that occurs between photoexcited D-/L-Trp enantiomers and rGO/γ-CD giving rise to an enantioselective photoluminescence quenching due to the tendency of chiral enantiomers to form complexes with γ-CD in different molecular orientations as demonstrated by molecular docking studies. The approach, which is the first demonstration of applicability of molecular docking to show both enantioselective electrochemical and photoluminescence quenching capabilities of a graphene-related hybrid material, is truly new and may have broad interest in combination of experimental and computational methods for enantiosensing of chiral molecules. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Novel selective catalytic reduction with tritium: synthesis of the GABAA receptor radioligand 1-(4-ethynylphenyl)-4-[2,3-3H2]propyl-2,6,7-trioxabicyclo[2.2.2 ]octane

    International Nuclear Information System (INIS)

    Palmer, C.J.; Casida, J.E.

    1991-01-01

    Protection of the terminal alkyne function in 1-(4-ethynylphenyl)-4-(prop-2-enyl)-2,6,7-trioxabicyclo[2.2.2] octane with a trimethylsilyl group permits the selective catalytic reduction of the olefin moiety with tritium gas to give after deprotection 1-(4-ethynylphenyl)-4-[2,3- 3 H 2 ] propyl-2,6,7-trioxabicyclo-[2.2.2] octane. The labeled product at high specific activity is an improved radioligand for the GABA-gated chloride channel of insects and mammals and the intermediate 4-[2,3- 3 H 2 ]propyl-1-[4-[(trimethylsilyl)ethynyl]phenyl]-2,6,7-trioxabicyclo[2.2.2]octane is useful for studies on the metabolic activation of this selective proinsecticide. (author)

  6. Novel selective catalytic reduction with tritium: synthesis of the GABA sub A receptor radioligand 1-(4-ethynylphenyl)-4-(2,3- sup 3 H sub 2 )propyl-2,6,7-trioxabicyclo(2. 2. 2 )octane

    Energy Technology Data Exchange (ETDEWEB)

    Palmer, C J; Casida, J E [California Univ., Berkeley, CA (United States). Pesticide Chemistry and Toxicology Lab.

    1991-07-01

    Protection of the terminal alkyne function in 1-(4-ethynylphenyl)-4-(prop-2-enyl)-2,6,7-trioxabicyclo(2.2.2) octane with a trimethylsilyl group permits the selective catalytic reduction of the olefin moiety with tritium gas to give after deprotection 1-(4-ethynylphenyl)-4-(2,3-{sup 3}H{sub 2}) propyl-2,6,7-trioxabicyclo-(2.2.2) octane. The labeled product at high specific activity is an improved radioligand for the GABA-gated chloride channel of insects and mammals and the intermediate 4-(2,3-{sup 3}H{sub 2})propyl-1-(4-((trimethylsilyl)ethynyl)phenyl)-2,6,7-trioxabicyclo(2.2.2)octane is useful for studies on the metabolic activation of this selective proinsecticide. (author).

  7. Green synthesis, characterization and catalytic activity of natural bentonite-supported copper nanoparticles for the solvent-free synthesis of 1-substituted 1H-1,2,3,4-tetrazoles and reduction of 4-nitrophenol

    Directory of Open Access Journals (Sweden)

    Akbar Rostami-Vartooni

    2015-12-01

    Full Text Available In this study, Cu nanoparticles were immobilized on the surface of natural bentonite using Thymus vulgaris extract as a reducing and stabilizing agent. The natural bentonite-supported copper nanoparticles (Cu NPs/bentonite were characterized by FTIR spectroscopy, X-ray diffraction (XRD, X-ray fluorescence (XRF, field emission scanning electron microscopy (FE-SEM, energy dispersive X-ray spectroscopy (EDS, transmission electron microscopy (TEM, selected area electron diffraction (SAED and Brunauer–Emmett–Teller (BET analysis. Afterward, the catalytic performance of the prepared catalyst was investigated for the solvent-free synthesis of 1-substituted 1H-1,2,3,4-tetrazoles and reduction of 4-nitrophenol (4-NP in water. It was found that the Cu NPs/bentonite is a highly active and recyclable catalyst for related reactions.

  8. Initial Reduction of CO2 on Pd-, Ru-, and Cu-Doped CeO2(111) Surfaces: Effects of Surface Modification on Catalytic Activity and Selectivity.

    Science.gov (United States)

    Guo, Chen; Wei, Shuxian; Zhou, Sainan; Zhang, Tian; Wang, Zhaojie; Ng, Siu-Pang; Lu, Xiaoqing; Wu, Chi-Man Lawrence; Guo, Wenyue

    2017-08-09

    Surface modification by metal doping is an effective treatment technique for improving surface properties for CO 2 reduction. Herein, the effects of doped Pd, Ru, and Cu on the adsorption, activation, and reduction selectivity of CO 2 on CeO 2 (111) were investigated by periodic density functional theory. The doped metals distorted the configuration of a perfect CeO 2 (111) by weakening the adjacent Ce-O bond strength, and Pd doping was beneficial for generating a highly active O vacancy. The analyses of adsorption energy, charge density difference, and density of states confirmed that the doped metals were conducive for enhancing CO 2 adsorption, especially for Cu/CeO 2 (111). The initial reductive dissociation CO 2 → CO* + O* on metal-doped CeO 2 (111) followed the sequence of Cu- > perfect > Pd- > Ru-doped CeO 2 (111); the reductive hydrogenation CO 2 + H → COOH* followed the sequence of Cu- > perfect > Ru- > Pd-doped CeO 2 (111), in which the most competitive route on Cu/CeO 2 (111) was exothermic by 0.52 eV with an energy barrier of 0.16 eV; the reductive hydrogenation CO 2 + H → HCOO* followed the sequence of Ru- > perfect > Pd-doped CeO 2 (111). Energy barrier decomposition analyses were performed to identify the governing factors of bond activation and scission along the initial CO 2 reduction routes. Results of this study provided deep insights into the effect of surface modification on the initial reduction mechanisms of CO 2 on metal-doped CeO 2 (111) surfaces.

  9. Synthesis of TiO2-loaded Co0.85Se thin films with heterostructure and their enhanced catalytic activity for p-nitrophenol reduction and hydrazine hydrate decomposition

    International Nuclear Information System (INIS)

    Zuo, Yong; Song, Ji-Ming; Niu, He-Lin; Mao, Chang-Jie; Zhang, Sheng-Yi; Shen, Yu-Hua

    2016-01-01

    P-nitrophenol (4-NP) and hydrazine hydrate are considered to be highly toxic pollutants in wastewater, and it is of great importance to remove them. Herein, TiO 2 -loaded Co 0.85 Se thin films with heterostructure were successfully synthesized by a hydrothermal route. The as-synthesized samples were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, transmission electron microscopy and selective-area electron diffraction. The results demonstrate that TiO 2 nanoparticles with a size of about 10 nm are easily loaded on the surface of graphene-like Co 0.85 Se nanofilms, and the NH 3  · H 2 O plays an important role in the generation and crystallization of TiO 2 nanoparticles. Brunauer–Emmett–Teller measurement shows that the obtained nanocomposites have a larger specific surface area (199.3 m 2 g −1 ) than that of Co 0.85 Se nanofilms (55.17 m 2 g −1 ) and TiO 2 nanoparticles (19.49 m 2 g −1 ). The catalytic tests indicate Co 0.85 Se–TiO 2 nanofilms have the highest activity for 4-NP reduction and hydrazine hydrate decomposition within 10 min and 8 min, respectively, compared with the corresponding precursor Co 0.85 Se nanofilms and TiO 2 nanoparticles. The enhanced catalytic performance can be attributed to the larger specific surface area and higher rate of interfacial charge transfer in the heterojunction than that of the single components. In addition, recycling tests show that the as-synthesized sample presents stable conversion efficiency for 4-NP reduction. (paper)

  10. Nickel(0)-catalyzed enantioselective annulations of alkynes and arylenoates enabled by a chiral NHC ligand: efficient access to cyclopentenones.

    Science.gov (United States)

    Ahlin, Joachim S E; Donets, Pavel A; Cramer, Nicolai

    2014-11-24

    Cyclopentenones are versatile structural motifs of natural products as well as reactive synthetic intermediates. The nickel-catalyzed reductive [3+2] cycloaddition of α,β-unsaturated aromatic esters and alkynes constitutes an efficient method for their synthesis. Here, nickel(0) catalysts comprising a chiral bulky C1-symmetric N-heterocyclic carbene ligand were shown to enable an efficient asymmetric synthesis of cyclopentenones from mesityl enoates and internal alkynes under mild conditions. The bulky NHC ligand provided the cyclopentenone products in very high enantioselectivity and led to a regioselective incorporation of unsymmetrically substituted alkynes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Ring-Contraction Strategy for the Practical, Scalable, Catalytic Asymmetric Synthesis of Versatile γ-Quaternary Acylcyclopentenes

    KAUST Repository

    Hong, Allen Y.

    2011-02-24

    Contraction action! A simple protocol for the catalytic asymmetric synthesis of highly functionalized γ-quaternary acylcyclopentenes (see schematic) in up to 91 % overall yield and 92 % ee has been developed. The reaction sequence employs a palladium-catalyzed enantioselective alkylation reaction and exploits the unusual stability of β-hydroxy cycloheptanones to achieve a general and robust method for performing two-carbon ring contractions.

  12. Ring-Contraction Strategy for the Practical, Scalable, Catalytic Asymmetric Synthesis of Versatile γ-Quaternary Acylcyclopentenes

    KAUST Repository

    Hong, Allen Y.; Krout, Michael R.; Jensen, Thomas; Bennett, Nathan B.; Harned, Andrew M.; Stoltz, Brian M.

    2011-01-01

    Contraction action! A simple protocol for the catalytic asymmetric synthesis of highly functionalized γ-quaternary acylcyclopentenes (see schematic) in up to 91 % overall yield and 92 % ee has been developed. The reaction sequence employs a palladium-catalyzed enantioselective alkylation reaction and exploits the unusual stability of β-hydroxy cycloheptanones to achieve a general and robust method for performing two-carbon ring contractions.

  13. Enantioselective rhodium/ruthenium photoredox catalysis en route to chiral 1,2-aminoalcohols.

    Science.gov (United States)

    Ma, Jiajia; Harms, Klaus; Meggers, Eric

    2016-08-09

    A rhodium-based chiral Lewis acid catalyst combined with [Ru(bpy)3](PF6)2 as a photoredox sensitizer allows for the visible-light-activated redox coupling of α-silylamines with 2-acyl imidazoles to afford, after desilylation, 1,2-amino-alcohols in yields of 69-88% and with high enantioselectivity (54-99% ee). The reaction is proposed to proceed via an electron exchange between the α-silylamine (electron donor) and the rhodium-chelated 2-acyl imidazole (electron acceptor), followed by a stereocontrolled radical-radical reaction. Substrate scope and control experiments reveal that the trimethylsilyl group plays a crucial role in this reductive umpolung of the carbonyl group.

  14. Catalytic reduction of NH4NO3 by NO. Effects of solid acids and implications for low temperature DeNOx processes

    International Nuclear Information System (INIS)

    Savara, Aditya; Li, Mei-Jun; Sachtler, Wolfgang M.H.; Weitz, Eric

    2008-01-01

    Ammonium nitrate is thermally stable below 250 C and could potentially deactivate low temperature NO x reduction catalysts by blocking active sites. It is shown that NO reduces neat NH 4 NO 3 above its 170 C melting point, while acidic solids catalyze this reaction even at temperatures below 100 C. NO 2 , a product of the reduction, can dimerize and then dissociate in molten NH 4 NO 3 to NO + + NO 3 - , and may be stabilized within the melt as either an adduct or as HNO 2 formed from the hydrolysis of NO + or N 2 O 4 . The other product of reduction, NH 4 NO 2 , readily decomposes at ≤100 C to N 2 and H 2 O, the desired end products of DeNO x catalysis. A mechanism for the acid catalyzed reduction of NH 4 NO 3 by NO is proposed, with HNO 3 as an intermediate. These findings indicate that the use of acidic catalysts or promoters in DeNO x systems could help mitigate catalyst deactivation at low operating temperatures (<150 C). (author)

  15. Catalytic asymmetric Meerwein-Ponndorf-Verley reduction of glyoxylates induced by a chiral N,N'-dioxide/Y(OTf)3 complex.

    Science.gov (United States)

    Wu, Wangbin; Zou, Sijia; Lin, Lili; Ji, Jie; Zhang, Yuheng; Ma, Baiwei; Liu, Xiaohua; Feng, Xiaoming

    2017-03-18

    An asymmetric Meerwein-Ponndorf-Verley (MPV) reduction of glyoxylates was for the first time accomplished via an N,N'-dioxide/Y(OTf) 3 complex with aluminium alkoxide and molecular sieves (MSs) as crucial additives. A variety of optically active α-hydroxyesters were obtained with excellent results. A possible reaction mechanism was proposed based on the experiments.

  16. Enantioselective ProPhenol-catalyzed addition of 1,3-diynes to aldehydes to generate synthetically versatile building blocks and diyne natural products.

    Science.gov (United States)

    Trost, Barry M; Chan, Vincent S; Yamamoto, Daisuke

    2010-04-14

    A highly enantioselective method for the catalytic addition of terminal 1,3-diynes to aldehydes was developed using our dinuclear zinc ProPhenol (1) system. Furthermore, triphenylphosphine oxide was found to interact synergistically with the catalyst to substantially enhance the chiral recognition. The generality of this catalytic transformation was demonstrated with aryl, alpha,beta-unsaturated and saturated aldehydes, of which the latter were previously limited in alkynyl zinc additions. The chiral diynol products are also versatile building blocks that can be readily elaborated; this was illustrated through highly selective trans-hydrosilylations, which enabled the synthesis of a beta-hydroxyketone and enyne. Additionally, the development of this method allowed for the rapid total syntheses of several biologically important diynol-containing natural products.

  17. 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.

  18. Enantioselective silver nanoclusters: Preparation, characterization and photoluminescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Farrag, Mostafa, E-mail: mostafafarrag@aun.edu.eg

    2016-09-01

    Herein, we report a new wet-synthesis method to separate some water-soluble chiral silver nanoclusters with high yield. The cluster material was obtained by the reduction of silver nitrate with NaBH{sub 4} in the presence of three ligands L-penicillamine (L-pen), D-penicillamine (D-pen) and racemic mixture of penicillamine (rac-pen), functioning as capping ligand. For characterizing all silver cluster samples, the particle size was assessed by transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) and their average chemical formula was determined from thermogravimetric analysis (TGA) and elemental analysis (EA). The particles sizes of all three clusters are 2.1 ± 0.2 nm. The optical properties of the samples were studied by four different methods: UV-vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), photoluminescence spectroscopy (PL) and circular dichroism (CD) spectroscopy. The spectra are dominated by the typical and intense plasmon peak at 486 nm accompanied by a small shoulder at 540 nm. Infrared spectroscopy was measured for the free ligand and protected silver nanoclusters, where the disappearance of the S-H vibrational band (2535–2570 cm{sup −1}) in the silver nanoclusters confirmed anchoring of ligand to the cluster surface through the sulfur atom. PL studies yielded the fluorescent properties of the samples. The main focus of this work, however, lies in the chirality of the particles. For all silver clusters CD spectra were recorded. While for clusters capped with one of the two enantiomers (D- or L-form) typical CD spectra were observed, no significant signals were detected for a racemic ligand mixture. Furthermore, silver clusters show quite large asymmetry factors (up to 3 × 10{sup −4}) in comparison to most other ligand protected clusters. These large factors and bands in the visible range of the spectrum suggest a strong chiral induction from the ligand to the metal core. Textural features of the

  19. Enantioselective conjugate addition of diethylzinc to chalcone catalyzed by Co(acac)2 and chiral amino alcohols

    NARCIS (Netherlands)

    Vries, André H.M. de; Feringa, Bernard

    1997-01-01

    Co(acac)2 in the presence of chiral ligands has been employed as catalyst for the enantioselective conjugate addition of diethylzinc to chalcone. With chiral amino alcohols derived from (+)-camphor, enantioselectivities up to 83% were achieved.

  20. Nitric Oxide Reduction by Carbon Monoxide over Supported Hexaruthenium Cluster Catalysts. 1. The Active Site Structure That Depends on Supporting Metal Oxide and Catalytic Reaction Conditions.

    Science.gov (United States)

    Minato, Taketoshi; Izumi, Yasuo; Aika, Ken-Ichi; Ishiguro, Atsushi; Nakajima, Takayuki; Wakatsuki, Yasuo

    2003-08-28

    Ruthenium site structures supported on metal oxide surfaces were designed by reacting organometallic Ru cluster [Ru6C(CO)16](2-) or [Ru6(CO)18](2-) with various metal oxides, TiO2, Al2O3, MgO, and SiO2. The surface Ru site structure, formed under various catalyst preparation and reaction conditions, was investigated by the Ru K-edge extended X-ray absorption fine structure (EXAFS). Samples of [Ru6C(CO)16](2-)/TiO2(anatase) and [Ru6C(CO)16](2-)/TiO2(rutile) were found to retain the original Ru6C framework when heated in the presence of NO (2.0 kPa) or NO (2.0 kPa) + CO (2.0 kPa) at 423 K, i.e., catalytic reaction conditions for NO decomposition. At 523 K, the Ru-Ru bonds of the Ru6C framework were cleaved by the attack of NO. In contrast, the Ru site became spontaneously dispersed over TiO2 (anatase). When being supported over TiO2 (mesoporous), MgO, or Al2O3, the Ru6C framework split into fragments in gaseous NO or NO + CO even at 423 K. The Ru6 framework of [Ru6(CO)18](2-) was found to break easily into smaller ensembles in the presence of NO and/or CO at 423 K on support. Taking into consideration the realistic environments in which these catalysts will be used, we also examined the effect of water and oxygen. When water was introduced to the sample [Ru6C(CO)16](2-)/TiO2(anatase) at 423 K, it did not have any effects on the stabilized Ru6C framework structure. In the presence of oxygen gas, however, the Ru hexanuclear structure decomposed into isolated Ru cations bound to surface oxygen atoms of TiO2 (anatase).

  1. A novel approach for the synthesis of ultrathin silica-coated iron oxide nanocubes decorated with silver nanodots (Fe3O4/SiO2/Ag) and their superior catalytic reduction of 4-nitroaniline

    Science.gov (United States)

    Abbas, Mohamed; Torati, Sri Ramulu; Kim, Cheolgi

    2015-07-01

    A novel sonochemical approach was developed for the synthesis of different core/shell structures of Fe3O4/SiO2/Ag nanocubes and SiO2/Ag nanospheres. The total reaction time of the three sonochemical steps for the synthesis of Fe3O4/SiO2/Ag nanocubes is shorter than that of the previously reported methods. A proposed reaction mechanism for the sonochemical functionalization of the silica and the silver on the surface of magnetic nanocubes was discussed in detail. Transmission electron microscopy revealed that the surface of Fe3O4/SiO2 nanocubes was decorated with small Ag nanoparticles of approximately 10-20 nm in size, and the energy dispersive spectroscopy mapping analysis confirmed the morphology of the structure. Additionally, X-ray diffraction data were used to confirm the formation of both phases of a cubic inverse spinel structure for Fe3O4 and bcc structures for Ag in the core/shell structure of the Fe3O4/SiO2/Ag nanocubes. The as-synthesized Fe3O4/SiO2/Ag nanocubes showed a high efficiency in the catalytic reduction reaction of 4-nitroaniline to 4-phenylenediamine and a better performance than both Ag and SiO2/Ag nanoparticles. The grafted silver catalyst was recycled and reused at least fifteen times without a significant loss of catalytic efficiency.A novel sonochemical approach was developed for the synthesis of different core/shell structures of Fe3O4/SiO2/Ag nanocubes and SiO2/Ag nanospheres. The total reaction time of the three sonochemical steps for the synthesis of Fe3O4/SiO2/Ag nanocubes is shorter than that of the previously reported methods. A proposed reaction mechanism for the sonochemical functionalization of the silica and the silver on the surface of magnetic nanocubes was discussed in detail. Transmission electron microscopy revealed that the surface of Fe3O4/SiO2 nanocubes was decorated with small Ag nanoparticles of approximately 10-20 nm in size, and the energy dispersive spectroscopy mapping analysis confirmed the morphology of the

  2. Engineering an enantioselective amine oxidase for the synthesis of pharmaceutical building blocks and alkaloid natural products.

    Science.gov (United States)

    Ghislieri, Diego; Green, Anthony P; Pontini, Marta; Willies, Simon C; Rowles, Ian; Frank, Annika; Grogan, Gideon; Turner, Nicholas J

    2013-07-24

    The development of cost-effective and sustainable catalytic methods for the production of enantiomerically pure chiral amines is a key challenge facing the pharmaceutical and fine chemical industries. This challenge is highlighted by the estimate that 40-45% of drug candidates contain a chiral amine, fueling a demand for broadly applicable synthetic methods that deliver target structures in high yield and enantiomeric excess. Herein we describe the development and application of a "toolbox" of monoamine oxidase variants from Aspergillus niger (MAO-N) which display remarkable substrate scope and tolerance for sterically demanding motifs, including a new variant, which exhibits high activity and enantioselectivity toward substrates containing the aminodiphenylmethane (benzhydrylamine) template. By combining rational structure-guided engineering with high-throughput screening, it has been possible to expand the substrate scope of MAO-N to accommodate amine substrates containing bulky aryl substituents. These engineered MAO-N biocatalysts have been applied in deracemization reactions for the efficient asymmetric synthesis of the generic active pharmaceutical ingredients Solifenacin and Levocetirizine as well as the natural products (R)-coniine, (R)-eleagnine, and (R)-leptaflorine. We also report a novel MAO-N mediated asymmetric oxidative Pictet-Spengler approach to the synthesis of (R)-harmicine.

  3. Innovative clean coal technology (ICCT): demonstration of selective catalytic reduction (SCR) technology for the control of nitrogen oxide (NOx) emission from high-sulfur, coal-fired boilers - economic evaluation of commercial-scale SCR applications for utility boilers

    International Nuclear Information System (INIS)

    Healy, E.C.; Maxwell, J.D.; Hinton, W.S.

    1996-09-01

    This report presents the results of an economic evaluation produced as part of the Innovative Clean Coal Technology project, which demonstrated selective catalytic reduction (SCR) technology for reduction of NO x emissions from utility boilers burning U.S. high-sulfur coal. The document includes a commercial-scale capital and O ampersand M cost evaluation of SCR technology applied to a new facility, coal-fired boiler utilizing high-sulfur U.S. coal. The base case presented herein determines the total capital requirement, fixed and variable operating costs, and levelized costs for a new 250-MW pulverized coal utility boiler operating with a 60-percent NO x removal. Sensitivity evaluations are included to demonstrate the variation in cost due to changes in process variables and assumptions. This report also presents the results of a study completed by SCS to determine the cost and technical feasibility of retrofitting SCR technology to selected coal-fired generating units within the Southern electric system

  4. Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

    KAUST Repository

    Thomas, Renee M.

    2010-11-24

    A highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.

  5. Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

    KAUST Repository

    Thomas, Renee M.; Widger, Peter C. B.; Ahmed, Syud M.; Jeske, Ryan C.; Hirahata, Wataru; Lobkovsky, Emil B.; Coates, Geoffrey W.

    2010-01-01

    A highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.

  6. Enhancing the potential of enantioselective organocatalysis with light

    Science.gov (United States)

    Silvi, Mattia; Melchiorre, Paolo

    2018-02-01

    Organocatalysis—catalysis mediated by small chiral organic molecules—is a powerful technology for enantioselective synthesis, and has extensive applications in traditional ionic, two-electron-pair reactivity domains. Recently, organocatalysis has been successfully combined with photochemical reactivity to unlock previously inaccessible reaction pathways, thereby creating new synthetic opportunities. Here we describe the historical context, scientific reasoning and landmark discoveries that were essential in expanding the functions of organocatalysis to include one-electron-mediated chemistry and excited-state reactivity.

  7. Enantioselective synthesis of alpha,beta-disubstituted-beta-amino acids.

    Science.gov (United States)

    Sibi, Mukund P; Prabagaran, Narayanasamy; Ghorpade, Sandeep G; Jasperse, Craig P

    2003-10-01

    Highly diastereoselective and enantioselective addition of N-benzylhydroxylamine to imides 17 and 20-30 produces alpha,beta-trans-disubstituted N-benzylisoxazolidinones 19 and 31-41. These reactions proceed in 60-96% ee with 93-99% de's using 5 mol % of Mg(NTf2)2 and ligand 18. The product isoxazolidinones can be hydrogenolyzed directly to provide alpha,beta-disubstituted-beta-amino acids.

  8. Enantioselective conjugate radical addition to alpha'-hydroxy enones.

    Science.gov (United States)

    Lee, Sunggi; Lim, Chae Jo; Kim, Sunggak; Subramaniam, Rajesh; Zimmerman, Jake; Sibi, Mukund P

    2006-09-14

    Enantioselective conjugate radical addition to alpha'-hydroxy alpha,beta-unsaturated ketones, compounds containing bidentate donors, has been investigated. It has been found that radical additions to alpha'-hydroxy alpha,beta-unsaturated ketones in the presence of Mg(NTf2)2 and bisoxazoline ligand 5a proceeded cleanly, yielding the addition products in high chemical yields and good enantiomeric excesses.

  9. Enantiomerization and enantioselective bioaccumulation of metalaxyl in Tenebrio molitor larvae.

    Science.gov (United States)

    Gao, Yongxin; Wang, Huili; Qin, Fang; Xu, Peng; Lv, Xiaotian; Li, Jianzhong; Guo, Baoyuan

    2014-02-01

    The enantiomerization and enantioselective bioaccumulation of metalaxyl by a single dose of exposure to Tenebrio molitor larvae under laboratory condition were studied by high-performance liquid chromatography tandem mass spectroscopy (HPLC-MS/MS) based on a ChiralcelOD-3R [cellulosetris-tris-(3, 5-dichlorophenyl-carbamate)] column. Exposure of enantiopure R-metalaxyl and S-metalaxyl in Tenebrio molitor larvae exhibited significant enantiomerization, with formation of the R enantiomers from the S enantiomers, and vice versa, which might be attributed to the chiral pesticide catalyzed by a certain enzyme in Tenebrio molitor larvae. Enantiomerization was not observed in wheat bran during the period of 21 d. In addition, bioaccumulation of rac-metalaxyl in Tenebrio molitor larvae was enantioselective with a preferential accumulation of S-metalaxyl. These results showed that enantioselectivity was caused not only by actual degradation and metabolism but also by enantiomerization, which was an important process in the environmental fate and behavior of metalaxyl enantiomers. Copyright © 2013 Wiley Periodicals, Inc.

  10. Flavin-cyclodextrin conjugates: effect of the structure on the catalytic activity in enantioselective sulfoxidations

    Czech Academy of Sciences Publication Activity Database

    Hartman, T.; Herzig, Vladimír; Buděšínský, Miloš; Jindřich, J.; Cibulka, R.; Kraus, Tomáš

    2012-01-01

    Roč. 23, 22/23 (2012), s. 1571-1583 ISSN 0957-4166 R&D Projects: GA ČR GA203/09/1919 Grant - others:GA ČR(CZ) GAP207/12/0447 Institutional support: RVO:61388963 Keywords : enzyme mimics * aqueous hydrogen-peroxide * asymmetric sulfide oxidation * kinetic resolution * molecular-oxygen Subject RIV: CC - Organic Chemistry Impact factor: 2.115, year: 2012

  11. HIGHLY ENANTIOSELECTIVE CATALYTIC DIRECT ADDITION OF ALKYNES TO IMINES IN WATER. (R828129)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  12. Catalytic enantioselective addition of organometallic reagents to N-formylimines using monodentate phosphoramidite ligands

    NARCIS (Netherlands)

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

    2008-01-01

    [GRAPHICS] The asymmetric synthesis of protected amines via the copper/phosphoramidite-catalyzed addition of organozine and organoaluminum reagents to N-acylimines, generated in situ from aromatic and aliphatic alpha-amidosulfones, is reported. High yields of optically active N-formyl-protected

  13. Catalytic Enantioselective Addition of Organometallic Reagents to N-Formylimines Using Monodentate Phosphoramidite Ligands

    NARCIS (Netherlands)

    Pizzuti, Maria Gabriella; Minnaard, Adriaan J.; Feringa, Bernard

    2008-01-01

    The asymmetric synthesis of protected amines via the copper/phosphoramidite-catalyzed addition of organozinc and organoaluminum reagents to N-acylimines, generated in situ from aromatic and aliphatic α-amidosulfones, is reported. High yields of optically active N-formyl-protected amines and

  14. Dicationic ionic liquid mediated fabrication of Au@Pt nanoparticles supported on reduced graphene oxide with highly catalytic activity for oxygen reduction and hydrogen evolution

    Science.gov (United States)

    Shi, Ya-Cheng; Chen, Sai-Sai; Feng, Jiu-Ju; Lin, Xiao-Xiao; Wang, Weiping; Wang, Ai-Jun

    2018-05-01

    Ionic liquids as templates or directing agents have attracted great attention for shaping-modulated synthesis of advanced nanomaterials. In this work, reduced graphene oxide supported uniform core-shell Au@Pt nanoparticles (Au@Pt NPs/rGO) were fabricated by a simple one-pot aqueous approach, using N-methylimidazolium-based dicationic ionic liquid (1,1-bis(3-methylimadazoilum-1-yl)butylene bromide, [C4(Mim)2]2Br) as the shape-directing agent. The morphology evolution, structural information and formation mechanism of Au@Pt NPs anchored on rGO were investigated by a series of characterization techniques. The obtained nanocomposites displayed superior electrocatalytic features toward hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) compared with commercial Pt/C catalyst. This approach provides a novel route for facile synthesis of nanocatalysts in fuel cells.

  15. Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Eraenen, K; Kumar, N; Lindfors, L E [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry

    1997-12-31

    Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

  16. Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Eraenen, K.; Kumar, N.; Lindfors, L.E. [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry

    1996-12-31

    Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

  17. Intercalation assembly of Li{sub 3}VO{sub 4} nanoribbons/graphene sandwich-structured composites with enhanced oxygen reduction catalytic performance

    Energy Technology Data Exchange (ETDEWEB)

    Huang, K.; Ling, Q.N.; Huang, C.H.; Bi, K. [State Key Laboratory of Information Photonics and Optical Communications & School of Science, Beijing University of Posts and Telecommunications, Beijing 100876 (China); Wang, W.J.; Yang, T.Z. [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China); Lu, Y.K. [School of Materials Science and Engineering, Central South University, Changsha, Hunan 410083 (China); Liu, J., E-mail: liujun4982004@csu.edu.cn [School of Materials Science and Engineering, Central South University, Changsha, Hunan 410083 (China); Zhang, R.; Fan, D.Y.; Wang, Y.G. [State Key Laboratory of Information Photonics and Optical Communications & School of Science, Beijing University of Posts and Telecommunications, Beijing 100876 (China); Lei, Ming, E-mail: mlei@bupt.edu.cn [State Key Laboratory of Information Photonics and Optical Communications & School of Science, Beijing University of Posts and Telecommunications, Beijing 100876 (China)

    2015-10-15

    Novel sandwich-like nanocomposites of alternative stacked ultrathin Li{sub 3}VO{sub 4} nanoribbons and graphene sheets (LVO-G) were successfully developed by a facile intercalation assembly method with a post heating treatment. The characterization results demonstrate that the average size of the Li{sub 3}VO{sub 4} nanoribbons with a non-layered crystal structure is a few micrometers in length, 50–100 nm in width and a few atomic layers in height. The addition of graphene sheets can modify the preferred orientation of the Li{sub 3}VO{sub 4} nanoribbons from (110) to (011) plane and restrict the growth of impurity phase at the same time. In addition, EIS analysis has also verified the reduced resistance and thus the enhance conductivity of LVO-G nanocomposites compared with bare Li{sub 3}VO{sub 4} nanoribbons. What's more, the electrocatalytic performances of these novel LVO-G nanocomposites for oxygen reduction reaction (ORR) in alkaline solution are further investigated by cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry test. It is found that the enhanced activity and stability of LVO-G can be attributed to the synergistic effect between the Li{sub 3}VO{sub 4} nanoribbons and graphene sheets with a larger reduction current density and a smaller onset potential value for LVO-G25 compared with LVO-G50 due to the change of components. - Highlights: • Novel sandwich-structured LVO-G by a facile intercalation assembly method. • Addition of G sheets can modify the preferred orientation of Li{sub 3}VO{sub 4} nanoribbon. • Enhanced ORR activity and stability due to synergistic effect are demonstrated.

  18. A Au/Cu2O-TiO2 system for photo-catalytic hydrogen production. A pn-junction effect or a simple case of in situ reduction?

    KAUST Repository

    Sinatra, Lutfan

    2015-02-01

    Photo-catalytic H2 production from water has been studied over Au-Cu2O nanoparticle deposited on TiO2 (anatase) in order to probe into both the plasmon resonance effect (Au nanoparticles) and the pn-junction at the Cu2O-TiO2 interface. The Au-Cu2O composite is in the form of ∼10 nm Au nanoparticles grown on ∼475 nm Cu2O octahedral nanocrystals with (111) facets by partial galvanic replacement. X-ray Photoelectron Spectroscopy (XPS) Cu2p and Auger L3M4,5M4,5 lines indicate that the surface of Cu2O is mainly composed of Cu+. The rate for H2 production (from 95 water/5 ethylene glycol; vol.%) over 2 wt.% (Au/Cu2O)-TiO2 is found to be ∼10 times faster than that on 2 wt.% Au-TiO2 alone. Raman spectroscopy before and after reaction showed the disappearance of Cu+ lines (2Eu) at 220 cm-1. These observations coupled with the induction time observed for the reaction rate suggest that in situ reduction from Cu+ to Cu0 occurs upon photo-excitation. The reduction requires the presence of TiO2 (electron transfer). The prolonged activity of the reaction (with no signs of deactivation) despite the reduction to Cu0 indicates that the latter takes part in the reaction by providing additional sites for the reaction, most likely as recombination centers for hydrogen atoms to form molecular hydrogen. This phenomenon provides an additional route for enhancing the efficiency and lifetime of Cu2O-TiO2 photocatalytic systems, beyond the usually ascribed pn-junction effect.

  19. Comparison of liquid and supercritical fluid chromatography mobile phases for enantioselective separations on polysaccharide stationary phases.

    Science.gov (United States)

    Khater, Syame; Lozac'h, Marie-Anne; Adam, Isabelle; Francotte, Eric; West, Caroline

    2016-10-07

    Analysis and production of enantiomerically pure compounds is a major topic of interest when active pharmaceutical ingredients are concerned. Enantioselective chromatography has become a favourite both at the analytical and preparative scales. High-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC) are dominating the scene and are often seen as complementary techniques. Nowadays, for economic and ecologic reasons, SFC may be preferred over normal-phase HPLC (NPLC) as it allows significant reductions in solvent consumption. However, the transfer of NPLC methods to SFC is not always straightforward. In this study, we compare the retention of achiral molecules and separation of enantiomers under supercritical fluid (carbon dioxide with ethanol or isopropanol) and liquid normal-phase (heptane with ethanol or isopropanol) elution modes with polysaccharide stationary phases in order to explore the differences between the retention and enantioseparation properties between the two modes. Chemometric methods (namely quantitative structure-retention relationships and discriminant analysis) are employed to compare the results obtained on a large set of analytes (171 achiral probes and 97 racemates) and gain some understanding on the retention and separation mechanisms. The results indicate that, contrary to popular belief, carbon dioxide - solvent SFC mobile phases are often weaker eluents than liquid mobile phases. It appears that SFC and NPLC elution modes provide different retention mechanisms. While some enantioseparations are unaffected, facilitating the transfer between the two elution modes, other enantioseparations may be drastically different due to different types and strength of interactions contributing to enantioselectivity. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. The poisoning effect of PbO on Mn-Ce/TiO{sub 2} catalyst for selective catalytic reduction of NO with NH{sub 3} at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Lingling [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China); Li, Caiting, E-mail: ctli@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China); Zhao, Lingkui; Zeng, Guangming; Gao, Lei; Wang, Yan; Yu, Ming’e [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China)

    2016-12-15

    Highlights: • The poisoning effects of PbO-doped Mn-Ce/TiO{sub 2} catalysts for low temperature NH{sub 3}-SCR were investigated. • Low concentration of Mn{sup 4+} and chemisorbed oxygen (O{sub b}) were not favorable for the generation of intermediates. • The decreased Ce{sup 3+} and less reducible of manganese oxides hindered the redox cycle (Mn{sup 3+} + Ce{sup 4+} ↔ Mn{sup 4+} + Ce{sup 3+}). • The doping of PbO not only altered acid sites but also inhibited ammonia adsorption as well as activation. • The poisoning of PbO resulted in the decrease of ad-NO{sub x} species (only a spot of bidentate nitrates remained). - Abstract: Lead oxide (PbO) as one of the typical heavy metals in flue gas from power plants has strong accumulation as well as poisoning effects on SCR catalysts. In this paper, a series of PbO-doped Mn-Ce/TiO{sub 2} catalysts were synthesized by impregnation method. The poisoning effects of PbO over Mn-Ce/TiO{sub 2} samples for selective catalytic reduction of NO by NH{sub 3} were investigated based on catalytic activity test and characterizations. The NO conversion of Mn-Ce/TiO{sub 2} was greatly decreased after the addition of PbO. It was obvious that the NO conversion efficiency of Mn-Ce/TiO{sub 2} catalyst declined from 96.75% to about 40% at 200 °C when Pb:Mn molar ratio reached 0.5. Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Hydrogen temperature programmed reduction (H{sub 2}-TPR), Ammonia temperature programmed desorption (NH{sub 3}-TPD) and Fourier transform infrared spectroscopy (FT-IR) were carried out to study the deactivation reasons of PbO poisoned catalysts. Manganese oxides’ crystallization, less reducible of manganese and cerium oxides, the decreasing of surface area, Mn{sup 4+} as well as Ce{sup 3+} concentration and chemisorbed oxygen (O{sub b}) after the introduction of PbO, all of these resulted in a poor SCR performance

  1. Enantioselective carbenoid insertion into C(sp3–H bonds

    Directory of Open Access Journals (Sweden)

    J. V. Santiago

    2016-05-01

    Full Text Available The enantioselective carbenoid insertion into C(sp3–H bonds is an important tool for the synthesis of complex molecules due to the high control of enantioselectivity in the formation of stereogenic centers. This paper presents a brief review of the early issues, related mechanistic studies and recent applications on this chemistry area.

  2. Application of enantioselective radical reactions: synthesis of (+)-ricciocarpins A and B.

    Science.gov (United States)

    Sibi, Mukund P; He, Liwen

    2004-05-27

    Enantioselective synthesis of (+)-ricciocarpins A and B has been achieved in 41 and 45% overall yields, respectively, starting from a beta-substituted oxazolidinone. The key steps in the strategy are an enantioselective conjugate radical addition and the addition of a furyl organometallic to a key aldehyde intermediate. [reaction--see text

  3. Copper(II)-catalyzed exo and enantioselective cycloadditions of azomethine imines.

    Science.gov (United States)

    Sibi, Mukund P; Rane, Digamber; Stanley, Levi M; Soeta, Takahiro

    2008-07-17

    A strategy for exo and enantioselective 1,3-dipolar cycloaddition of azomethine imines to 2-acryloyl-3-pyrazolidinone is described. The corresponding cycloadducts are isolated with high diastereoselectivities (up to >96:4 exo/endo) and enantioselectivities (up to 98% ee).

  4. Enantioselective rhodium enolate protonations. A new methodology for the synthesis of beta2-amino acids.

    Science.gov (United States)

    Sibi, Mukund P; Tatamidani, Hiroto; Patil, Kalyani

    2005-06-23

    [reaction: see text] Rhodium-catalyzed conjugate addition of an aryl boronic acid to alpha-methylamino acrylates followed by enantioselective protonation of the oxa-pi-allylrhodium intermediate provides access to aryl-substituted beta(2)-amino acids. The impact of the different variables of the reaction on the levels of enantioselectivity has been assessed.

  5. Enantioselective H-atom transfer reaction: a strategy to synthesize formaldehyde aldol products.

    Science.gov (United States)

    Sibi, Mukund P; Patil, Kalyani

    2005-04-14

    [reaction: see text] Enantioselective radical alkylation of Baylis-Hillman adducts furnished aldol products in good yield and selectivity. The results illustrate that the selectivity in the hydrogen atom transfer is dependent on the size of the ester substituent, with smaller substituents providing better enantioselectivity.

  6. Enantioselective Rhodium Enolate Protonations. A New Methodology for the Synthesis of β2-Amino Acids

    Science.gov (United States)

    Sibi, Mukund P.; Tatamidani, Hiroto; Patil, Kalyani

    2008-01-01

    Rhodium catalyzed conjugate addition of an aryl boronic acid to α-methylamino acrylates followed by enantioselective protonation of the oxa-π-allylrhodium intermediate provides access to aryl substituted β2-amino acids. The impact of the different variables of the reaction on the levels of enantioselectivity has been assessed. PMID:15957893

  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. Selective catalytic reduction of NO{sub x} in lean-burn engine exhaust over a Pt/V/MCM-41 catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, Jong Yeol; Kim, Hee Young [Division of Advanced Chemical Technology, Korea Reasearch Institute of Chemical Technology, P.O. Box 107, Yusong, Taejon 305-600 (Korea, Republic of); Woo, Seong Ihl [Department of Chemical and Biomolecular Engineering, Center for Ultramicrochemical Process Systems, Korea Advanced Institute of Science and Technology, 373-1, Kusong-dong, Yusong-gu, Taejon, 305-701 (Korea, Republic of)

    2003-09-08

    The activities of Pt supported on various metal-substituted MCM-41 (V-, Ti-, Fe-, Al-, Ga-, La-, Co-, Mo-, Ce-, and Zr-MCM-41) and V-impregnated MCM-41 were investigated for the reduction of NO by C{sub 3}H{sub 6}. Among these catalysts, Pt supported on V-impregnated MCM-41 showed the best activity. The maximum conversion of NO into N{sub 2}+N{sub 2}O over this Pt/V/MCM-41 catalyst (Pt=1wt.%, V=3.8wt.%) was 73%, and this maximum conversion was sustained over a temperature range of 70C from 270 to 340C. The high activity of Pt/V/MCM-41 over a broad temperature range resulted from two additional reactions besides the reaction occurring on usual supported Pt, the reaction of NO with surface carbonaceous materials, and the reaction of NO occurring on support V-impregnated MCM-41. The former additional reaction showed an oscillation characteristic, a phenomenon in which the concentrations of parts of reactant and product gases oscillate continuously. At low temperature, some water vapor injected into the reactant gas mixture promoted the reaction occurring on usual supported Pt, whereas at high temperature, it suppressed the additional reaction related to carbonaceous materials. Five-hundred parts per million of SO{sub 2} added to the reactant gas mixture only slightly decreased the NO conversion of Pt/V/MCM-41.

  9. 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.

  10. 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.

  11. An enantioselective synthesis of S-[gamma]-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3-[sup 14]C] hydrochloride, an important metabolite of fluoxetine hydrochloride

    Energy Technology Data Exchange (ETDEWEB)

    Wheeler, W.J. (Lilly (Eli) and Co., Indianapolis, IN (United States). Lilly Research Labs.)

    1992-06-01

    The S-enantiomer of [gamma]-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3-[sup 14]C] hydrochloride has been prepared in eight steps from acetophenone-[carbonyl-[sup 14]C]. The key step in the synthesis involved the enantioselective reduction of R-2-chloroacetophenone-[1-[sup 14]C]with (-)-diisopinocampheyl-chloroborane in an 86.5% yield. The chlorohydrin was converted to R-phenyloxirane-[1-[sup 14]C], which was subsequently converted to the corresponding R-cyanohydrin by reaction with TMS-CN/CaO. Borane reduction and arylation, followed by salt formation yielded S-[gamma]-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3-[sup 14]C] hydrochloride. (author).

  12. An enantioselective synthesis of S-γ-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3-14C] hydrochloride, an important metabolite of fluoxetine hydrochloride

    International Nuclear Information System (INIS)

    Wheeler, W.J.

    1992-01-01

    The S-enantiomer of γ-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3- 14 C] hydrochloride has been prepared in eight steps from acetophenone-[carbonyl- 14 C]. The key step in the synthesis involved the enantioselective reduction of R-2-chloroacetophenone-[1- 14 C]with (-)-diisopinocampheyl-chloroborane in an 86.5% yield. The chlorohydrin was converted to R-phenyloxirane-[1- 14 C], which was subsequently converted to the corresponding R-cyanohydrin by reaction with TMS-CN/CaO. Borane reduction and arylation, followed by salt formation yielded S-γ-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3- 14 C] hydrochloride. (author)

  13. Higher-order human telomeric G-quadruplex DNA metalloenzymes enhance enantioselectivity in the Diels-Alder reaction.

    Science.gov (United States)

    Li, Yinghao; Jia, Guoqing; Wang, Changhao; Cheng, Mingpan; Li, Can

    2015-03-02

    Short human telomeric (HT) DNA sequences form single G-quadruplex (G4 ) units and exhibit structure-based stereocontrol for a series of reactions. However, for more biologically relevant higher-order HT G4 -DNAs (beyond a single G4 unit), the catalytic performances are unknown. Here, we found that higher-order HT G4 -DNA copper metalloenzymes (two or three G4 units) afford remarkably higher enantioselectivity (>90 % ee) and a five- to sixfold rate increase, compared to a single G4 unit, for the Diels-Alder reaction. Electron paramagnetic resonance (EPR) and enzymatic kinetic studies revealed that the distinct catalytic function between single and higher-order G4 -DNA copper metalloenzymes can be attributed to different Cu(II) coordination environments and substrate specificity. Our finding suggests that, like protein enzymes and ribozymes, higher-order structural organization is crucial for G4 -DNA-based catalysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Enantioselective N-demethylation and hydroxylation of sibutramine in human liver microsomes and recombinant cytochrome p-450 isoforms.

    Science.gov (United States)

    Shinde, Dhananjay D; Kim, Min-Jung; Jeong, Eun-Sook; Kim, Yang-Weon; Lee, Ji-Woo; Shin, Jae-Gook; Kim, Dong-Hyun

    2014-01-01

    The enantioselective metabolism of sibutramine was examined using human liver microsomes (HLM) and recombinant cytochrome P-450 (CYP) isoforms. This drug is metabolized to N-mono-desmethyl- (M1) and N,N-di-desmethylsibutramine (M2), and subsequent hydroxylation results in hydroxyl M1 (HM1) and hydroxyl M2 (HM2). No significant difference was noted in formation of M1from sibutramine between R- and S-sibutramine in HLM. However, S-enantiomers of M1 and M2 were preferentially metabolized to M2, HM1, and HM2compared to R-enantiomers in HLM, and intrinsic clearance (Clint) ratios of S-enantiomers/R-enantiomers were 1.97, 4.83, and 9.94 for M2, HM1, and HM2, respectively. CYP3A4 and CYP3A5 were only involved in the formation of M1, whereas CYP2B6 and CYP2C19 were responsible for all metabolic reactions of sibutramine. CYP2C19 and CYP3A5 displayed catalytic preference for S-sibutramine to S-M1, whereas CYP2B6 and CYP3A4 showed little or no stereoselectivity in metabolism of sibutramine to M1. In the case of M2 formation, CYP2B6 metabolized S-M1 more rapidly than R-M1 with a Clint ratio of 2.14. However, CYP2C19 catalyzed less S-M1 than R-M1 and the Clint ratio of S-M1 to R-M1 was 0.65. The most significant enantioselectivity was observed in formation of HM1 from M1, and HM2 from M2. CYP2B6 and CYP2C19 exhibited preferential catalysis of formation of hydroxyl metabolites from S-enantiomers rather than R-enantiomers. These results indicate that S-sibutramine was more rapidly metabolized by CYP isoforms than R-sibutramine, and that enantioselective metabolism needs to be considered in drug interactions involving sibutramine and co-administered drugs.

  15. Enhanced catalysis and enantioselective resolution of racemic naproxen methyl ester by lipase encapsulated within iron oxide nanoparticles coated with calix[8]arene valeric acid complexes.

    Science.gov (United States)

    Sayin, Serkan; Akoz, Enise; Yilmaz, Mustafa

    2014-09-14

    In this study, two types of nanoparticles have been used as additives for the encapsulation of Candida rugosa lipase via the sol-gel method. In one case, the nanoparticles were covalently linked with a new synthesized calix[8]arene octa valeric acid derivative (C[8]-C4-COOH) to produce new calix[8]arene-adorned magnetite nanoparticles (NP-C[8]-C4-COOH), and then NP-C[8]-C4-COOH was used as an additive in the sol-gel encapsulation process. In the other case, iron oxide nanoparticles were directly added into the sol-gel encapsulation process in order to interact electrostatically with both C[8]-C4-COOH and Candida rugosa lipase. The catalytic activities and enantioselectivities of two novel encapsulated lipases (Enc-NP-C[8]-C4-COOH and Enc-C[8]-C4-COOH@Fe3O4) in the hydrolysis reaction of racemic naproxen methyl ester were evaluated. The results showed that the activity and enantioselectivity of the lipase were improved when the lipase was encapsulated in the presence of calixarene-based additives. Indeed, the encapsulated lipases have an excellent rate of enantioselectivity, with E = 371 and 265, respectively, as compared to the free enzyme (E = 137). The lipases encapsulated with C[8]-C4-COOH and iron oxide nanoparticles (Enc-C[8]-C4-COOH@Fe3O4) retained more than 86% of their initial activities after 5 repeated uses and 92% with NP-C[8]-C4-COOH.

  16. Catalytic Asymmetric Piancatelli Rearrangement: Brønsted Acid Catalyzed 4π Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

    KAUST Repository

    Cai, Yunfei

    2016-10-13

    The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral Brønsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields as well as excellent enantioselectivities and diastereoselectivities. The high value of the aza-Piancatelli rearrangement was demonstrated by the synthesis of a cyclopentane-based hNK1 antagonist analogue.

  17. Catalytic Asymmetric Total Synthesis of (+)- and (-)-Paeoveitol via a Hetero-Diels-Alder Reaction.

    Science.gov (United States)

    Li, Tian-Ze; Geng, Chang-An; Yin, Xiu-Juan; Yang, Tong-Hua; Chen, Xing-Long; Huang, Xiao-Yan; Ma, Yun-Bao; Zhang, Xue-Mei; Chen, Ji-Jun

    2017-02-03

    The first catalytic asymmetric total synthesis of (+)- and (-)-paeoveitol has been accomplished in 42% overall yield via a biomimetic hetero-Diels-Alder reaction. The chiral phosphoric acid catalyzed hetero-Diels-Alder reaction showed excellent diastereo- and enantioselectivity (>99:1 dr and 90% ee); two rings and three stereocenters were constructed in a single step to produce (-)-paeoveitol on a scale of 452 mg. This strategy enabled us to selectively synthesize both paeoveitol enantiomers from the same substrates by simply changing the enantiomer of the catalyst.

  18. Development of Environment-Friendly Insecticides Based on Enantioselectivity: Bifenthrin as a Case.

    Science.gov (United States)

    Qian, Yi; Zhou, Peixue; Zhang, Quan

    2017-01-01

    Chiral insecticides significantly contribute to the environmental pollutions recently. As the development of industry and agriculture, increasing number of chiral insecticides are to be introduced into the market. However, their enantioselective toxicology to ecosystem still remains uncertain. In this review, we embarked on a structured search of bibliographic databases for peer-reviewed articles regarding the enantioselective effects of bifenthrin, a typical chiral insecticide, on both target and non-target species. With this enantioselective property of chiral insecticides, they often exhibit adverse effects on non-target species enantioselectively. Specifically, the enantioselective effects of bifenthrin on target and non-target organisms were discussed. In target species, R-bifenthrin exerts more significant activities in deinsectization, compared with S-bifenthrin. On the other hand, Sbifenthrin is more toxic to non-target species than R-bifenthrin, which suggests that the application of sole enantiomer is more efficient and environment-friendly than that of racemate. This review confirms the choice of environment-friendly insecticides from the perspective of the enantioselectivity of chiral insecticides. To make insecticides more efficient to target species and less toxic to non-target species, further research should be done to investigated the potential effects of targetactive enantiomers on non-target organisms as well as the enantioselective fate of enantiomers in multiple environmental matrix.

  19. In situ IR studies of Co and Ce doped Mn/TiO{sub 2} catalyst for low-temperature selective catalytic reduction of NO with NH{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, Lu; Pang, Dandan; Zhang, Changliang; Meng, Jiaojiao; Zhu, Rongshu; Ouyang, Feng, E-mail: ouyangfh@hit.edu.cn

    2015-12-01

    Highlights: • A SCR mechanistic pathway over Mn–Co–Ce/TiO{sub 2} is proposed. • The cobalt oxide produces lots of Brønsted acid sites, which favor to the adsorption of coordinated NH{sub 3} through NH{sub 3} migration. • Ce addition improves amide ions formation to reach best NO reduction selectivity. • At low-temperature coordinated NH{sub 3} reacts with NO{sub 2}{sup −}, or amide reacts with NO (ad) or NO (g) to form N{sub 2}. At high temperature, the reaction also occurs between coordinated NH{sub 3} and nitrate species. - Abstract: The Mn–Co–Ce/TiO{sub 2} catalyst was prepared by wet co-impregnation method for selective catalytic reduction of NO by NH{sub 3} in the presence of oxygen. The adsorption and co-adsorption of NH{sub 3}, NO and O{sub 2} on catalysts were investigated by in situ FTIR spectroscopy. The results suggested that addition of cobalt and cerium oxides increased the numbers of acid and redox sites. Especially, the cobalt oxide produced lots of Brønsted acid sites, which favor to the adsorption of coordinated NH{sub 3} through NH{sub 3} migration. Ce addition improved amide ions formation to reach best NO reduction selectivity. A mechanistic pathway over Mn–Co–Ce/TiO{sub 2} was proposed. At low-temperature SCR reaction, coordinated NH{sub 3} reacted with NO{sub 2}{sup −}, and amide reacted with NO (ad) or NO (g) to form N{sub 2}. NO{sub 2} was related to the formation of nitrite on Co-contained catalysts and the generation of −NH{sub 2}{sup −} on Ce-contained catalysts. At high temperature, the other branch reaction also occurred between the coordinated NH{sub 3} and nitrate species, resulting in N{sub 2}O yield increase.

  20. Preparation of Cu/La{sub 2}O{sub 3}-ZrO{sub 2}-Al{sub 2}O{sub 3} catalyst and its catalytic properties for selective reduction of NO

    Energy Technology Data Exchange (ETDEWEB)

    Xi-kun Guo; Ping-ping Xie; Shu-dong Lin [Shantou University, Shantou (China). Department of Chemistry

    2008-12-15

    An La{sub 2}O{sub 3}-ZrO{sub 2}-Al{sub 2}O{sub 3} composite support was prepared by co-precipitation with the mixed aqueous solution of La(NO{sub 3}{sub 3}, Al(NO{sub 3){sub 3}, and ZrOCl{sub 2} dropping into the precipitant of (NH{sub 4})2CO{sub 3} aqueous solution. The Cu/La{sub 2}O{sub 3}-ZrO{sub 2}-Al{sub 2}O{sub 3} catalyst was prepared by the impregnation of La{sub 2}O{sub 3}-ZrO{sub 2}-Al{sub 2}O{sub 3} with active component Cu{sup 2+} aqueous solution. The effects of the catalyst on the selective catalytic reduction of NO with propylene in excess oxygen were investigated. The relationships between the preparation method, structure and properties of the Cu/La{sub 2}O{sub 3}-ZrO{sub 2}-Al{sub 2}O{sub 3} catalyst were also explored by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), surface area measurements (BET), pyridine absorption infrared spectrum (Py-IR), thermal gravimetry (TG), and temperature-programmed reduction (TPR). The results indicate that the support {gamma}-Al{sub 2}O{sub 3} prepared by Al(NO{sub 3})3 dropping into (NH{sub 4}{sub 2} CO{sub 3} can remarkably enlarge the surface area; the addition of La{sub 2}O{sub 3} contributes mainly to the enhancement of the thermal stability; and the introduction of ZrO{sub 2} can increase the amount of Lewis and Broenstead acid. Consequently, the catalyst Cu/La{sub 2}O{sub 3}-ZrO{sub 2}-Al{sub 2}O{sub 3} has excellent activity for the selective reduction of NO with propylene in excess oxygen. NO conversion is up to 88.9% at 300{sup o}C and 81.9% even at the presence of 10% volume fraction of water vapor. 15 refs., 8 figs., 1 tab.

  1. 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

  2. Enantioselective synthesis of α-oxy amides via Umpolung amide synthesis.

    Science.gov (United States)

    Leighty, Matthew W; Shen, Bo; Johnston, Jeffrey N

    2012-09-19

    α-Oxy amides are prepared through enantioselective synthesis using a sequence beginning with a Henry addition of bromonitromethane to aldehydes and finishing with Umpolung Amide Synthesis (UmAS). Key to high enantioselection is the finding that ortho-iodo benzoic acid salts of the chiral copper(II) bis(oxazoline) catalyst deliver both diastereomers of the Henry adduct with high enantiomeric excess, homochiral at the oxygen-bearing carbon. Overall, this approach to α-oxy amides provides an innovative complement to alternatives that focus almost entirely on the enantioselective synthesis of α-oxy carboxylic acids.

  3. Highly Enantioselective Rhodium-Catalyzed Addition of Arylboroxines to Simple Aryl Ketones: Efficient Synthesis of Escitalopram.

    Science.gov (United States)

    Huang, Linwei; Zhu, Jinbin; Jiao, Guangjun; Wang, Zheng; Yu, Xingxin; Deng, Wei-Ping; Tang, Wenjun

    2016-03-24

    Highly enantioselective additions of arylboroxines to simple aryl ketones have been achieved for the first time with a Rh/(R,R,R,R)-WingPhos catalyst, thus providing a range of chiral diaryl alkyl carbinols with excellent ee values and yields. (R,R,R,R)-WingPhos has been proven to be crucial for the high reactivity and enantioselectivity. The method has enabled a new, concise, and enantioselective synthesis of the antidepressant drug escitalopram. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Infrared-thermographic screening of the activity and enantioselectivity of enzymes.

    Science.gov (United States)

    Reetz, M T; Hermes, M; Becker, M H

    2001-05-01

    The infrared radiation caused by the heat of reaction of an enantioselective enzyme-catalyzed transformation can be detected by modern photovoltaic infrared (IR)-thermographic cameras equipped with focal-plane array detectors. Specifically, in the lipase-catalyzed enantioselective acylation of racemic 1-phenylethanol, the (R)- and (S)-substrates are allowed to react separately in the wells of microtiter plates, the (R)-alcohol showing hot spots in the IR-thermographic images. Thus, highly enantioselective enzymes can be identified at kinetic resolution.

  5. Dual Enantioselective Control using D-phenylglycine-L-proline-derived Catalysts for the Enantioselective Addition of Diethylzinc to Aldehyde

    International Nuclear Information System (INIS)

    Kang, Seock Yong; Park, Yong Sun

    2016-01-01

    Dipeptide-derived catalysts are of great interest in various asymmetric transformations because of their short and simple preparation and easy modification of their modular structure by using different α-amino acids. We recently reported the first example of dipeptide-catalyzed enantioselective addition of dialkylzinc to aldehydes. We have developed a novel D-Phg-L-Pro dipeptide-derived catalyst for the addition of diethylzinc to aromatic aldehydes. We also disclosed an effective chiral switching by simply modifying nonchiral part of D-Phg-L-Pro dipeptide.

  6. Demonstration of Selective Catalytic Reduction (SCR) technology for the control of nitrogen oxide (NO{sub x}) emissions from high-sulfur coal-fired boilers. Technical progress report, first and second quarters 1994

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-11-01

    The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from U.S., Japanese and European catalyst suppliers on a high-sulfur U.S. coal-fired boiler. SCR is a post-combustion nitrogen oxide (NO{sub x}) control technology that involve injecting ammonia into the flue gas generated from coal combustion in a boiler. The flue gas containing ammonia is then passed through a reactor that contains a specialized catalyst. In the presence of the catalyst, the ammonia reacts with NO{sub x} to form nitrogen and water vapor. Although SCR is widely practiced in Japan and Europe on gas-, oil-, and low-sulfur coal-fired boilers, there are several technical uncertainties associated with applying SCR to U.S. coals. These uncertainties include: (1) potential catalyst deactivation due to poisoning by trace metal species present in U.S. coals that are not present in other fuels; (2) performance of the technology and effects on the balance-of-plant equipment in the presence of high amounts of SO{sub 2} and SO{sub 3}; and (3) performance of a wide variety of SCR catalyst compositions, geometries and methods of manufacture under typical high-sulfur coal-fired utility operating conditions. These uncertainties are being explored by operating a series of small-scale SCR reactors and simultaneously exposing different SCR catalysts to flue gas derived from the combustion of high sulfur U.S. coal. The project is being conducted in the following three phases: permitting, environmental monitoring plan and preliminary engineering; detailed design engineering and construction; and operation, testing, disposition and final report. The project was in the operation and testing phase during this reporting period. Accomplishments for this period are described.

  7. Innovative Clean Coal Technology (ICCT): Demonstration of selective catalytic reduction (SCR) technology for the control of nitrogen oxide (NO{sub x}) emissions from high-sulfur coal-fired boilers. Technical progress report, third and fourth quarters 1994

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-11-01

    The objective of this project is to demonstrate and evaluate commercially available selective catalytic reduction (SCR) catalysts from U.S., Japanese, and European catalyst suppliers on a high-sulfur U.S. Coal-fired boiler. SCR is a post-combustion nitrogen oxide (NO{sub x}) control technology that involves injecting ammonia into the flue gas generated from coal combustion in an electric utility boiler. The flue gas containing ammonia is then passed through a reactor that contains a specialized catalyst. In the presence of the catalyst, the ammonia reacts with NO{sub x} to form nitrogen and water vapor. Although SCR is widely practiced in Japan and European gas-, oil-, and low-sulfur coal-fired boilers, there are several technical uncertainties associated with applying SCR to U.S. coals. These uncertainties include: (1) potential catalyst deactivation due to poisoning by trace metal species present in U.S. coals that are not present in other fuels; (2) performance of the technology and effects on the balance-of-plant equipment in the presence of high amounts of SO{sub 2} and SO{sub 3}; performance of a wide variety of SCR catalyst compositions, geometries, and methods of manufacture under typical high-sulfur coal-fired utility operating conditions. These uncertainties are being explored by operating a series of small- scale SCR reactors and simultaneously exposing different SCR catalysts to flue gas derived from the combustion of high sulfur U.S. coal. The demonstration is being performed at Gulf Power Company`s Plant Crist Unit No. 5 (75 MW capacity) near Pensacola, Florida. The project is funded by the U.S. Department of Energy (DOE), Southern Company Services, Inc. (SCS on behalf of the entire Southern electric system), the Electric Power Research Institute (EPRI), and Ontario Hydro. SCS is the participant responsible for managing al aspects of this project. 1 ref., 69 figs., 45 tabs.

  8. Enantioselective degradation and enantiomerization of indoxacarb in soil.

    Science.gov (United States)

    Sun, Dali; Pang, Junxiao; Qiu, Jing; Li, Li; Liu, Chenglan; Jiao, Bining

    2013-11-27

    In this study, the enantioselective degradation and enantiomerizaton of indoxacarb were investigated in two soils under nonsterilized and sterilized conditions using a chiral OD-RH column on a reversed-phase HPLC. Under nonsterilized conditions, the degradation of indoxacarb in two soils was enantioselective. In acidic soil, the half-lives of R-(-)- and S-(+)-indoxacarb were 10.43 and 14.00 days, respectively. Acidic soil was preferential to the degradation of R-(-)-indoxacarb. In alkaline soil, the half-lives of R-(-)- and S-(+)-indoxacarb were 12.14 and 4.88 days, respectively. S-(+)-Indoxacarb was preferentially degraded. Under sterilized conditions, approximately 5-10% of the initial concentration degraded after 75 days of incubation in acidic soil, whereas in alkaline soil, approximately half of the initial concentration degraded due to chemical hydrolysis under alkaline conditions. Enantiomerization was also discovered in acidic and alkaline soils. The results showed that mutual transformation existed between two enantiomers and that S-(+)-indoxacarb had a significantly higher inversion rate to R-(-)-indoxacarb than its antipode.

  9. Chiral separation and enantioselective degradation of vinclozolin in soils.

    Science.gov (United States)

    Liu, Hui; Liu, Donghui; Shen, Zhigang; Sun, Mingjing; Zhou, Zhiqiang; Wang, Peng

    2014-03-01

    Vinclozolin is a chiral fungicide with potential environmental problems. The chiral separation of the enantiomers and enantioselective degradation in soil were investigated in this work. The enantiomers were separated by high-performance liquid chromatography (HPLC) on Chiralpak IA, IB, and AZ-H chiral columns under normal phase and the influence of the mobile phase composition on the separation was also studied. Complete resolutions were obtained on all three chiral columns under optimized conditions with the same elution order of (+)/(-). The residual analysis of the enantiomers in soil was conducted using accelerate solvent extraction followed by HPLC determination. The recoveries of the enantiomers ranged from 85.7-105.7% with relative standard deviation (SD) of 0.12-3.83%, and the limit of detection (LOD) of the method was 0.013 µg/g. The results showed that the degradations of vinclozolin enantiomers in the soils followed first-order kinetics. Preferential degradation of the (-)-enantiomer was observed only in one soil with the largest |ES| value of 0.047, and no obvious enantioselective degradation was observed in other soils. It was found that the persistence of vinclozolin in soil was related to pH values based on the half-lives. The two enantiomers disappeared about 8 times faster in basic soils than that in neutral or acidic soils. © 2014 Wiley Periodicals, Inc.

  10. Rhodium-Catalyzed Enantioselective Cyclopropanation of Olefins with N-Sulfonyl 1,2,3-Triazoles

    Science.gov (United States)

    Chuprakov, Stepan; Kwok, Sen Wai; Zhang, Li; Lercher, Lukas; Fokin, Valery V.

    2009-01-01

    N-Sulfonyl 1,2,3-triazoles readily form rhodium(II) azavinyl carbenes, which react with olefins to produce cyclopropanes with excellent diastereo- and enantioselectivity and in high yield. PMID:19928917

  11. Optimisation of stabilised carboxylesterase NP for enantioselective hydrolysis of naproxen methyl ester

    CSIR Research Space (South Africa)

    Steenkamp, Lucia H

    2008-12-01

    Full Text Available Although the enantioselective kinetic resolution of ester racemates of the non-steroidal antiinflammatory drug naproxen ([2-(6-methoxy-2-naphthyl) propionic acid]) is a common demonstration for biocatalysis, the enantiomeric excess of the reactions...

  12. BIOACCUMULATION AND ENANTIOSELECTIVE BIOTRANSFORMATION OF FIPRONIL BY RAINBOW TROUT (ONCORHYNCHUS MYKISS)

    Science.gov (United States)

    Dietary accumulation and enantioselective biotransformation was determined for rainbow trout (Oncorhynchus mykiss) exposed to fipronil, a widely used chiral pesticide. Measurement of the fish carcass tissue (whole fish minus GI tract and liver) showed a rapid accumulation of fip...

  13. Purification and characterisation of a novel enantioselective epoxide hydrolase from Aspergillus niger M200

    Czech Academy of Sciences Publication Activity Database

    Kotík, Michael; Kyslík, Pavel

    2006-01-01

    Roč. 1760, - (2006), s. 245-252 ISSN 0006-3002 Institutional research plan: CEZ:AV0Z50200510 Keywords : epoxide hydrolase * enantioselectivity * aspergillus niger Subject RIV: EE - Microbiology, Virology

  14. A New Mn–Salen Micellar Nanoreactor for Enantioselective Epoxidation of Alkenes in Water

    Directory of Open Access Journals (Sweden)

    Francesco P. Ballistreri

    2018-03-01

    Full Text Available A new chiral Mn–salen catalyst, functionalized with a long aliphatic chain and a choline group, able to act as surfactant catalyst for green epoxidation in water, is here described. This catalyst was employed with a commercial surfactant (CTABr leading to a nanoreactor for the enantioselective epoxidation of some selected alkenes in water, using NaClO as oxidant. This is the first example of a nanoreactor for enantioselective epoxidation of non-functionalized alkenes in water.

  15. Direct enantioselective conjugate addition of carboxylic acids with chiral lithium amides as traceless auxiliaries.

    Science.gov (United States)

    Lu, Ping; Jackson, Jeffrey J; Eickhoff, John A; Zakarian, Armen

    2015-01-21

    Michael addition is a premier synthetic method for carbon-carbon and carbon-heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B.

  16. Enantioselective 1,3-dipolar cycloadditions of diazoacetates with electron-deficient olefins.

    Science.gov (United States)

    Sibi, Mukund P; Stanley, Levi M; Soeta, Takahiro

    2007-04-12

    [reaction: see text] A general strategy for highly enantioselective 1,3-dipolar cycloaddition of diazoesters to beta-substituted, alpha-substituted, and alpha,beta-disubstituted alpha,beta-unsaturated pyrazolidinone imides is described. Cycloadditions utilizing less reactive alpha,beta-disubstituted dipolarophiles require elevated reaction temperatures, but still provide the corresponding pyrazolines with excellent enantioselectivities. Finally, an efficient synthesis of (-)-manzacidin A employing this cycloaddition methodology as a key step is illustrated.

  17. Formal total syntheses of classic natural product target molecules via palladium-catalyzed enantioselective alkylation

    Directory of Open Access Journals (Sweden)

    Yiyang Liu

    2014-10-01

    Full Text Available Pd-catalyzed enantioselective alkylation in conjunction with further synthetic elaboration enables the formal total syntheses of a number of “classic” natural product target molecules. This publication highlights recent methods for setting quaternary and tetrasubstituted tertiary carbon stereocenters to address the synthetic hurdles encountered over many decades across multiple compound classes spanning carbohydrate derivatives, terpenes, and alkaloids. These enantioselective methods will impact both academic and industrial settings, where the synthesis of stereogenic quaternary carbons is a continuing challenge.

  18. Enantioselective Addition of Allyltin Reagents to Amino Aldehydes Catalyzed with Bis(oxazolinylphenylrhodium(III Aqua Complexes

    Directory of Open Access Journals (Sweden)

    Hisao Nishiyama

    2011-06-01

    Full Text Available Bis(oxazolinylphenylrhodium(III aqua complexes, (PheboxRhX2(H2O [X = Cl, Br], were found to be efficient Lewis acid catalysts for the enantioselective addition of allyl- and methallyltributyltin reagents to amino aldehydes. The reactions proceed smoothly in the presence of 5–10 mol % of (PheboxRhX2(H2O complex at ambient temperature to give the corresponding amino alcohols with modest to good enantioselectivity (up to 94% ee.

  19. Direct Enantioselective Conjugate Addition of Carboxylic Acids with Chiral Lithium Amides as Traceless Auxiliaries

    Science.gov (United States)

    2016-01-01

    Michael addition is a premier synthetic method for carbon–carbon and carbon–heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B. PMID:25562717

  20. Flexible Enantioselectivity of Tryptophanase Attributable to Benzene Ring in Heterocyclic Moiety of D-Tryptophan

    Directory of Open Access Journals (Sweden)

    Akihiko Shimada

    2012-05-01

    Full Text Available The invariance principle of enzyme enantioselectivity must be absolute because it is absolutely essential to the homochiral biological world. Most enzymes are strictly enantioselective, and tryptophanase is one of the enzymes with extreme absolute enantioselectivity for L-tryptophan. Contrary to conventional knowledge about the principle, tryptophanase becomes flexible to catalyze D-tryptophan in the presence of diammonium hydrogenphosphate. Since D-amino acids are ordinarily inert or function as inhibitors even though they are bound to the active site, the inhibition behavior of D-tryptophan and several inhibitors involved in this process was examined in terms of kinetics to explain the reason for this flexible enantioselectivity in the presence of diammonium hydrogenphosphate. Diammonium hydrogenphosphate gave tryptophanase a small conformational change so that D-tryptophan could work as a substrate. As opposed to other D-amino acids, D-tryptophan is a very bulky amino acid with a benzene ring in its heterocyclic moiety, and so we suggest that this structural feature makes the catalysis of D-tryptophan degradation possible, consequently leading to the flexible enantioselectivity. The present results not only help to understand the mechanism of enzyme enantioselectivity, but also shed light on the origin of homochirality.

  1. Integrative assessment of enantioselectivity in endocrine disruption and immunotoxicity of synthetic pyrethroids

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Meirong [Research Center of Environmental Science, College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China); Chen Fang [College of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310018 (China); Wang Cui; Zhang Quan [Research Center of Environmental Science, College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China); Gan Jianying [Department of Environmental Sciences, University of California, Riverside, CA 92521 (United States); Liu Weiping, E-mail: wliu@zjut.edu.c [Research Center of Environmental Science, College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China)

    2010-05-15

    The increasing release of chiral chemicals into the environment dictates attention to a better understanding of enantioselectivity in their human and ecotoxicological effects. Although enantioselectivity has been considered in many recent studies, there is little effort for discerning the connection between different processes, and as such, our current knowledge about chiral contaminants is rather scattered and incoherent. In this study, we simultaneously evaluated enantioselectivity of two chiral pesticides, lambda-cyhalothrin (LCT) and (Z)-cis-bifenthrin (cis-BF), in immunotoxicity to macrophage cells (RAW264.7), and endocrine disruption activity in human breast carcinoma cell line MCF-7. Analysis of cell proliferation, cell viability, apoptosis, and receptor gene expression showed significant differences between the enantiomers of LCT or cis-BF in estrogenic potential and immunocytotoxicity. The selectivity in these effects consistently followed the same direction, with (-)-LCT or 1S-cis-BF displaying a greater activity than its counterpart. The consistency was attributed to interplaying mechanisms in the closely interacting immune and endocrine systems. The underlying interplays suggest that other chiral xenobiotics may also show a directional enantioselectivity in immunotoxicity and endocrine toxicity. Given that many biological processes are inter-related, enantioselectivity may follow specific patterns that can be revealed via integrative assessments as demonstrated in this study. - Chiral contaminants should consider multiple effects and relate directions of enantioselectivity to their interplaying processes.

  2. Integrative assessment of enantioselectivity in endocrine disruption and immunotoxicity of synthetic pyrethroids

    International Nuclear Information System (INIS)

    Zhao Meirong; Chen Fang; Wang Cui; Zhang Quan; Gan Jianying; Liu Weiping

    2010-01-01

    The increasing release of chiral chemicals into the environment dictates attention to a better understanding of enantioselectivity in their human and ecotoxicological effects. Although enantioselectivity has been considered in many recent studies, there is little effort for discerning the connection between different processes, and as such, our current knowledge about chiral contaminants is rather scattered and incoherent. In this study, we simultaneously evaluated enantioselectivity of two chiral pesticides, lambda-cyhalothrin (LCT) and (Z)-cis-bifenthrin (cis-BF), in immunotoxicity to macrophage cells (RAW264.7), and endocrine disruption activity in human breast carcinoma cell line MCF-7. Analysis of cell proliferation, cell viability, apoptosis, and receptor gene expression showed significant differences between the enantiomers of LCT or cis-BF in estrogenic potential and immunocytotoxicity. The selectivity in these effects consistently followed the same direction, with (-)-LCT or 1S-cis-BF displaying a greater activity than its counterpart. The consistency was attributed to interplaying mechanisms in the closely interacting immune and endocrine systems. The underlying interplays suggest that other chiral xenobiotics may also show a directional enantioselectivity in immunotoxicity and endocrine toxicity. Given that many biological processes are inter-related, enantioselectivity may follow specific patterns that can be revealed via integrative assessments as demonstrated in this study. - Chiral contaminants should consider multiple effects and relate directions of enantioselectivity to their interplaying processes.

  3. 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

  4. 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

  5. Enantioselective behaviour of tetraconazole during strawberry wine-making process.

    Science.gov (United States)

    Liu, Na; Pan, Xinglu; Zhang, Shuang; Ji, Mingshan; Zhang, Zhihong

    2018-05-01

    The fate of tetraconazole enantiomers in strawberries during wine-making process was studied. The residues were determined by ultra-performance convergence chromatography tandem triple quadrupole mass spectrometry after each process steps. Results indicated that there was significant enantioselective dissipation of tetraconazole enantiomers during the fermentation process. And (-)-tetraconazole degraded faster than (+)-tetraconazole. The half-lives of (-)-tetraconazole and (+)-tetraconazole were 3.12, 3.76 days with washing procedure and 3.18, 4.05 days without washing procedure. The processing factors of strawberry wine samples after each step were generally less than 1. In particular, the processing factors of the fermentation process were the lowest. The results could help facilitate more accurate risk assessments of tetraconazole during wine-making process. © 2018 Wiley Periodicals, Inc.

  6. Enantioselective organo-photocatalysis mediated by atropisomeric thiourea derivatives.

    Science.gov (United States)

    Vallavoju, Nandini; Selvakumar, Sermadurai; Jockusch, Steffen; Sibi, Mukund P; Sivaguru, Jayaraman

    2014-05-26

    Can photocatalysis be performed without electron or energy transfer? To address this, organo-photocatalysts that are based on atropisomeric thioureas and display lower excited-state energies than the reactive substrates have been developed. These photocatalysts were found to be efficient in promoting the [2+2] photocycloaddition of 4-alkenyl-substituted coumarins, which led to the corresponding products with high enantioselectivity (77-96% ee) at low catalyst loading (1-10 mol%). The photocatalytic cycle proceeds by energy sharing via the formation of both static and dynamic complexes (exciplex formation), which is aided by hydrogen bonding. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Chemo- and Enantioselective Intramolecular Silver-Catalyzed Aziridinations.

    Science.gov (United States)

    Ju, Minsoo; Weatherly, Cale D; Guzei, Ilia A; Schomaker, Jennifer M

    2017-08-07

    Asymmetric nitrene-transfer reactions are a powerful tool for the preparation of enantioenriched amine building blocks. Reported herein are chemo- and enantioselective silver-catalyzed aminations which transform di- and trisubstituted homoallylic carbamates into [4.1.0]-carbamate-tethered aziridines in good yields and with ee values of up to 92 %. The effects of the substrate, silver counteranion, ligand, solvent, and temperature on both the chemoselectivity and ee value were explored. Stereochemical models were proposed to rationalize the observed absolute stereochemistry of the aziridines, which undergo nucleophilic ring opening to yield enantioenriched amines with no erosion in stereochemical integrity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Enantioselective bioaccumulation of diniconazole in Tenebrio molitor larvae.

    Science.gov (United States)

    Liu, Chen; LV, Xiao Tian; Zhu, Wen Xue; QU, Hao Yang; Gao, Yong Xin; Guo, Bao Yuan; Wang, Hui Li

    2013-12-01

    The enantioselective bioaccumulation of diniconazole in Tenebrio molitor Linne larva was investigated with liquid chromatography tandem mass spectrometry based on the ChiralcelOD-3R[cellulose tri-(3,5-dimethylphenyl carbamate)] column. In this study we documented the effects of dietary supplementation with wheat bran contaminated by racemic diniconazole at two dose levels of 20 mg kg(-1) and 2 mg kg(-1) (dry weight) in Tenebrio molitor. The results showed that both doses of diniconazole were taken up by Tenebrio molitor rapidly in the first few days, the concentrations of R-enantiomer and S-enantiomer at high doses reached the highest level of 0.55 mg kg(-1) and 0.48 mg kg(-1) , respectively, on the 1(st) d, and the concentrations of them obtained a maxima of 0.129 mg kg(-1) and 0.128 mg kg(-1) at low dose, respectively, on the 3(rd) d, which means that the concentration of diniconazole was proportional to the time of achieving the highest accumulated level. It afterwards attained equilibrium after a sharp decline at both 20 mg kg(-1) and 2 mg kg(-1) of diniconazole. The determination results from the feces of Tenebrio molitor demonstrated that the extraction recovery (ER) values of the high dose group were higher than that of the low dose group and the values were all above 1; therefore, it could be inferred that enantiomerization existed in Tenebrio molitor. Additionally, the biota accumulation factor was used to evaluate the bioaccumulation of diniconazole enantiomers, showing that the bioaccumulation of diniconazole in Tenebrio molitor was enantioselective with preferential accumulation of S-enantiomer. © 2013 Wiley Periodicals, Inc.

  9. A Au/Cu2O-TiO2 system for photo-catalytic hydrogen production. A pn-junction effect or a simple case of in situ reduction?

    KAUST Repository

    Sinatra, Lutfan; LaGrow, Alec P.; Peng, Wei; Kirmani, Ahmad R.; Amassian, Aram; Idriss, Hicham; Bakr, Osman

    2015-01-01

    Photo-catalytic H2 production from water has been studied over Au-Cu2O nanoparticle deposited on TiO2 (anatase) in order to probe into both the plasmon resonance effect (Au nanoparticles) and the pn-junction at the Cu2O-TiO2 interface. The Au-Cu2O

  10. 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

  11. 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 ...

  12. 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.

  13. 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.

  14. Enantioselective radical addition/trapping reactions with alpha,beta-disubstituted unsaturated imides. Synthesis of anti-propionate aldols.

    Science.gov (United States)

    Sibi, Mukund P; Petrovic, Goran; Zimmerman, Jake

    2005-03-02

    This manuscript describes a highly diastereo- and enantioselective intermolecular radical addition/hydrogen atom transfer to alpha,beta-disubstituted enoates. Additionally, we show that anti-propionate aldol-like products can be easily prepared from alpha-methyl-beta-acyloxyenoates in good yields and high diastereo- and enantioselectivities.

  15. Enantioselective conjugate addition of diethylzinc to chalcone catalyzed by Co(acac)(2) and chiral amino alcohols

    NARCIS (Netherlands)

    de Vries, A.H.M.; Feringa, B.L.

    1997-01-01

    Co(acac)(2) in the presence of chiral ligands has been employed as catalyst for the enantioselective conjugate addition of diethylzinc to chalcone. With chiral amino alcohols derived from (+)-camphor, enantioselectivities up to 83% were achieved. (C) 1997 Elsevier Science Ltd.

  16. Cu(I)-Catalyzed Enantioselective Friedel-Crafts Alkylation of Indoles with 2-Aryl-N-sulfonylaziridines as Alkylating Agents.

    Science.gov (United States)

    Ge, Chen; Liu, Ren-Rong; Gao, Jian-Rong; Jia, Yi-Xia

    2016-07-01

    A highly enantioselective Friedel-Crafts alkylation of indoles with N-sulfonylaziridines as alkylating agents has been developed by utilizing the complex of Cu(CH3CN)4BF4/(S)-Segphos as a catalyst. A range of optically active tryptamine derivatives are obtained in good to excellent yields and enantioselectivities (up to >99% ee) via a kinetic resolution process.

  17. Ruthenium Catalyzed Diastereo- and Enantioselective Coupling of Propargyl Ethers with Alcohols: Siloxy-Crotylation via Hydride Shift Enabled Conversion of Alkynes to π-Allyls.

    Science.gov (United States)

    Liang, Tao; Zhang, Wandi; Chen, Te-Yu; Nguyen, Khoa D; Krische, Michael J

    2015-10-14

    The first enantioselective carbonyl crotylations through direct use of alkynes as chiral allylmetal equivalents are described. Chiral ruthenium(II) complexes modified by Josiphos (SL-J009-1) catalyze the C-C coupling of TIPS-protected propargyl ether 1a with primary alcohols 2a-2o to form products of carbonyl siloxy-crotylation 3a-3o, which upon silyl deprotection-reduction deliver 1,4-diols 5a-5o with excellent control of regio-, anti-diastereo-, and enantioselectivity. Structurally related propargyl ethers 1b and 1c bearing ethyl- and phenyl-substituents engage in diastereo- and enantioselective coupling, as illustrated in the formation of adducts 5p and 5q, respectively. Selective mono-tosylation of diols 5a, 5c, 5e, 5f, 5k, and 5m is accompanied by spontaneous cyclization to deliver the trans-2,3-disubstituted furans 6a, 6c, 6e, 6f, 6k, and 6m, respectively. Primary alcohols 2a, 2l, and 2p were converted to the siloxy-crotylation products 3a, 3l, and 3p, which upon silyl deprotection-lactol oxidation were transformed to the trans-4,5-disubstituted γ-butyrolactones 7a, 7l, and 7p. The formation of 7p represents a total synthesis of (+)-trans-whisky lactone. Unlike closely related ruthenium catalyzed alkyne-alcohol C-C couplings, deuterium labeling studies provide clear evidence of a novel 1,2-hydride shift mechanism that converts metal-bound alkynes to π-allyls in the absence of intervening allenes.

  18. Enantioselective Cytotoxicity Profile of o,p’-DDT in PC 12 Cells

    Science.gov (United States)

    Zhang, Chunlong; Wen, Yuezhong; Liu, Weiping

    2012-01-01

    Background The continued uses of dichlordiphenyltrichloroethane (DDT) for indoor vector control in some developing countries have recently fueled intensive debates toward the global ban of this persistent legacy contaminant. Current approaches for ecological and health risk assessment has ignored the chiral nature of DDT. In this study by employing an array of cytotoxicity related endpoints, we investigated the enantioselective cytotoxicity of o,p’-DDT. Principal Findings we demonstrated for the first time that R-(−)-o,p’-DDT caused more neuron cell death by inducing more severe oxidative stress, which selectively imbalanced the transcription of stress-related genes (SOD1, SOD2, HSP70) and enzyme (superoxide dismutase and lactate dehydrogenase) activities, and greater cellular apoptosis compared to its enantiomer S-(+)-o,p’-DDT at the level comparable to malaria area exposure (parts per million). We further elucidated enantioselective modes of action using microarray combined with enzyme-linked immunosorbent assay. The enantioselective apoptosis might involve three signaling pathways via caspase 3, tumor protein 53 (p53) and NFkB. Conclusions Based on DDT stereochemistry and results reported for other chiral pesticides, our results pointed to the same directional enantioselectivity of chiral DDT toward mammalian cells. We proposed that risk assessment on DDT should consider the enantiomer ratio and enantioselectivities. PMID:22937105

  19. 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.

  20. Enantioselective Effect of Flurbiprofen on Lithium Disposition in Rats.

    Science.gov (United States)

    Uwai, Yuichi; Matsumoto, Masashi; Kawasaki, Tatsuya; Nabekura, Tomohiro

    2017-01-01

    Lithium is administered for treating bipolar disorders and is mainly excreted into urine. Nonsteroidal anti-inflammatory drugs inhibit this process. In this study, we examined the enantioselective effect of flurbiprofen on the disposition of lithium in rats. Pharmacokinetic experiments with lithium were performed. Until 60 min after the intravenous administration of lithium chloride at 30 mg/kg as a bolus, 17.8% of lithium injected was recovered into the urine. Its renal clearance was calculated to be 1.62 mL/min/kg. Neither creatinine clearance (Ccr) nor pharmacokinetics of lithium was affected by the simultaneous injection of (R)-flurbiprofen at 20 mg/kg. (S)-flurbiprofen impaired the renal function and interfered with the urinary excretion of lithium. The ratio of renal clearance of lithium to Ccr was decreased by the (S)-enantiomer. This study clarified that the (S)-flurbiprofen but not (R)-flurbiprofen inhibited the renal excretion of lithium in rats. © 2017 S. Karger AG, Basel.

  1. 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.

  2. Silica-Supported Catalyst for Enantioselective Arylation of Aldehydes under Batch and Continuous-Flow Conditions.

    Science.gov (United States)

    Watanabe, Satoshi; Nakaya, Naoyuki; Akai, Junichiro; Kanaori, Kenji; Harada, Toshiro

    2018-05-04

    A silica-supported 3-aryl H 8 -BINOL-derived titanium catalyst exhibited high performance in the enantioselective arylation of aromatic aldehydes using Grignard and organolithium reagents not only under batch conditions but also under continuous-flow conditions. Even with a simple pipet reactor packed with the heterogeneous catalyst, the enantioselective production of chiral diarylmethanols could be achieved through a continuous introduction of aldehydes and mixed titanium reagents generated from the organometallic precursors. The pipet reactor could be used repeatedly in different reactions without appreciable deterioration of the activity.

  3. Asymmetric Hydrogenation of Seven-Membered C=N-containing Heterocycles and Rationalization of the Enantioselectivity.

    Science.gov (United States)

    Balakrishna, Bugga; Bauzá, Antonio; Frontera, Antonio; Vidal-Ferran, Anton

    2016-07-18

    Iridium(I) complexes with phosphine-phosphite ligands efficiently catalyze the enantioselective hydrogenation of diverse seven-membered C=N-containing heterocyclic compounds (eleven examples; up to 97 % ee). The P-OP ligand L3, which incorporates an ortho-diphenyl substituted octahydrobinol phosphite fragment, provided the highest enantioselectivities in the hydrogenation of most of the heterocyclic compounds studied. The observed stereoselection was rationalized by means of DFT calculations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Influence of biochar on the enantioselective behavior of the chiral fungicide metalaxyl in soil

    Science.gov (United States)

    Gámiz, Beatriz; Pignatello, Joseph J.; Hermosín, María Carmen; Cox, Lucía; Celis, Rafael

    2015-04-01

    Chiral pesticides comprise an emerging and important class of organic pollutants currently, accounting for more than a quarter of used pesticides. Consequently, the contamination problems caused by chiral pesticides are concern matter and factors affecting enantioselective processes of chiral pesticides in soil need to be understood. For example, certain soil management practices, such as the use of organic amendments, can affect the enantioselective behavior of chiral pesticides in soils. Recently, biochar (BC), i.e. organic matter subjected to pyrolysis, has been proposed as organic amendment due to beneficial properties such as its high stability against decay in soil environments and its apparent ability to influence the availability of nutrients. BC is considered to be more biologically inert as compared to otherforms of organic carbon. However, its side-effects on the enantioselectivity of processes affecting the fate of chiral pesticides is unknown. The aim of this study was to assess the effect of biochar (BC) on the enantioselectivity of sorption, degradation, and leaching of the chiral fungicide metalaxyl in an agricultural soil. Amending the soil with BC (2% w/w) resulted in 3 times higher sorption of metalaxyl enantiomers compared to unamended soil, but no enantioselectivity in the process was observed. Moreover, both enantiomers showed some resistance to be desorbed in BC-amended soil compared to unamended soil. Dissipation studies revealed that the degradation of metalaxylwas more enantioselective in the unamended soil than in BC-amended soil. In unamended soil, R-metalaxyl(biologically active) and S- metalaxyl had half-lives (t1/2) of 3 and 34 days, respectively. BC enhanced the persistence of both enantiomers in the soil, with R-metalaxyl being degraded faster (t1/2=43 days) than S-metalaxyl (t1/2= 100 days). The leaching of both S-and R-metalaxyl was almost suppressed after amending the soil with BC; less than 10% of the fungicide applied to soil

  5. Albendazole-praziquantel interaction in healthy volunteers: kinetic disposition, metabolism and enantioselectivity

    Science.gov (United States)

    Lima, Renata Monteiro; Ferreira, Maria Augusta Drago; de Jesus Ponte Carvalho, Teresa Maria; Dumêt Fernandes, Bruno José; Takayanagui, Osvaldo Massaiti; Garcia, Hector Hugo; Coelho, Eduardo Barbosa; Lanchote, Vera Lucia

    2011-01-01

    AIM This study investigated the kinetic disposition, metabolism and enantioselectivity of albendazole (ABZ) and praziquantel (PZQ) administered alone and in combination to healthy volunteers. METHODS A randomized crossover study was carried out in three phases (n = 9), in which some volunteers started in phase 1 (400 mg ABZ), others in phase 2 (1500 mg PZQ), and the remaining volunteers in phase 3 (400 mg ABZ + 1500 mg PZQ). Serial blood samples were collected from 0–48 h after drug administration. Pharmacokinetic parameters were calculated using a monocompartmental model with lag time and were analyzed using the Wilcoxon test; P≤ 0.05. RESULTS The administration of PZQ increased the plasma concentrations of (+)-ASOX (albendazole sulphoxide) by 264% (AUC 0.99 vs. 2.59 µg ml−1 h), (−)-ASOX by 358% (0.14 vs. 0.50 µg ml−1 h) and albendazole sulfone (ASON) by 187% (0.17 vs. 0.32 µg ml−1 h). The administration of ABZ did not change the kinetic disposition of (+)-(S)-PZQ (–)-(R)-4-OHPZQ or (+)-(S)-4-OHPZQ, but increased the plasma concentration of (–)-(R)-PZQ by 64.77% (AUC 0.52 vs. 0.86 µg ml−1 h). CONCLUSIONS The pharmacokinetic interaction between ABZ and PZQ in healthy volunteers was demonstrated by the observation of increased plasma concentrations of ASON, both ASOX enantiomers and (–)-(R)-PZQ. Clinically, the combination of ABZ and PZQ may improve the therapeutic efficacy as a consequence of higher concentration of both active drugs. On the other hand, the magnitude of this elevation may represent an increased risk of side effects, requiring, certainly, reduction of the dosage. However, further studies are necessary to evaluate the efficacy and safety of this combination. PMID:21395645

  6. 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.)

  7. 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...

  8. 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.)

  9. 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.

  10. 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...

  11. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

    Preferred Customer

    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 ...

  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. Quinine-Promoted, Enantioselective Boron-Tethered Diels-Alder Reaction by Anomeric Control of Transition State Conformation.

    Science.gov (United States)

    Scholl, Katie; Dillashaw, John; Timpy, Evan; Lam, Yu-Hong; DeRatt, Lindsey; Benton, Tyler R; Powell, Jacqueline P; Houk, Kendall N; Morgan, Jeremy B

    2018-05-01

    Diels-Alder reactions of tethered vinyl-metal species offer the opportunity to fashion highly functionalized diol intermediates for synthesis. We have developed the first enantioselective boron-tethered Diels-Alder reaction using quinine as a chiral promoter. Quinine recovery, enantioselectivity enhancement, and manipulation of the cyclohexene core are also investigated. DFT modeling calculations confirm the role of quinine as a bidentate ligand enhancing reaction rates. The enantioselectivity of the cycloaddition is proposed to originate from a boron-centered anomeric effect.

  14. Enantioselective Alkylation of 2-Oxindoles Catalyzed by a Bifunctional Phase-Transfer Catalyst: Synthesis of (-)-Debromoflustramine B.

    Science.gov (United States)

    Craig, Ryan; Sorrentino, Emiliano; Connon, Stephen J

    2018-03-26

    A new bifunctional phase-transfer catalyst that employs hydrogen bonding as a control element was developed to promote efficient enantioselective S N 2 reactions for the construction all-carbon quaternary stereocenters in high yield and excellent enantioselectivity (up to 97 % ee) utilizing the alkylation of a malleable oxindole substrate. The utility of the methodology was demonstrated through a concise and highly enantioselective synthesis of (-)-debromoflustramine B. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Palladium-Catalyzed Enantioselective C-H Olefination of Diaryl Sulfoxides through Parallel Kinetic Resolution and Desymmetrization.

    Science.gov (United States)

    Zhu, Yu-Chao; Li, Yan; Zhang, Bo-Chao; Zhang, Feng-Xu; Yang, Yi-Nuo; Wang, Xi-Sheng

    2018-03-07

    The first example of Pd II -catalyzed enantioselective C-H olefination with non-chiral or racemic sulfoxides as directing groups was developed. A variety of chiral diaryl sulfoxides were synthesized with high enantioselectivity (up to 99 %) through both desymmetrization and parallel kinetic resolution (PKR). This is the first report of Pd II -catalyzed enantioselective C(sp 2 )-H functionalization through PKR, and it represents a novel strategy to construct sulfur chiral centers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Application of Zeolitic Additives in the Fluid Catalytic Cracking (FCC

    Directory of Open Access Journals (Sweden)

    A. Nemati Kharat

    2013-06-01

    Full Text Available Current article describes application of zeolites in fluid catalytic cracking (FCC. The use of several zeolitic additives for the production light olefins and reduction of pollutants is described. Application of zeolites as fluid catalytic cracking (FCC catalysts and additives due to the presence of active acid sites in the zeolite framework  increase the formation of desired cracking products (i.e., olefin and branched products  in the FCC unit.

  17. Hydroxynitrile Lyases with α/β-Hydrolase Fold: Two Enzymes with Almost Identical 3D Structures but Opposite Enantioselectivities and Different Reaction Mechanisms

    Science.gov (United States)

    Andexer, Jennifer N; Staunig, Nicole; Eggert, Thorsten; Kratky, Christoph; Pohl, Martina; Gruber, Karl

    2012-01-01

    Hydroxynitrile lyases (HNLs) catalyze the cleavage of cyanohydrins to yield hydrocyanic acid (HCN) and the respective carbonyl compound and are key enzymes in the process of cyanogenesis in plants. In organic syntheses, HNLs are used as biocatalysts for the formation of enantiopure cyanohydrins. We determined the structure of the recently identified, R-selective HNL from Arabidopsis thaliana (AtHNL) at a crystallographic resolution of 2.5 Å. The structure exhibits an α/β-hydrolase fold, very similar to the homologous, but S-selective, HNL from Hevea brasiliensis (HbHNL). The similarities also extend to the active sites of these enzymes, with a Ser-His-Asp catalytic triad present in all three cases. In order to elucidate the mode of substrate binding and to understand the unexpected opposite enantioselectivity of AtHNL, complexes of the enzyme with both (R)- and (S)-mandelonitrile were modeled using molecular docking simulations. Compared to the complex of HbHNL with (S)-mandelonitrile, the calculations produced an approximate mirror image binding mode of the substrate with the phenyl rings located at very similar positions, but with the cyano groups pointing in opposite directions. A catalytic mechanism for AtHNL is proposed, in which His236 from the catalytic triad acts as a general base and the emerging negative charge on the cyano group is stabilized by main-chain amide groups and an α-helix dipole very similar to α/β-hydrolases. This mechanistic proposal is additionally supported by mutagenesis studies. PMID:22851196

  18. Enantioselective Synthesis of (-)-Vallesine: Late-Stage C17-Oxidation via Complex Indole Boronation.

    Science.gov (United States)

    Antropow, Alyssa H; Garcia, Nicholas R; White, Kolby L; Movassaghi, Mohammad

    2018-06-04

    The first enantioselective total synthesis of (-)-vallesine via a strategy that features a late-stage regioselective C17-oxidation followed by a highly stereoselective transannular cyclization is reported. The versatility of this approach is highlighted by the divergent synthesis of the archetypal alkaloid of this family, (+)-aspidospermidine, and an A-ring-oxygenated derivative, (+)-deacetylaspidospermine, the precursor to (-)-vallesine, from a common intermediate.

  19. In-silico driven engineering of enantioselectivity of a penicillin G acylase towards active pharmaceutical ingredients

    Czech Academy of Sciences Publication Activity Database

    Grulich, Michal; Brezovský, J.; Štěpánek, Václav; Palyzová, Andrea; Marešová, Helena; Zahradník, Jiří; Kyslíková, Eva; Kyslík, Pavel

    2016-01-01

    Roč. 133, Supplement 1 (2016), s. 53-59 ISSN 1381-1177 Institutional support: RVO:61388971 Keywords : Docking experiments * Enantioselectivity * Penicillin G acylase Subject RIV: EE - Microbiology, Virology OBOR OECD: Microbiology Impact factor: 2.269, year: 2016

  20. Aziridino Alcohols as Catalysts for the Enantioselective Addition of Diethylzinc to Aldehydes

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Kornø, Hanne Tøfting; Guijarro, David

    1998-01-01

    The chiral aziridino alcohols 1 -3 have been prepared either from amino acids (1a from serine; 1b - 1i and 3 from threonine; 2a - 2e from allo-threonine) or via asymmetric synthesis (1j, 1k, 1l and 2f from methyl cinnamate). These easily available ligands act as catalysts for the enantioselective...