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Sample records for catalytic enantioselective reductions

  1. Catalytic enantioselective reductions and allylations of prochiral ketones

    CERN Document Server

    Cunningham, A

    2002-01-01

    The use of LiGaH sub 4 in combination with the S,O-chelate 2-hydroxy-2'-mercapto-1,1'-binaphthyl (monothiobinaphthol, MTBH sub 2), forms an active catalyst (2 mol %) for the asymmetric reduction of prochiral ketones, when using catecholborane as the hydride source. This catalyst has successfully been applied to the enantioselective reduction of aryl/n-alkyl ketones, providing the chiral sec-alcohols in yields of 82 - 96% and with enantiomeric excess values of 59 - 93%. Alkyl/methyl ketones are reduced in yields of 72 - 93% and in 46 - 79% enantiomeric excess. Enantioface differentiation is on the basis of the steric requirements of the ketone substituents. The X-ray structure of the pre-catalyst, Li(THF) sub 3 Ga(MTB) sub 2 has been determined and in solution is in equilibrium with a dimeric species of constitution Li sub 2 Ga sub 2 (MTB) sub 4. An indium analogue whose X-ray structure was determined as Li sub 2 (THF) sub 5 lnCI(MTB) sub 2 has also been prepared. The indium- based catalyst does not form an en...

  2. CATALYTIC ENANTIOSELECTIVE ALLYLIC OXIDATION

    NARCIS (Netherlands)

    Rispens, Minze T.; Zondervan, Charon; Feringa, Bernard

    1995-01-01

    Several chiral Cu(II)-complexes of cyclic amino acids catalyse the enantioselective allylic oxidation of cyclohexene to cyclohexenyl esters. Cyclohexenyl propionate was obtained in 86% yield with e.e.'s up to 61%.

  3. Catalytic Enantioselective Reduction of Prochiral Ketones with Chiral Ferrocenyl Amino Alcohols

    Institute of Scientific and Technical Information of China (English)

    CHEN, Wei-Yi(陈维一); LU, Jun(陆军); SHEN, Zong-Xuan(沈宗旋); ZHANG, Ya-Wen(张雅文)

    2004-01-01

    The asymmetric reduction of prochiral ketones was catalyzed by a class of recoverable and highly stable chiral ferrocenyl amino alcohols derived from natural amino acids to yield optically active secondary alcohols in high chemical yields and moderate to good enantiomeric excesses.

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

    DEFF Research Database (Denmark)

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

    2011-01-01

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

  5. Towards chiral diamines as chiral catalytic precursors for the borane-mediated enantioselective reduction of prochiral ketones

    Indian Academy of Sciences (India)

    Deevi Basavaiah; Utpal Das; Suparna Roy

    2009-11-01

    Two chiral diamines (3)-3-anilinomethyl-1,2,3,4-tetrahydroisoquinoline (1) and (2)-2-anilinomethylpiperidine (2) have been employed as chiral catalytic sources in the borane-mediated asymmetric reduction of prochiral ketones thus providing the resulting secondary alcohols in good enantiomeric purities (up to 81% ).

  6. Catalytic enantioselective synthesis of quaternary carbon stereocentres

    Science.gov (United States)

    Quasdorf, Kyle W.; Overman, Larry E.

    2014-12-01

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

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

    Science.gov (United States)

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

    2016-12-01

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

  8. 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.

  9. The enantioselective b-keto ester reductions by Saccharomyces cerevisiae

    OpenAIRE

    HASSAN TAJIK; KHALIL TABATABAEIAN; MAHMOOD SHAHBAZI

    2006-01-01

    The enantioselective yeast reduction of aromatic b-keto esters, by use of potassium dihydrogen phosphate, calcium phosphate (monobasic), magnesium sulfate and ammonium tartrate (diammonium salt) (10:1:1:50) in water at pH 7 as a buffer for 72–120 h with 45–90 % conversion to the corresponding aromatic -hydroxy esters was achieved by means of Saccharomyces cerevisiae.

  10. Catalytic Enantioselective 1,2-Addition of Terminal 1,3-Diynes to Trifluoromethyl Ketones

    Institute of Scientific and Technical Information of China (English)

    Yan Zheng; Hai Ma; Jun-An Ma

    2016-01-01

    A facile catalytic enantioselective 1,2-addition of diynes to trifluoromethyl ketones was developed.By a combination of Me2Zn,Ti(OPr-i)4,BaF2 and quinine,the reaction of a series of terminal diynes with trifluoromethyl ketones proceeded to afford trifluoromethylated chrial tertiary alcohols with the diyne moiety in good to high yields with moderate to high enantioselectivities.Furthermore,this catalytic asymmetric diyne addition to trifluoromethylketone was applied in the synthesis of the Efavirenz analogue.

  11. The enantioselective b-keto ester reductions by Saccharomyces cerevisiae

    Directory of Open Access Journals (Sweden)

    HASSAN TAJIK

    2006-09-01

    Full Text Available The enantioselective yeast reduction of aromatic b-keto esters, by use of potassium dihydrogen phosphate, calcium phosphate (monobasic, magnesium sulfate and ammonium tartrate (diammonium salt (10:1:1:50 in water at pH 7 as a buffer for 72–120 h with 45–90 % conversion to the corresponding aromatic -hydroxy esters was achieved by means of Saccharomyces cerevisiae.

  12. Enantioselective reduction of acetophenone analogues using carrot and celeriac enzymes system

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The enantioselective reduction of acetophenone analogues catalyzed by carrot and celeriac was performed in moderate conversions and excellent enantiomeric excesses.The steric factors and electronic effects of the substituents at the aromatic ring were found to significantly affect the efficiency of the enantioselective reduction of acetophenone analogues,while they had a little effect on the enantioselectivity of acetophenone analogues reduction.It was also found that the conversions of acetophenone anal...

  13. Catalytic enantioselective cyclization and C3-fluorination of polyenes.

    Science.gov (United States)

    Cochrane, Nikki A; Nguyen, Ha; Gagne, Michel R

    2013-01-16

    (Xylyl-phanephos)Pt(2+) in combination with XeF(2) mediates the consecutive diastereoselective cation-olefin cyclization/fluorination of polyene substrates. Isolated yields were typically in the 60-69% range while enantioselectivities reached as high as 87%. The data are consistent with a stereoretentive fluorination of a P(2)Pt-alkyl cation intermediate.

  14. 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.

  15. Catalytic enantioselective amination of alcohols by the use of borrowing hydrogen methodology: cooperative catalysis by iridium and a chiral phosphoric acid.

    Science.gov (United States)

    Zhang, Yao; Lim, Ching-Si; Sim, Derek Sui Boon; Pan, Hui-Jie; Zhao, Yu

    2014-01-27

    The catalytic asymmetric reduction of ketimines has been explored extensively for the synthesis of chiral amines, with reductants ranging from Hantzsch esters, silanes, and formic acid to H2 gas. Alternatively, the amination of alcohols by the use of borrowing hydrogen methodology has proven a highly atom economical and green method for the production of amines without an external reductant, as the alcohol substrate serves as the H2 donor. A catalytic enantioselective variant of this process for the synthesis of chiral amines, however, was not known. We have examined various transition-metal complexes supported by chiral ligands known for asymmetric hydrogenation reactions, in combination with chiral Brønsted acids, which proved essential for the formation of the imine intermediate and the transfer-hydrogenation step. Our studies led to an asymmetric amination of alcohols to provide access to a wide range of chiral amines with good to excellent enantioselectivity.

  16. Catalytic enantioselective addition of organoboron reagents to fluoroketones controlled by electrostatic interactions

    Science.gov (United States)

    Lee, Kyunga; Silverio, Daniel L.; Torker, Sebastian; Robbins, Daniel W.; Haeffner, Fredrik; van der Mei, Farid W.; Hoveyda, Amir H.

    2016-08-01

    Organofluorine compounds are central to modern chemistry, and broadly applicable transformations that generate them efficiently and enantioselectively are in much demand. Here we introduce efficient catalytic methods for the addition of allyl and allenyl organoboron reagents to fluorine-substituted ketones. These reactions are facilitated by readily and inexpensively available catalysts and deliver versatile and otherwise difficult-to-access tertiary homoallylic alcohols in up to 98% yield and >99:1 enantiomeric ratio. Utility is highlighted by a concise enantioselective approach to the synthesis of the antiparasitic drug fluralaner (Bravecto, presently sold as the racemate). Different forms of ammonium-organofluorine interactions play a key role in the control of enantioselectivity. The greater understanding of various non-bonding interactions afforded by these studies should facilitate the future development of transformations that involve fluoroorganic entities.

  17. Catalytic enantioselective Michael addition reactions of alpha-nitroesters to alpha,beta-unsaturated ketones

    NARCIS (Netherlands)

    Keller, E; Veldman, N; Spek, AL; Feringa, BL

    1997-01-01

    Enantioselective Michael additions of alpha-nitroesters 2a-d with alpha,beta-unsaturated ketones were carried out in the presence of a catalytic amount of chiral Al-Li-(R,R')-2,2'-dihydroxy-1,1'-binaphthyl ('AlLiBINOL') complex prepared in situ from LiAlH4 and 2.45 equiv. of (R,R')-BINOL. The enanti

  18. Catalytic enantioselective Michael addition reactions of α-nitroesters to α,β-unsaturated ketones

    NARCIS (Netherlands)

    Keller, Erik; Veldman, Nora; Spek, Anthony L.; Feringa, Bernard

    1997-01-01

    Enantioselective Michael additions of α-nitroesters 2a-d with α,β-unsaturated ketones were carried out in the presence of a catalytic amount of chiral Al-Li-(R,R')-2,2'-dihydroxy-1,1'-binaphthyl (‘AlLiBINOL’) complex prepared in situ from LiAlH4 and 2.45 equiv. of (R,R')-BINOL. The enantioselectivit

  19. Enantioselective Synthesis of 2,2-Disubstituted Terminal Epoxides via Catalytic Asymmetric Corey-Chaykovsky Epoxidation of Ketones

    Directory of Open Access Journals (Sweden)

    Shigeki Matsunaga

    2012-02-01

    Full Text Available Catalytic asymmetric Corey-Chaykovsky epoxidation of various ketones with dimethyloxosulfonium methylide using a heterobimetallic La-Li3-BINOL complex (LLB is described. The reaction proceeded smoothly at room temperature in the presence of achiral phosphine oxide additives, and 2,2-disubstituted terminal epoxides were obtained in high enantioselectivity (97%–91% ee and yield ( > 99%–88% from a broad range of methyl ketones with 1–5 mol% catalyst loading. Enantioselectivity was strongly dependent on the steric hindrance, and other ketones, such as ethyl ketones and propyl ketones resulted in slightly lower enantioselectivity (88%–67% ee.

  20. Catalytic enantioselective 1,6-conjugate additions of propargyl and allyl groups

    Science.gov (United States)

    Meng, Fanke; Li, Xiben; Torker, Sebastian; Shi, Ying; Shen, Xiao; Hoveyda, Amir H.

    2016-09-01

    Conjugate (or 1,4-) additions of carbanionic species to α,β-unsaturated carbonyl compounds are vital to research in organic and medicinal chemistry, and there are several chiral catalysts that facilitate the catalytic enantioselective additions of nucleophiles to enoates. Nonetheless, catalytic enantioselective 1,6-conjugate additions are uncommon, and ones that incorporate readily functionalizable moieties, such as propargyl or allyl groups, into acyclic α,β,γ,δ-doubly unsaturated acceptors are unknown. Chemical transformations that could generate a new bond at the C6 position of a dienoate are particularly desirable because the resulting products could then be subjected to further modifications. However, such reactions, especially when dienoates contain two equally substituted olefins, are scarce and are confined to reactions promoted by a phosphine-copper catalyst (with an alkyl Grignard reagent, dialkylzinc or trialkylaluminium compounds), a diene-iridium catalyst (with arylboroxines), or a bisphosphine-cobalt catalyst (with monosilyl-acetylenes). 1,6-Conjugate additions are otherwise limited to substrates where there is full substitution at the C4 position. It is unclear why certain catalysts favour bond formation at C6, and—although there are a small number of catalytic enantioselective conjugate allyl additions—related 1,6-additions and processes involving a propargyl unit are non-existent. Here we show that an easily accessible organocopper catalyst can promote 1,6-conjugate additions of propargyl and 2-boryl-substituted allyl groups to acyclic dienoates with high selectivity. A commercially available allenyl-boron compound or a monosubstituted allene may be used. Products can be obtained in up to 83 per cent yield, >98:2 diastereomeric ratio (for allyl additions) and 99:1 enantiomeric ratio. We elucidate the mechanistic details, including the origins of high site selectivity (1,6- versus 1,4-) and enantioselectivity as a function of the catalyst

  1. Whole cells in enantioselective reduction of benzyl acetoacetate

    Directory of Open Access Journals (Sweden)

    Joyce Benzaquem Ribeiro

    2014-09-01

    Full Text Available The β-ketoester benzyl acetoacetate was enantioselectively reduced to benzyl (S-3-hydroxybutanoate by seven microorganism species. The best result using free cells was obtained with the yeast Hansenula sp., which furnished 97% ee and 85% of conversion within 24 h. After immobilization in calcium alginate spheres, K.marxianus showed to be more stable after 2 cycles of reaction.

  2. 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.

  3. 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

  4. 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

    2013-07-01

    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 (k(cat), K(m), and k(cat)/K(m)), 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 (k(cat) and K(m)) were more consistent with experimental values than those for catalytic efficiency (k(cat)/K(m)). 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.

  5. SELECTIVE CATALYTIC REDUCTION MERCURY FIELD SAMPLING PROJECT

    Science.gov (United States)

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

  6. Baker's yeast mediated reduction of substituted acenaphthenequinones: Regio- and enantioselective preparation of mono-hydroxyacenaphthenones

    Institute of Scientific and Technical Information of China (English)

    Xing Yong Wang; Jing Nan Cui; Wei Min Ren; Feng Li; Chun Liang Lu; Xu Hong Qian

    2007-01-01

    Baker's yeast mediated reduction of acenaphthenequinone within 4-10 h afforded mono-hydroxyacenaphthenone mainly with low enantioselectivity, the substrate and mono-hydroxyacenaphthenone product almost converted to dihydroxyacenaphthene after 48 h.By control of the reaction time and in the presence of DMF as co-solvent, the reduction of 6-substituted acenaphthenequinones under vigorous agitation afforded the corresponding 2-hydroxyacenaphthenones in 24-84% yields with 10-93% ee.

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

    Science.gov (United States)

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

    2016-07-01

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

  8. Catalytic Enantioselective Alkylation of Benzaldehyde with Diethylzinc Using Chiral Nonracemic (Thio)-phosphoramidates

    NARCIS (Netherlands)

    Hulst, Ron; Heres, Hero; Fitzpatrick, Kevin; Peper, Nathalie C.M.W.; Kellogg, Richard M.

    1996-01-01

    Two chiral nonracemic γ-amino alcohols, ephedrine thiol and the corresponding (thio)-phosphoramidates have been examined as catalysts for the enantioselective alkylation of benzaldehyde by diethylzinc. Addition of titanium tetraisopropoxide increases the yield as well as the enantioselectivity; 1-ph

  9. Practical and Broadly Applicable Catalytic Enantioselective Additions of Allyl-B(pin) Compounds to Ketones and α-Ketoesters.

    Science.gov (United States)

    Robbins, Daniel W; Lee, KyungA; Silverio, Daniel L; Volkov, Alexey; Torker, Sebastian; Hoveyda, Amir H

    2016-08-01

    A set of broadly applicable methods for efficient catalytic additions of easy-to-handle allyl-B(pin) (pin=pinacolato) compounds to ketones and acyclic α-ketoesters was developed. Accordingly, a large array of tertiary alcohols can be obtained in 60 to >98 % yield and up to 99:1 enantiomeric ratio. At the heart of this development is rational alteration of the structures of the small-molecule aminophenol-based catalysts. Notably, with ketones, increasing the size of a catalyst moiety (tBu to SiPh3 ) results in much higher enantioselectivity. With α-ketoesters, on the other hand, not only does the opposite hold true, since Me substitution leads to substantially higher enantioselectivity, but the sense of the selectivity is reversed as well.

  10. Selective Catalytic Reduction of NO with Methane

    Institute of Scientific and Technical Information of China (English)

    Xiang Gao; Qi Yu; Limin Chen

    2003-01-01

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

  11. Catalytic Enantioselective Electrophilic Aminations of Acyclic α-Alkyl β-Carbonyl Nucleophilies.

    Science.gov (United States)

    Liu, Xiaofeng; Sun, Bingfeng; Deng, Li

    2009-06-01

    Highly enantioselective aminations of acyclic α-alkyl β-keto thioesters and trifluoroethyl α-methyl α-cyanoacetate (12) with as low as 0.05 mol % of a bifunctional cinchona alkaloid catalyst were established. This ability to afford highly enantioselectivity for the amination of α-alkyl β-carbonyl compounds renders the 6'-OH cinchona alkaloid-catalyzed amination applicable for the enantioselective synthesis of acyclic chiral compounds bearing N-substituted quaternary stereocenters. The synthetic application of this reaction is illustrated in a concise asymmetric synthesis of α-methylserine, a key intermediate previously utilized in the total synthesis of a small molecule immunomodulator, conagenin.

  12. Quantum chemical study on the mechanism of enantioselective reduction of prochiral ketones catalyzed by oxazaborolidines

    Institute of Scientific and Technical Information of China (English)

    LI; Ming

    2001-01-01

    [1]Corey, E. J., Bakshi, R. K., Shibata, S., Highly enantioselective borane reduction ketones catalyzed by chiral oxazaborolidines, J. Am. Chem. Soc., 1987, 109:5551-5553.[2]Wallbaum, S., Martens, J., Asymmetric syntheses with chiral oxazaborolidines, Tetrahedron Asymmetry, 1992, 3: 1475-1504.[3]Deloux, L., Srebnik, M., Asymmetric borane-catalyzed reactions, Chem. Rev., 1993, 93: 763-784.[4]Togni, A., Venanzi, L. M., Nitrogen donors in organometallic chemistry and in homogeneous catalysis, Angew Chem. Int. Ed. Engl., 1994, 33: 497-562.[5]Ager, D. J., Prakash, I., Schaad, D. R., 1,2-amino alcohols and their heterocyclic derivatives as chiral auxiliaries in asymmetric synthesis, Chem. Rev., 1996, 96: 835-875.[6]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 4. On the hydride transfer in ketone complexes of borane adducts of oxazaborolidines and regeneration of catalyst, Tetrahedron Asymmetry, 1991, 2:1133-1155.[7]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 8. On the conformational freedom of the ketone of ketone-borane complexes of oxazaborolidines used as catalysts in the enantioselective reduction of ketones, Tetrahedron Asymmetry. 1992, 3: 1563-1572.[8]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 7. On the effects controlling the coordination of borane to chiral oxazaborolidines used as catalysts in the enantioselective reduction of ketones, Tetrahedron Asymmetry,1992, 3: 1441-1453.[9]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 12. On the influence of the nature of the ring system on binding in ketone-borane complexes of chiral oxazaborolidines used as catalysts in the enantioselective reduction of ketones. Tetrahedron Asymmetry, 1993, 4: 1597-1602.[10]Nevalainen, V., Quantum chemical modeling of chiral catalysis, Part 19. Strain and stability-oxazadiboretanes potentially involved in the enantioselective reduction of ketones promoted

  13. Catalytic Enantioselective Allylic Amination of Olefins for the Synthesis of ent-Sitagliptin.

    Science.gov (United States)

    Bao, Hongli; Bayeh, Liela; Tambar, Uttam K

    2013-11-01

    The presence of nitrogen atoms in most chiral pharmaceutical drugs has motivated the development of numerous strategies for the synthesis of enantioenriched amines. Current methods are based on the multi-step transformation of pre-functionalized allylic electrophiles into chiral allylic amines. The enantioselective allylic amination of unactivated olefins represents a more direct and attractive strategy. We report the enantioselective synthesis of ent-sitagliptin via an allylic amination of an unactivated terminal olefin.

  14. Quantum chemical study on the mechanism of enantioselective reduction of prochiral ketones catalyzed by oxazaborolidines

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The ab initio molecular orbital study on the mechanism of enantioselective reduction of 3,3-dimethyl butanone-2 with borane catalyzed by chiral oxazaborolidine is performed. As illus trated, this enantioselective reduction is exothermic and goes mainly through the formations of the catalyst-borane adduct, the catalyst-borane-3,3-dimethyl butanone-2 adduct, and the cata lyst-alkoxyborane adduct with a B-O-B-N 4-member ring and through the decomposition of the catalyst-alkoxyborane adduct with the regeneration of the catalyst. During the hydride transfer in the catalyst-borane-3,3-dimethyl butanone-2 adduct to form the catalyst-alkoxyborane adduct, the hydride transfer and the formation of the B-O-B-N 4-member ring in the catalyst-alkoxyborane ad duct happen simultaneously. The controlling step for the reduction is the transfer of hydride from the borane moiety to the carbonyl carbon of 3,3-dimethyl butanone-2. The transition state for the hydride transfer is a twisted chair structure and the reduction leads to R-chiral alcohols.

  15. Catalytic Kinetic Resolution of Saturated N-Heterocycles by Enantioselective Amidation with Chiral Hydroxamic Acids.

    Science.gov (United States)

    Kreituss, Imants; Bode, Jeffrey W

    2016-12-20

    The preparation of enantioenriched chiral compounds by kinetic resolution dates back to the laboratories of Louis Pasteur in the middle of the 19th century. Unlike asymmetric synthesis, this process can always deliver enantiopure material (ee > 99%) if the reactions are allowed to proceed to sufficient conversion and the selectivity of the process is not unity (s > 1). One of the most appealing and practical variants is acylative kinetic resolution, which affords easily separable reaction products, and several highly efficient enzymatic and small molecule catalysts are available. Unfortunately, this method is applicable to limited substrate classes such as alcohols and primary benzylamines. This Account focuses on our work in catalytic acylative kinetic resolution of saturated N-heterocycles, a class of molecules that has been notoriously difficult to access via asymmetric synthesis. We document the development of hydroxamic acids as suitable catalysts for enantioselective acylation of amines through relay catalysis. Alongside catalyst optimization and reaction development, we present mechanistic studies and theoretical calculation accounting for the origins of selectivity and revealing the concerted nature of many amide-bond forming reactions. Immobilization of the hydroxamic acid to form a polymer supported reagent allows simplification of the experimental setup, improvement in product purification, and extension of the substrate scope. The kinetic resolutions are operationally straight forward: reactions proceed at room temperature and open to air conditions, without generation of difficult-to-remove side products. This was utilized to achieve decagram scale resolution of antimalarial drug mefloquine to prepare more than 50 g of (+)-erythro-meflqouine (er > 99:1) from the racemate. The immobilized quasienantiomeric acyl hydroxamic acid reagents were also exploited for a rare practical implementation of parallel kinetic resolution that affords both enantiomers of

  16. Catalytic enantioselective addition of hydrogen cyanide to benzaldehyde and p-methoxybenzaldehyde using cyclo-His-(αMe)Phe as catalyst

    NARCIS (Netherlands)

    Hulst, Ron; Broxterman, Quirinus B.; Kamphuis, Johan; Formaggio, Fernando; Crisma, Marco; Toniolo, Claudio; Kellogg, Richard M.

    1997-01-01

    Two cyclo-dipeptides based on His and the unnatural (αMe)Phe have been examined as catalysts in the enantioselective addition of hydrogen cyanide to benzaldehyde and p-methoxy-benzaldehyde. The synthesis, catalytic activity and NMR study towards the mechanism of this reaction are presented.

  17. Catalytic enantioselective addition of hydrogen cyanide to benzaldehyde and p-methoxybenzaldehyde using cyclo-His-(alpha-Me)Phe as catalyst

    NARCIS (Netherlands)

    Hulst, R; Broxterman, QB; Kamphuis, J; Formaggio, F; Crisma, M; Toniolo, C; Kellogg, RM

    1997-01-01

    Two cyclo-dipeptides based on His and the unnatural (alpha Me)Phe have been examined as catalysts in the enantioselective addition of hydrogen cyanide to benzaldehyde and p-methoxy-benzaldehyde. The synthesis, catalytic activity and NMR study towards the mechanism of this reaction are presented. (C)

  18. Catalytic Enantioselective Synthesis of Tetrahydocarbazoles and Exocyclic Pictet-Spengler-Type Reactions

    DEFF Research Database (Denmark)

    Hansen, Casper Lykke; Ohm, Ragnhild Gaard; Olsen, Lasse Bohn;

    2016-01-01

    A synthetic strategy for the synthesis of chiral tetrahydrocarbazoles (THCAs) has been developed. The strategy relies on two types of 6-exo-trig cyclization of 3-substituted indole substrates. Enantioselective domino Friedel-Crafts-type reactions leading to THCAs can be catalyzed by chiral phosph...

  19. Enantioselective Hydroaminomethylation of Olefins Enabled by Rh/Brønsted Acid Relay Catalysis.

    Science.gov (United States)

    Meng, Jing; Li, Xing-Han; Han, Zhi-Yong

    2017-03-03

    Herein, by employing a rhodium catalyst with a commercial ligand and a phosphoric acid catalyst, highly chemo-, regio-, and enantioselective hydroaminomethylation of olefins is realized through a relay catalytic hydroformylation/dynamic kinetic reductive amination process. The method features mild conditions (1 bar of syngas, room temperature in most cases), high yields (up to 99%), and high enantioselectivities (up to >99.5:0.5 er). Besides styrenes, acrylamides also provided the products with high yields and enantioselectivities. Aliphatic alkenes and vinyl esters are also applicable for the current method, albeit lower yields and enantioselectivities were obtained.

  20. Density functional study on enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine

    Institute of Scientific and Technical Information of China (English)

    LI; Ming; ZHENG; Wenxu

    2006-01-01

    The enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine is discussed by the density functional theory (DFT) method. The main intermediates and transition states for this reaction are optimized completely at the B3LYP/6-31g(d) level, and the transition states are verified by vibrational modes. As shown, the chirality-controlled steps for this reaction are the hydride transfer from borane to carbonyl carbon and oxime carbon of keto oxime ether, and the chirality for the reduced products is determined in these two reaction steps. In all examined reaction paths, the first hydride is transferred via a six-membered ring and the second hydride via a five-membered ring or a four-membered ring.

  1. Catalytic enantioselective construction of quaternary stereocenters: assembly of key building blocks for the synthesis of biologically active molecules.

    Science.gov (United States)

    Liu, Yiyang; Han, Seo-Jung; Liu, Wen-Bo; Stoltz, Brian M

    2015-03-17

    The ever-present demand for drugs with better efficacy and fewer side effects continually motivates scientists to explore the vast chemical space. Traditionally, medicinal chemists have focused much attention on achiral or so-called "flat" molecules. More recently, attention has shifted toward molecules with stereogenic centers since their three-dimensional structures represent a much larger fraction of the chemical space and have a number of superior properties compared with flat aromatic compounds. Quaternary stereocenters, in particular, add greatly to the three-dimensionality and novelty of the molecule. Nevertheless, synthetic challenges in building quaternary stereocenters have largely prevented their implementation in drug discovery. The lack of effective and broadly general methods for enantioselective formation of quaternary stereocenters in simple molecular scaffolds has prompted us to investigate new chemistry and develop innovative tools and solutions. In this Account, we describe three approaches to constructing quaternary stereocenters: nucleophilic substitution of 3-halooxindoles, conjugate addition of boronic acids to cyclic enones, and allylic alkylation of enolates. In the first approach, malonic ester nucleophiles attack electrophilic 3-halooxindoles, mediated by a copper(II)-bisoxazoline catalyst. A variety of oxindoles containing a benzylic quaternary stereocenter can be accessed through this method. However, it is only applicable to the specialized 3,3-disubstituted oxindole system. To access benzylic quaternary stereocenters in a more general context, we turned our attention to the enantioselective conjugate addition of carbon nucleophiles to α,β-unsaturated carbonyl acceptors. We discovered that in the presence of catalytic palladium-pyridinooxazoline complex, arylboronic acids add smoothly to β-substituted cyclic enones to furnish ketones with a β-benzylic quaternary stereocenter in high yields and enantioselectivities. The reaction is

  2. Highly enantioselective oxazaborolidine-catalyzed reduction of 1,3-dicarbonyl compounds: role of the additive diethylaniline.

    Science.gov (United States)

    Chein, Rong-Jie; Yeung, Ying-Yeung; Corey, E J

    2009-04-02

    The oxazaborolidine-catalyzed reduction of 2,2-disubstituted cycloalkan-1,3-diones or hindered 2,2-disubstituted cyclic ketones using catecholborane as reductant proceeds with greater enantioselectivity when N,N-diethylaniline is added. It has now been shown that the effect of this additive is to catalyze the conversion of a harmful minor impurity in catalyst preparations to the active catalyst.

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

    Science.gov (United States)

    Denmark, Scott E; Heemstra, John R

    2007-07-20

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

  4. NOX REMOVAL WITH COMBINED SELECTIVE CATALYTIC REDUCTION AND SELECTIVE NONCATALYTIC REDUCTION: PILOT- SCALE TEST RESULTS

    Science.gov (United States)

    Pilot-scale tests were conducted to develop a combined nitrogen oxide (NOx) reduction technology using both selective catalytic reduction (SCR) and selective noncatalytic reduction (SNCR). A commercially available vanadium-and titatnium-based composite honeycomb catalyst and enh...

  5. Highly Catalytic Enantioselective Addition of Diethyl Zinc to Aldehydes and Chalcone in the Presence of Chiral Ligands

    Institute of Scientific and Technical Information of China (English)

    WANG; Rui

    2001-01-01

    Catalytic asymmetric carbon-carbon bond formation is one of the most important reactions and have attracted much attention to develop more efficient enantioselective C-C formation methods in organic synthesis. In this field, asymmetric addition of diethylzinc to aldehydes[1] and conjugate addition to enones[2] have drawn special interests and have been greatly developed. Regardless of it, much spaces in these areas still exist, so it needs more extensive and intensive researches for the purpose of as follows: (1) attaching ligands to a polymer for the easy separation of the catalysts so as to be able to allow very efficient recovery and reuse of the catalysts, and the possibility of carrying out the desired transfomation in continuous mode in a flow reactor, etc., (2) searching for novel chiral catalysts with such features as more suitable for more extensive substrates varieties, and more convenient and economical as well as possessing applicable prospect, and so on. Here we report some works in these areas done in our laboratory.  ……

  6. Highly Catalytic Enantioselective Addition of Diethyl Zinc to Aldehydes and Chalcone in the Presence of Chiral Ligands

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Catalytic asymmetric carbon-carbon bond formation is one of the most important reactions and have attracted much attention to develop more efficient enantioselective C-C formation methods in organic synthesis. In this field, asymmetric addition of diethylzinc to aldehydes[1] and conjugate addition to enones[2] have drawn special interests and have been greatly developed. Regardless of it, much spaces in these areas still exist, so it needs more extensive and intensive researches for the purpose of as follows: (1) attaching ligands to a polymer for the easy separation of the catalysts so as to be able to allow very efficient recovery and reuse of the catalysts, and the possibility of carrying out the desired transfomation in continuous mode in a flow reactor, etc., (2) searching for novel chiral catalysts with such features as more suitable for more extensive substrates varieties, and more convenient and economical as well as possessing applicable prospect, and so on. Here we report some works in these areas done in our laboratory.

  7. 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

  8. Coupling of permeabilized microorganisms for efficient enantioselective reduction of ketone with cofactor recycling.

    Science.gov (United States)

    Zhang, Jie; Witholt, Bernard; Li, Zhi

    2006-01-28

    A novel, simple and efficient cofactor recycling method for enantioselective bioreduction has been developed by the use of permeabilized cells of a reductase-containing microorganism and a glucose dehydrogenase-containing microorganism

  9. 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.

  10. AM1 Transition State Modeling for the Enantioselectivities in the Chiral Oxazaborolidine-Catalyzed Reductions of a- and β-Aminoketones

    Institute of Scientific and Technical Information of China (English)

    FAN Jian-Fen; LU Yun-Xiang; WANG Qiu-Xia; WU Li-Fen

    2005-01-01

    AM1 transition state (TS) models were developed for the enantioselectivities in the reductions of α- and β-aminoketones catalyzed by (S)-4-benzyl-5,5-diphenyl-1,3,2-oxazaborolidine. The result showed that β-aminoketone gave better enantioselectivity than its α-analog. Different chiralities of the final products were obtained, R for the former and S for the latter. These semiempirical TS models are consistent with the experimental data.

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

    Science.gov (United States)

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

    2003-09-01

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

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

    Institute of Scientific and Technical Information of China (English)

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

    2003-01-01

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

  13. Studies on catalytic reduction of nitrate in groundwater

    Institute of Scientific and Technical Information of China (English)

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

    2007-01-01

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

  14. 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...

  15. Electro-catalytic reduction of nitrogen oxides

    Energy Technology Data Exchange (ETDEWEB)

    McLarnon, C.R.

    1989-12-01

    Nitrogen oxides have been linked to a broad range of air pollution problems including acid rain and the atmospheric production of photochemical ozone. Over twenty million tons of nitrogen oxides are emitted into the atmosphere each year as a result of the high temperature combustion of fossil fuels. Efforts to control nitrogen oxides emissions have lagged because of the generally low discharge concentrations of nitrogen oxides in combustion exhaust and because nitrogen oxides are more difficult to remove due to their lower reactivity. No catalyst has yet been found that will achieve significant reduction of nitrogen oxides in an oxidizing environment. Oxygen in the exhaust stream competes with nitrogen oxides for the active catalyst sites. Also, the dissociated oxygen atoms produced by decomposition of nitrogen oxides deactivate the surface of the catalyst. Externally applied electric fields have been used to control oxygen adsorption on metal and semi-conductor surfaces. In this investigation, a stream containing nitric oxide has been subjected to intense electric fields in the presence of catalyst materials including steel, stainless steel, and gold plated stainless steel wools and glass wool. The electric fields have been generated using DC, AC and rectified AC potentials in the range of 0--20 KV. The effect of parameters such as inlet nitric oxide concentration, oxygen and water content, gas residence time and temperature have also been studied.

  16. Palladacyclic imidazoline-naphthalene complexes: synthesis and catalytic performance in Pd(II)-catalyzed enantioselective reactions of allylic trichloroacetimidates.

    Science.gov (United States)

    Cannon, Jeffrey S; Frederich, James H; Overman, Larry E

    2012-02-17

    A new family of air- and moisture-stable enantiopure C,N-palladacycles (PIN-acac complexes) were prepared in good overall yield in three steps from 2-iodo-1-naphthoic acid and enantiopure β-amino alcohols. Three of these PIN complexes were characterized by single-crystal X-ray analysis. As anticipated, the naphthalene and imidazoline rings of PIN-acac complexes 18a and 18b were canted significantly from planarity and projected the imidazoline substituents R(1) and R(2) on opposite faces of the palladium square plane. Fifteen PIN complexes were evaluated as catalysts for the rearrangement of prochiral (E)-allylic trichloroacetimidate 19 (eq 2) and the S(N)2' allylic substitution of acetic acid with prochiral (Z)-allylic trichloroacetimidate 23. Although these complexes were kinetically poor catalysts for the Overman rearrangement, they were good catalysts for the allylic substitution reaction, providing branched allylic esters in high yield. However, enantioselectivities were low to moderate and significantly less than that realized with palladacyclic complexes of the COP family. Computational studies support an anti-acetoxypalladation/syn-deoxypalladation mechanism analogous to that observed with COP catalysts. The computational study further suggests that optimizing steric influence in the vicinity of the carbon ligand of a chiral C,N-palladacycle, rather than near the nitrogen heterocycle, is the direction to pursue in future development of improved enantioselective catalysts of this motif.

  17. 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.

  18. Alkali resistivity of Cu based selective catalytic reduction catalysts

    DEFF Research Database (Denmark)

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

    2012-01-01

    The deactivation of V2O5–WO3–TiO2, Cu–HZSM5 and Cu–HMOR plate type monolithic catalysts was investigated when exposed to KCl aerosols in a bench-scale reactor. Fresh and exposed catalysts were characterized by selective catalytic reduction (SCR) activity measurements, scanning electron microscope...... catalysts revealed that the potassium salt not only deposited on the catalyst surface, but also penetrated into the catalyst wall. Thus, the K/M ratio (M = V or Cu) was high on V2O5–WO3–TiO2 catalyst and comparatively less on Cu–HZSM5 and Cu–HMOR catalysts. NH3-TPD revealed that the KCl exposed Cu–HZSM5...

  19. First One-step Enantioselective Reduction of á-Haloacetophenones into Styrene Oxides using Sodium Borohydride in Water

    Institute of Scientific and Technical Information of China (English)

    LI Jing-wei; XU Li-wen; XIA Chun-gu

    2004-01-01

    The synthesis of enantiomerically enriched epoxides especially styrene oxides is an interesting challenge1,2 since they are often valuable building blocks for various fine chemical products and pharmaceuticals such as (a)2-, (a)3-, and á1-adrenergic receptor agonists3, 4. In recent years,there has been a flood of papers describing the synthetical methods of the chiral non-racemic epoxides5,6. Here we firstly developed a green, simple and potential epoxidation system by enantioselective reduction of a-haloacetophenones using NaBH4 in water.The procedure of the unexpected epoxidation was firstly found accidentally in the study of L-proline-catalyzed asymmetric reduction of aldehydes, ketones in water. In that time, we observed not only reductive product a-bromophenethyl alcohol but also a small quantity of styrene oxide after three hour reduction of a-bromoacephenone in water. It is impossible to produce the epoxide in the reduction when THF acts as solvent. Then we optimized the reaction conditions and extended reaction time to 5 hr until we obtained the epoxide as a major product.Encouraged by the front results, we tried a-CD as a chiral inducement and catalyst. Cyclodextrins (CDs), a cyclic oligosaccharide composed of several D-glucose units with an a-1, 4 linkage (6, 7, 8for á-, (a)-, (a)-CD, respectively), have been recognized as versatile enzyme mimics since every one molecule of them possesses a hydrophilic outside, which can dissolve in water, and a hydrophobic cavity, which provides an apolar matrix, described as "micro heterogeneous enwronment"7. All the experiments were carried out in water under room temperature. The procedure is a green, simple and potential, although the optically active styrene oxides are obtained in only moderate ees. and yields.When á-bromoacephenone and Sodium Borohydride (1.2 equiv, to ketone) reacts in water using 150mol% (a)-CD as catalyst, a 41% chemical yield and 45% optical yield of the corresponding epoxide were obtained

  20. Atmospheric emissions from a passenger ferry with selective catalytic reduction.

    Science.gov (United States)

    Nuszkowski, John; Clark, Nigel N; Spencer, Thomas K; Carder, Daniel K; Gautam, Mridul; Balon, Thomas H; Moynihan, Paul J

    2009-01-01

    The two main propulsion engines on Staten Island Ferry Alice Austen (Caterpillar 3516A, 1550 hp each) were fitted with selective catalytic reduction (SCR) aftertreatment technology to reduce emissions of oxides of nitrogen (NOx). After the installation of the SCR system, emissions from the ferry were characterized both pre- and post-aftertreatment. Prior research has shown that the ferry operates in four modes, namely idle, acceleration, cruise, and maneuvering modes. Emissions were measured for both engines (designated NY and SI) and for travel in both directions between Manhattan and Staten Island. The emissions characterization used an analyzer system, a data logger, and a filter-based particulate matter (PM) measurement system. The measurement of NOx, carbon monoxide (CO), and carbon dioxide (CO2) were based on federal reference methods. With the existing control strategy for the SCR urea injection, the SCR provided approximately 64% reduction of NOx for engine NY and 36% reduction for engine SI for a complete round trip with less than 6.5 parts per million by volume (ppmv) of ammonia slip during urea injection. Average reductions during the cruise mode were 75% for engine NY and 47% for engine SI, which was operating differently than engine NY. Reductions for the cruise mode during urea injection typically exceeded 94% from both engines, but urea was injected only when the catalyst temperature reached a 300 degrees C threshold pre- and postcatalyst. Data analysis showed a total NOx mass emission split with 80% produced during cruise, and the remaining 20% spread across idle, acceleration, and maneuvering. Examination of continuous NOx data showed that higher reductions of NOx could be achieved on both engines by initiating the urea injection at an earlier point (lower exhaust temperature) in the acceleration and cruise modes of operation. The oxidation catalyst reduced the CO production 94% for engine NY and 82% for engine SI, although the high CO levels

  1. 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...

  2. 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

    Previously, it could be demonstrated, that the monophasic, enzymatic reduction of aliphatic 2-ketones into the corresponding (R)-2-alcohols is an adequate and viable method as carried out in a cascade of two enzyme–membrane reactors (Leuchs, S.; Na’amnieh, S. N.; Greiner, L. Green Chemistry 2013......, 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...

  3. 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.

  4. 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.

  5. Method and apparatus for monitoring a hydrocarbon-selective catalytic reduction device

    Science.gov (United States)

    Schmieg, Steven J; Viola, Michael B; Cheng, Shi-Wai S; Mulawa, Patricia A; Hilden, David L; Sloane, Thompson M; Lee, Jong H

    2014-05-06

    A method for monitoring a hydrocarbon-selective catalytic reactor device of an exhaust aftertreatment system of an internal combustion engine operating lean of stoichiometry includes injecting a reductant into an exhaust gas feedstream upstream of the hydrocarbon-selective catalytic reactor device at a predetermined mass flowrate of the reductant, and determining a space velocity associated with a predetermined forward portion of the hydrocarbon-selective catalytic reactor device. When the space velocity exceeds a predetermined threshold space velocity, a temperature differential across the predetermined forward portion of the hydrocarbon-selective catalytic reactor device is determined, and a threshold temperature as a function of the space velocity and the mass flowrate of the reductant is determined. If the temperature differential across the predetermined forward portion of the hydrocarbon-selective catalytic reactor device is below the threshold temperature, operation of the engine is controlled to regenerate the hydrocarbon-selective catalytic reactor device.

  6. A New Type of NADH Model Compound: Synthesis and Enantioselective Reduction of Benzoylformates to the Corresponding Mandelates

    Directory of Open Access Journals (Sweden)

    Xin-Liang Tang

    2007-05-01

    Full Text Available A new type of NADH model compound with good reactivity and enantioselectivity has been synthesized in good yields by an efficient and convenient synthetic method. The structures of these model compounds were confirmed by 1H and 13C-NMR and MS.

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

    OpenAIRE

    VENNESTROM, PETER NICOLAI RAVNBORG

    2014-01-01

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

  8. Stability and activity of alcohol dehydrogenases in W/O-microemulsions: enantioselective reduction including cofactor regeneration.

    Science.gov (United States)

    Orlich, B; Berger, H; Lade, M; Schomäcker, R

    2000-12-20

    Microemulsions provide an interesting alternative to classical methods for the conversion of less water-soluble substrates by alcohol dehydrogenase, but until now stability and activity were too low for economically useful processes. The activity and stability of the enzymes are dependent on the microemulsion composition, mostly the water and the surfactant concentration. Therefore, it is necessary to know the exact phase behavior of a given microemulsion reaction system and the corresponding enzyme behavior therein. Because of their economic and ecologic suitability polyethoxylated fatty alcohols were investigated concerning their phase behavior and their compatibility with enzymes in ternary mixtures. The phase behavior of Marlipal O13-60 (C13EO6 in industrial quality)/cyclohexane/water and its effect on the activity and stability of alcohol dehydrogenase from Yeast (YADH) and horse liver (HLADH) and the carbonyl reductase from Candida parapsilosis (CPCR) is presented in this study. Beside the macroscopic phase behavior of the reaction system, the viscosity of the system indicates structural changes of aggregates in the microemulsion. The changes of the enzyme activities with the composition are discussed on the basis of transitions from reverse micelles to swollen reverse micelles and finally, the transition to the phase separation. The formate dehydrogenase from Candida boidinii was used for the NADH-regeneration during reduction reactions. While the formate dehydrogenase did not show any kinetic effect on the microemulsion composition, the other enzymes show significant changes of activity and stability varying the water or surfactant concentration of the microemulsion. Under certain conditions, stability could be maintained with HLADH for several weeks. Successful experiments with semi-batch processes including cofactor regeneration and product separation were performed.

  9. A Novel Cu-Mo/ZSM-5 Catalyst for NOx Catalytic Reduction with Ammonia

    Institute of Scientific and Technical Information of China (English)

    Zhe Li; Dang Li; Wei Huang; Kechang Xie

    2005-01-01

    The Cu-Mo/ZSM-5 catalysts with different Cu/Mo ratios were prepared by wet impregnation method, and their catalytic performance for selective catalytic reduction of NOx was studied. The results showed that Cu-Mo/ZSM-5 is a very effective catalyst for NOx catalytic reduction with ammonia, especially when Cu/Mo molar ratio is about 1.5. It not only exhibited the extremely high catalytic activity, but also showed good stability for O2. The bulk phase structure of Cu-Mo/ZSM-5 catalysts was determined by XRD technique, and the results indicated that there is a maximum dispersion for Cu species when Cu/Mo molar ratio is 1.5, and an interaction between Cu and Mo along with HZSM-5 may be present in Cu-Mo/ZSM-5, which may possibly result in a special structure favorable for the catalytic reduction of NOx over Cu-Mo/ZSM-5 catalyst.

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

    Science.gov (United States)

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

    2014-05-01

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

  11. Novel, Regenerable Microlith Catalytic Reactor for CO2 Reduction via Bosch Process Project

    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...

  12. Efficient anti-Prelog enantioselective reduction of acetyltrimethylsilane to (R-1-trimethylsilylethanol by immobilized Candida parapsilosis CCTCC M203011 cells in ionic liquid-based biphasic systems

    Directory of Open Access Journals (Sweden)

    Zhang Bo-Bo

    2012-08-01

    Full Text Available Abstract Background Biocatalytic asymmetric reductions with whole cells can offer high enantioselectivity, environmentally benign processes and energy-effective operations and thus are of great interest. The application of whole cell-mediated bioreduction is often restricted if substrate and product have low water solubility and/or high toxicity to the biocatalyst. Many studies have shown that a biphasic system is often useful in this instance. Hence, we developed efficient biphasic reaction systems with biocompatible water-immiscible ionic liquids (ILs, to improve the biocatalytic anti-Prelog enantioselective reduction of acetyltrimethylsilane (ATMS to (R-1-trimethylsilylethanol {(R-1-TMSE}, which is key synthon for a large number of silicon-containing drugs, using immobilized Candida parapsilosis CCTCC M203011 cells as the biocatalyst. Results It was found that the substrate ATMS and the product 1-TMSE exerted pronounced toxicity to immobilized Candida parapsilosis CCTCC M203011 cells. The biocompatible water-immiscible ILs can be applied as a substrate reservoir and in situ extractant for the product, thus greatly enhancing the efficiency of the biocatalytic process and the operational stability of the cells as compared to the IL-free aqueous system. Various ILs exerted significant but different effects on the bioreduction and the performances of biocatalysts were closely related to the kinds and combination of cation and anion of ILs. Among all the water-immiscible ILs investigated, the best results were observed in 1-butyl-3-methylimidazolium hexafluorophosphate (C4mim·PF6/buffer biphasic system. Furthermore, it was shown that the optimum substrate concentration, volume ratio of buffer to IL, buffer pH, reaction temperature and shaking rate for the bioreduction were 120 mM, 8/1 (v/v, 6.0, 30°C and 180 r/min, respectively. Under these optimized conditions, the initial reaction rate, the maximum yield and the product e.e. were 8.1

  13. Catalytic reduction of 4-nitrophenol with gold nanoparticles synthesized by caffeic acid

    Science.gov (United States)

    Seo, Yu Seon; Ahn, Eun-Young; Park, Jisu; Kim, Tae Yoon; Hong, Jee Eun; Kim, Kyeongsoon; Park, Yohan; Park, Youmie

    2017-01-01

    In this study, various concentrations of caffeic acid (CA) were used to synthesize gold nanoparticles (CA-AuNPs) in order to evaluate their catalytic activity in the 4-nitrophenol reduction reaction. To facilitate catalytic activity, caffeic acid was removed by centrifugation after synthesizing CA-AuNPs. The catalytic activity of CA-AuNPs was compared with that of centrifuged CA-AuNPs ( cf-CA-AuNPs). Notably, cf-CA-AuNPs exhibited up to 6.41-fold higher catalytic activity compared with CA-AuNPs. The catalytic activity was dependent on the caffeic acid concentration, and the lowest concentration (0.08 mM) produced CA-AuNPs with the highest catalytic activity. The catalytic activities of both CA-AuNPs and cf-CA-AuNPs decreased with increasing caffeic acid concentration. Furthermore, a conversion yield of 4-nitrophenol to 4-aminophenol in the reaction mixture was determined to be 99.8% using reverse-phase high-performance liquid chromatography. The product, 4-aminophenol, was purified from the reaction mixture, and its structure was confirmed by 1H-NMR. It can be concluded that the removal of the reducing agent, caffeic acid in the present study, significantly enhanced the catalytic activity of CA-AuNPs in the 4-nitrophenol reduction reaction.

  14. Highly efficient catalytic enantioselective Mannich reaction of malonates with N-tert-butoxycarbonyl imines by using Yb(OTf)3/pybox catalysts at room temperature.

    Science.gov (United States)

    Karimi, Babak; Jafari, Ehsan; Enders, Dieter

    2013-07-29

    Go Mannich! A highly efficient and enantioselective method for the direct asymmetric reaction of dibenzyl malonate with N-tert-butoxycarbonyl aldimines in the presence of Yb(OTf)3 and iPr-pybox complexes is described (see scheme; pybox = pyridine bisoxazoline).

  15. Modular Terpenoid Construction via Catalytic Enantioselective Formation of All-Carbon Quaternary Centers: Total Synthesis of Oridamycin A, Triptoquinones B and C, and Isoiresin.

    Science.gov (United States)

    Feng, Jiajie; Noack, Florian; Krische, Michael J

    2016-09-28

    Total syntheses of oridamycin A, triptoquinones B and C, and isoiresin are accomplished from a common intermediate prepared via iridium-catalyzed alcohol C-H tert-(hydroxy)prenylation - a byproduct-free process that forms an all-carbon quaternary stereocenter with excellent control of diastereo- and enantioselectivity.

  16. 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…

  17. Tuning the catalytic activity of graphene nanosheets for oxygen reduction reaction via size and thickness reduction.

    Science.gov (United States)

    Benson, John; Xu, Qian; Wang, Peng; Shen, Yuting; Sun, Litao; Wang, Tanyuan; Li, Meixian; Papakonstantinou, Pagona

    2014-11-26

    Currently, the fundamental factors that control the oxygen reduction reaction (ORR) activity of graphene itself, in particular, the dependence of the ORR activity on the number of exposed edge sites remain elusive, mainly due to limited synthesis routes of achieving small size graphene. In this work, the synthesis of low oxygen content (graphene nanosheets with lateral dimensions smaller than a few hundred nanometers were achieved using a combination of ionic liquid assisted grinding of high purity graphite coupled with sequential centrifugation. We show for the first time that the graphene nanosheets possessing a plethora of edges exhibited considerably higher electron transfer numbers compared to the thicker graphene nanoplatelets. This enhanced ORR activity was accomplished by successfully exploiting the plethora of edges of the nanosized graphene as well as the efficient electron communication between the active edge sites and the electrode substrate. The graphene nanosheets were characterized by an onset potential of -0.13 V vs Ag/AgCl and a current density of -3.85 mA/cm2 at -1 V, which represent the best ORR performance ever achieved from an undoped carbon based catalyst. This work demonstrates how low oxygen content nanosized graphene synthesized by a simple route can considerably impact the ORR catalytic activity and hence it is of significance in designing and optimizing advanced metal-free ORR electrocatalysts.

  18. 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.

  19. Water Soluble Iron aminoclay for Catalytic Reduction of Nitrophenol

    Directory of Open Access Journals (Sweden)

    S. ANBU ANJUGAM VANDARKUZHALI

    2013-06-01

    Full Text Available Water soluble iron decorated phyllosilicate is synthesized through one pot sol-gel synthesis by a wet chemical method using NaBH4 as reducing agent. The as-synthesized nanocomposite is characterized by powder-XRD and TGA techniques. The morphology of the composite is obtained using HRSEM and HRTEM. The prepared nanocomposite is an efficient catalyst for the reduction of nitrophenol.

  20. 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

    The catalytic NO reduction by methane was studied using a (NO,CH4,Ar),Pt|polybenzimidazole(PBI)–H3PO4|Pt,(H2,Ar) fuel cell at 135 and 165°C. It has been found that, without any reducing agent (like CH4), NO can be electrochemically reduced in the (NO, Ar), Pt/C|PBI–H3PO4|Pt/C, (H2,Ar) fuel cell...... 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...

  1. Enantioselectivity of Photochemical Reactions within Polymer Microcapsules

    Institute of Scientific and Technical Information of China (English)

    MA,Lei; WU,Li-Zhu; ZHANG,Li-Ping; TUNG,Chen-Ho

    2003-01-01

    Polymer microcapsule was employed as a reaction medium to achieve enantioselectivity in photochemical reduction of phenyl cyclohexyl ketone and photoelectrocyclization of tropolone methyl ether unader the influence of various chiral inductors. In all cases,low but evident enantioselectivity was observed. The poor enantioselectivity is probably due to the facts that not all the capsules include simultaneously both the chiral inductor and the reactant molecules, and the wall of the microcapsule is not rigid enough tohold the reactant and the chiral inductor moleculesin close contact.

  2. Long-time experience in catalytic flue gas cleaning and catalytic NO{sub x} reduction in biofueled boilers

    Energy Technology Data Exchange (ETDEWEB)

    Ahonen, M. [Tampella Power Inc., Tampere (Finland)

    1996-12-31

    NO emissions are reduced by primary or secondary methods. Primary methods are based on NO reduction in the combustion zone and secondary methods on flue gas cleaning. The most effective NO reduction method is selective catalytic reduction (SCR). It is based on NO reduction by ammonia on the surface of a catalyst. Reaction products are water and nitrogen. A titanium-dioxide-based catalyst is very durable and selective in coal-fired power plants. It is not poisoned by sulphur dioxide and side reactions with ammonia and sulphur dioxide hardly occur. The long time experience and suitability of a titanium-dioxide-based catalyst for NO reduction in biofuel-fired power plants was studied. The biofuels were: peat, wood and bark. It was noticed that deactivation varied very much due to the type of fuel and content of alkalinities in fuel ash. The deactivation in peat firing was moderate, close to the deactivation noticed in coal firing. Wood firing generally had a greater deactivation effect than peat firing. Fuel and fly ash were analyzed to get more information on the flue gas properties. The accumulation of alkali and alkaline earth metals and sulphates was examined together with changes in the physical composition of the catalysts. In the cases where the deactivation was the greatest, the amount of alkali and alkaline earth metals in fuels and fly ashes and their accumulation were very significant. (author) (3 refs.)

  3. 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...

  4. 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.

  5. Chemical deactivation of Cu-SSZ-13 ammonia selective catalytic reduction (NH3-SCR) systems

    NARCIS (Netherlands)

    Lezcano-Gonzalez, I.; Deka, U.; van der Bij, H. E.; Paalanen, P.; Arstad, B.; Weckhuysen, B. M.; Beale, A. M.

    2014-01-01

    The chemical deactivation of Cu-SSZ-13 Ammonia Selective Catalytic Reduction (NH3-SCR) catalysts by Pt, Zn, Ca and P has been systematically investigated using a range of analytical techniques in order to study the influence on both the zeolitic framework and the active Cu2+ ions. The results obtain

  6. Isolated Cu2+ ions: active sites for selective catalytic reduction of NO

    NARCIS (Netherlands)

    Korhonen, S.T.; Fickel, D.W.; Lobo, R.F.; Weckhuysen, B.M.; Beale, A.M.

    2011-01-01

    Cu chabazite catalysts show remarkable low temperature activity in selective catalytic reduction (SCR) of NO. This high activity is due to the unique character of the zeolite framework that allows only the presence of one type of isolated mononuclear Cu2+ species. These Cu2+ species are the active s

  7. INVESTIGATION OF SELECTIVE CATALYTIC REDUCTION IMPACT ON MERCURY SPECIATION UNDER SIMULATED NOX EMISSION CONTROL CONDITIONS

    Science.gov (United States)

    Selective catalytic reduction (SCR) technology is being increasingly applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury in the coal com...

  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. Unification of catalytic water oxidation and oxygen reduction reactions: amorphous beat crystalline cobalt iron oxides.

    Science.gov (United States)

    Indra, Arindam; Menezes, Prashanth W; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Das, Chittaranjan; Tallarida, Massimo; Schmeißer, Dieter; Strasser, Peter; Driess, Matthias

    2014-12-17

    Catalytic water splitting to hydrogen and oxygen is considered as one of the convenient routes for the sustainable energy conversion. Bifunctional catalysts for the electrocatalytic oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are pivotal for the energy conversion and storage, and alternatively, the photochemical water oxidation in biomimetic fashion is also considered as the most useful way to convert solar energy into chemical energy. Here we present a facile solvothermal route to control the synthesis of amorphous and crystalline cobalt iron oxides by controlling the crystallinity of the materials with changing solvent and reaction time and further utilize these materials as multifunctional catalysts for the unification of photochemical and electrochemical water oxidation as well as for the oxygen reduction reaction. Notably, the amorphous cobalt iron oxide produces superior catalytic activity over the crystalline one under photochemical and electrochemical water oxidation and oxygen reduction conditions.

  10. In situ synthesized gold nanoparticles in hydrogels for catalytic reduction of nitroaromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Xiao-Qiong; Wu, Xing-Wen; Huang, Qing [Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021 (China); Shen, Jiang-Shan, E-mail: jsshen@iue.ac.cn [Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021 (China); Ningbo Urban Environment Observation and Research Station, Chinese Academy of Sciences, Ningbo 315800 (China); Zhang, Hong-Wu, E-mail: hwzhang@iue.ac.cn [Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021 (China)

    2015-03-15

    Graphical abstract: - Highlights: • In situ preparing Au nanoparticles by photoreduction in chitosan hydrogels was firstly achieved. • In situ photoreduction for creating Au nanoparticles is environmentally friendly and the operation procedure is very simple. • The as-prepared Au nanoparticles have good catalytic performance. • Affording an effective strategy for converting some high explosive compounds such as 2,4,6-tNT to nonexplosive. - Abstract: Developing hydrogel systems featured by catalytic active is of importance to construct highly effective platforms for removing environmental pollutants/hazardous substances or for bio-/chemosensing. Reported herein are our recent finding that Au nanoparticles could be in situ prepared in chitosan-Au{sup III} hydrogel system via photoreduction, and the as-prepared Au nanoparticles could be employed for the catalytic reduction of a series of nitroaromatic compounds by sodium borohydride (NaBH{sub 4}). Experimental conditions of synthesizing Au nanoparticles, including pH, concentration of Au{sup III}, and light irradiation time were systematically investigated. The as-prepared Au nanoparticles were characterized by UV–vis absorption spectroscopy, X-ray diffraction (XRD), transmission and field emission scanning electron microscopy (TEM and FESEM). This is the first example for in situ formed metal nanoparticles in chitosan hydrogel systems via photoreduction. The effectiveness of the as-prepared Au nanoparticles as nanocatalysts was evaluated by employing the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by NaBH{sub 4} as a model reaction. The catalytic reduction reaction was found to be very efficient and to follow a pseudo-first-order kinetics. The as-prepared Au nanoparticles demonstrated good reusability and stability. The reduction of a series of other nitroaromatic compounds including highly explosives 2,4,6-trinitrophenol (2,4,6-tNP) and 2,4,6-trinitrotoluene (2,4,6-tNT) was achieved by means

  11. The mechanism of selective catalytic reduction of NOx on Cu-SSZ-13 - a computational study.

    Science.gov (United States)

    Crandell, Douglas W; Zhu, Haiyang; Yang, Xiaofan; Hochmuth, John; Baik, Mu-Hyun

    2017-01-03

    The copper-exchanged aluminosilicate zeolite SSZ-13 is a leading catalyst for the selective catalytic reduction of NO. Density functional theory calculations are used to construct a complete catalytic cycle of this process paying special attention to the coordination geometries and redox states of copper. N2 can be produced in the reduction half-cycle via a nitrosamine intermediate generated from the reaction of the additive reductant NH3 with a NO(+) intermediate stabilized by the zeolite lattice. The decomposition of this nitrosamine species can be assisted by incipient Brønsted acid sites generated during catalysis. Our calculations also suggest that the reoxidation of Cu(i) to Cu(ii) requires the addition of both NO and O2. The production of a second equivalent of N2 during the oxidation half-cycle proceeds through a peroxynitrite intermediate to form a Cu-nitrite intermediate, which may react with an acid, either HNO2 or NH4(+) to close the catalytic cycle. Models of copper neutralized by an external hydroxide ligand are also examined. These calculations form a key basis for understanding the mechanism of NO reduction in Cu-SSZ-13 in order to develop strategies for rationally optimizing the performance in future experiments.

  12. 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.

  13. Effect of oxidation and catalytic reduction of trace organic contaminants on their activated carbon adsorption.

    Science.gov (United States)

    Schoutteten, Klaas V K M; Hennebel, Tom; Dheere, Ellen; Bertelkamp, Cheryl; De Ridder, David J; Maes, Synthia; Chys, Michael; Van Hulle, Stijn W H; Vanden Bussche, Julie; Vanhaecke, Lynn; Verliefde, Arne R D

    2016-12-01

    The combination of ozonation and activated carbon (AC) adsorption is an established technology for removal of trace organic contaminants (TrOCs). In contrast to oxidation, reduction of TrOCs has recently gained attention as well, however less attention has gone to the combination of reduction with AC adsorption. In addition, no literature has compared the removal behavior of reduction vs. ozonation by-products by AC. In this study, the effect of pre-ozonation vs pre-catalytic reduction on the AC adsorption efficiency of five TrOCs and their by-products was compared. All compounds were susceptible to oxidation and reduction, however the catalytic reductive treatment proved to be a slower reaction than ozonation. New oxidation products were identified for dinoseb and new reduction products were identified for carbamazepine, bromoxynil and dinoseb. In terms of compatibility with AC adsorption, the influence of the oxidative and reductive pretreatments proved to be compound dependent. Oxidation products of bromoxynil and diatrizoic acid adsorbed better than their parent TrOCs, but oxidation products of atrazine, carbamazepine and dinoseb showed a decreased adsorption. The reductive pre-treatment showed an enhanced AC adsorption for dinoseb and a major enhancement for diatrizoic acid. For atrazine and bromoxynil, no clear influence on adsorption was noted, while for carbamazepine, the reductive pretreatment resulted in a decreased AC affinity. It may thus be concluded that when targeting mixtures of TrOCs, a trade-off will undoubtedly have to be made towards overall reactivity and removal of the different constituents, since no single treatment proves to be superior to the other.

  14. 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

  15. Solid-phase reduction of Cr2O3 under chemical catalytic conditions

    Science.gov (United States)

    Simonov, V. K.; Grishin, A. M.

    2016-06-01

    The kinetics of the solid-phase reduction of Cr2O3 with carbon under chemical catalytic action on the reacting system is studied. A significant intensification of the process in the presence of small amounts of potassium and sodium salts is established. The concepts of the catalyst action mechanism are considered and experimentally substantiated. Manufacture of iron-chromium master alloys with a restricted content of carbon can be organized at low temperatures, and they can be used in steelmaking.

  16. PILLARED CLAYS AS SUPERIOR CATALYSTS FOR SELECTIVE CATALYTIC REDUCTION OF NITRIC OXIDE

    Energy Technology Data Exchange (ETDEWEB)

    R. Q. LONG; R.T. YANG

    1998-09-30

    Selective catalytic reduction (SCR) of NO{sub x} by hydrocarbons was investigated on Pt doped MCM-41 and copper ion and/or cerium ion-exchanged Al-MCM-41 in the presence of excess oxygen. It was found that Pt/MCM-41 provided the highest specific NO reduction rates as compared with other Pt doped catalysts reported in the literature, such as Pt/Al{sub 2}O{sub 3} and Pt/ZSM-5. For different hydrocarbons, the catalytic activity decreased according to the sequence of C{sub 3}H{sub 6} {approx} C{sub 2}H{sub 4} >> C{sub 3}H{sub 8} > CH{sub 4}. This catalyst was also stable in the presence of H{sub 2}O and SO{sub 2}. Cu exchanged Al-MCM-41 and cerium promoted Cu-Al-MCM-41 (i.e., Ce-Cu-Al-MCM-41) were also found to be active in this reaction. Higher NO{sub x} conversions to N2 were obtained on the Ce-Cu-Al-MCM-41 as compared with Cu-Al-MCM-41. The activity of Ce-Cu-Al-MCM-41 was approximately the same as that of Cu-ZSM-5; but the former had a wider temperature window. TPR results indicated that only isolated Cu{sup 2+} and Cu{sup +} ions were detected in the Cu{sup 2+}-exchanged Al-MCM-41 samples, which may play an important role in the selective catalytic reduction of NO{sub x} to N{sub 2}. After some cerium ions were introduced into Cu-Al-MCM-41, Cu{sup 2+} in the molecular sieve became more easily reducible by H{sub 2}. This may be related to the increase of catalytic activity of NO{sub x} reduction by ethylene.

  17. Enantioselective olefin metathesis with cyclometalated ruthenium complexes.

    Science.gov (United States)

    Hartung, John; Dornan, Peter K; Grubbs, Robert H

    2014-09-17

    The success of enantioselective olefin metathesis relies on the design of enantioenriched alkylidene complexes capable of transferring stereochemical information from the catalyst structure to the reactants. Cyclometalation of the NHC ligand has proven to be a successful strategy to incorporate stereogenic atoms into the catalyst structure. Enantioenriched complexes incorporating this design element catalyze highly Z- and enantioselective asymmetric ring opening/cross metathesis (AROCM) of norbornenes and cyclobutenes, and the difference in ring strain between these two substrates leads to different propagating species in the catalytic cycle. Asymmetric ring closing metathesis (ARCM) of a challenging class of prochiral trienes has also been achieved. The extent of reversibility and effect of reaction setup was also explored. Finally, promising levels of enantioselectivity in an unprecedented Z-selective asymmetric cross metathesis (ACM) of a prochiral 1,4-diene was demonstrated.

  18. Enantioselective Olefin Metathesis with Cyclometalated Ruthenium Complexes

    Science.gov (United States)

    2015-01-01

    The success of enantioselective olefin metathesis relies on the design of enantioenriched alkylidene complexes capable of transferring stereochemical information from the catalyst structure to the reactants. Cyclometalation of the NHC ligand has proven to be a successful strategy to incorporate stereogenic atoms into the catalyst structure. Enantioenriched complexes incorporating this design element catalyze highly Z- and enantioselective asymmetric ring opening/cross metathesis (AROCM) of norbornenes and cyclobutenes, and the difference in ring strain between these two substrates leads to different propagating species in the catalytic cycle. Asymmetric ring closing metathesis (ARCM) of a challenging class of prochiral trienes has also been achieved. The extent of reversibility and effect of reaction setup was also explored. Finally, promising levels of enantioselectivity in an unprecedented Z-selective asymmetric cross metathesis (ACM) of a prochiral 1,4-diene was demonstrated. PMID:25137310

  19. Appropriate conditions or maximizing catalytic reduction efficiency of nitrate into nitrogen gas in groundwater.

    Science.gov (United States)

    Chen, Ying-Xue; Zhang, Yan; Chen, Guang-Hao

    2003-05-01

    This study focused on the appropriate catalyst preparation and operating conditions for maximizing catalytic reduction efficiency of nitrate into nitrogen gas from groundwater. Batch experiments were conducted with prepared Pd and/or Cu catalysts with hydrogen gas supplied under specific operating conditions. It has been found that Pd-Cu combined catalysts prepared at a mass ratio of 4:1 can maximize the nitrate reduction into nitrogen gas. With an increase in the quantity of the catalysts, both nitrite intermediates and ammonia can be kept at a low level. It has also been found that the catalytic activity is mainly affected by the mass ratio of hydrogen gas to nitrate nitrogen, and hydrogen gas gauge pressure. Appropriate operating values of H(2)/NO(3)-N ratio, hydrogen gas gauge pressure, pH, and initial nitrate concentration have been determined to be 44.6g H(2)/g N, 0.15 atm, 5.2 (-), 100 mg x L(-1) for maximizing the catalytic reduction of nitrate from groundwater.

  20. An Efficient Method for Catalytic Asymmetric Reduction of Diketones and Application of Synthesis to Chiral 2,5-Diphenylpyrrolidine and 2,5-Diphenylthiolane

    Institute of Scientific and Technical Information of China (English)

    LI Xiang; ZHAO Gang; CAO Wei-Guo

    2006-01-01

    Asymmetric reduction of diketones with borane reagents generated in situ using cheap and available NaBH4 and SnCl2 in the presence of (S)-(-)-α,α-diphenyl-2-pyrrolidinemethanol was successfully achieved to yield the corresponding chiral diols with excellent stereoselectivity and enantioselectivity. And the chiral diol was transformed into optically pure C2-symmetricl chiral amine or thioether.

  1. Kinetics of Carbothermic Reduction of MnO2 and Catalytic Effect of La2O3

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Kinetics of carbothermic reduction of manganese oxide and the catalytic effect of La2O3 on the reduction have been studied by the measurement of mass loss in N2 atmosphere at different temperatures and followed by SEM analysis. It is concluded that the kinetics of carbothermic reduction of manganese oxide is divided into three stages: gas diffusion controlling stage, carbon gasification controlling stage and solid state diffusion controlling stage. La2O3 has catalytic effect on the reduction. The catalytic effect of La2O3 increases with the added amount of La2O3. SEM analysis shows that the catalytic mechanism is that Laa2O3 promotes the transfer of oxygen ions so that carbon gasifying is catalyzed and thus carbothermic reduction of MnO3 is catalyzed.

  2. Synthesis of Functionalized Furans via Chemoselective Reduction/Wittig Reaction Using Catalytic Triethylamine and Phosphine.

    Science.gov (United States)

    Lee, Chia-Jui; Chang, Tzu-Hsiu; Yu, Jhen-Kuei; Madhusudhan Reddy, Ganapuram; Hsiao, Ming-Yu; Lin, Wenwei

    2016-08-05

    An efficient protocol for the synthesis of highly functionalized furans via intramolecular Wittig reaction has been developed using catalytic amounts of phosphine and triethylamine. Silyl chloride served as the initial promoter to activate the phosphine oxide. Reduction of the activated phosphine oxide by hydrosilane resulted in generation of phosphine, while decomposition of Et3N·HCl resulted in regeneration of base, which mediated formation of phosphorus ylide. Remarkably, the in situ generated byproduct, Et3N·HCl, also catalyzes reduction of phosphine oxide.

  3. 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.

  4. 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.

  5. Heteropoly acid promoted Cu and Fe catalysts for the selective catalytic reduction of NO with ammonia

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Mossin, Susanne L.; Riisager, Anders

    2011-01-01

    Cu/TiO2, Fe/TiO2 and heteropoly acid promoted Cu/TiO2, Fe/TiO2 catalysts were prepared and characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR and EPR. The catalysts exhibited only crystalline TiO2 phases with the active metals and promoters in highly dispersed state. The acidic properties...... activity and acidity was lower for promoted catalysts than for unpromoted catalysts. In the heteropoly acid promoted catalysts the SCR active Cu and Fe metals were protected from potassium poisons by bonding of the potassium to the Brønsted acid centres. Thus heteropoly acid promoted catalysts might...... were studied and compared with the catalytic activity for the selective catalytic reduction (SCR) of NO with ammonia. The SCR activities and acidity values of heteropoly acid promoted catalysts were found to be much higher than unpromoted catalysts. The influence of potassium poisons on the SCR...

  6. Use of formic acid as reducing agent for application in catalytic reduction of nitrate in water.

    Science.gov (United States)

    Garron, Anthony; Epron, Florence

    2005-08-01

    The reduction of nitrate in nitrogen using bimetallic palladium tin catalysts and hydrogen is an interesting process for water treatment. The aim of the present study is to use formic acid (FA) as a reducing agent and a pH buffer in order to substitute the mixture of hydrogen and carbon dioxide. The catalytic performances of a palladium tin catalyst supported on silica were evaluated in the presence of FA, as a function of the initial acid concentration and of the gas phase (N(2), CO(2), or H(2)). Results were compared to those obtained with hydrogen in the presence of carbon dioxide. Similar mechanisms seem to explain the identical catalytic performances observed with these two reducing agents.

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

    Energy Technology Data Exchange (ETDEWEB)

    Moreno-Tost, Ramon; Santamaria-Gonzalez, Jose; Rodriguez-Castellon, Enrique; Jimenez-Lopez, Antonio [Departamento de Quimica Inorganica, Cristalografia y Mineralogia, Facultad de Ciencias, Unidad Asociada del Instituto de Catalisis y Petroleoquimica, CSIC, Universidad de Malaga, Campus de Teatinos, 29071 Malaga (Spain); Autie, Miguel A.; Glacial, Marisol Carreras [Centro Nacional de Investigaciones Cientificas, Ciudad de la Habana, La Habana (Cuba); Gonzalez, Edel [Instituto Superior Pedagogico ' Enrique Jose Varona' , La Habana (Cuba); Pozas, Carlos De las [Centro de Gerencia de Programas y Proyectos Priorizados, La Habana (Cuba)

    2004-07-15

    The catalytic selective reduction of NO over Cu-exchanged natural zeolites (mordenite (MP) and clinoptilolite (HC)) from Cuba using NH{sub 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{sub 2} at low temperatures, and exhibiting good water tolerance. The chemical state of the Cu(II) in exchanged zeolites was characterized by H{sub 2}-TPR and XPS. Cu(II)-exchanged clinoptilolite underwent a severe deactivation in the presence of SO{sub 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{sub 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. Biomimetic Modeling of Copper Complexes: A Study of Enantioselective Catalytic Oxidation on D-(+-Catechin and L-(−-Epicatechin with Copper Complexes

    Directory of Open Access Journals (Sweden)

    Francesco G. Mutti

    2008-01-01

    Full Text Available The biomimetic catalytic oxidations of the dinuclear and trinuclear copper(II complexes versus two catechols, namely, D-(+-catechin and L-(−-epicatechin to give the corresponding quinones are reported. The unstable quinones were trapped by the nucleophilic reagent, 3-methyl-2-benzothiazolinone hydrazone (MBTH, and have been calculated the molar absorptivities of the different quinones. The catalytic efficiency is moderate, as inferred by kinetic constants, but the complexes exhibit significant enantio-differentiating ability towards the catechols, albeit for the dinuclear complexes, this enantio-differentiating ability is lower. In all cases, the preferred enantiomeric substrate is D-(+-catechin to respect the other catechol, because of the spatial disposition of this substrate.

  10. Using Acetylene for Selective Catalytic Reduction of NO in Excess Oxygen

    Institute of Scientific and Technical Information of China (English)

    YU Shan-Shan; WANG Xin-Ping; WANG Chong; XU Yan

    2006-01-01

    Acetylene as a reducing agent for selective catalytic reduction of NO (C2H2-SCR) was investigated over a series of metal exchanged HY catalysts, in the reaction system of 0.16% NO, 0.08% C2H2, and 9.95% O2 (volume percent)in He. 75% of NO conversion to N2 with hydrocarbon efficiency about 1.5 was achieved over a Ce-HY catalyst around 300 ℃. The NO removal level was comparable with that of selective catalytic reduction of NOx by C3H6reported in literatures, although only one third of the reducing agent in carbon moles was used in the C2H2-SCR of NO. The protons in zeolite were crucial to the C2H2-SCR of NO, and the performance of HY in the reaction was significantly promoted by cerium incorporation into the zeolite. NO2 was proposed to be the intermediate of NO reduction to N2, and the oxidation of NO to NO2 was rate-determining step of the C2H2-SCR of NO over Ce-HY.The suggestion was well supported by the results of the NO oxidation with O2, and the C2H2 consumption under the conditions in the presence or absence of NO.

  11. Controlling Enantioselectivity in Additions to Cyclic Oxocarbenium Ions via Transition Metal Catalysis.

    Science.gov (United States)

    Watson, Mary P; Maity, Prantik

    2012-01-01

    Controlling enantioselectivity in additions to oxocarbenium ions remains a challenge in asymmetric catalysis. By catalytically generating a chiral organometallic intermediate, a copper acetylide, we have developed a novel approach for additions of carbon nucleophiles to cyclic oxocarbenium ions in high enantioselectivities and yields.

  12. 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.

  13. 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

    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...... conversion observed experimentally. Simulations also suggested that it may be advantageous with respect to the emission of NO to use smallinstead of big limestone particles for desulphurisation in fluidised bed combustors due to the ways different sized particles capture SO2....

  14. 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.

  15. Palladium-Catalyzed, Enantioselective Heine Reaction.

    Science.gov (United States)

    Punk, Molly; Merkley, Charlotte; Kennedy, Katlyn; Morgan, Jeremy B

    2016-07-01

    Aziridines are important synthetic intermediates for the generation of nitrogen-containing molecules. N-Acylaziridines undergo rearrangement by ring expansion to produce oxazolines, a process known as the Heine reaction. The first catalytic, enantioselective Heine reaction is reported for meso-N-acylaziridines where a palladium(II)-diphosphine complex is employed. The highly enantioenriched oxazoline products are valuable organic synthons and potential ligands for transition-metal catalysis.

  16. Catalytic Reductive Degradation of Methyl Orange Using Air Resilient Copper Nanostructures

    Directory of Open Access Journals (Sweden)

    Razium Ali Soomro

    2015-01-01

    Full Text Available The study describes the application of oxidation resistant copper nanostructures as an efficient heterogeneous catalyst for the treatment of organic dye containing waste waters. Copper nanostructures were synthesized in an aqueous environment using modified surfactant assisted chemical reduction route. The synthesized nanostructures have been characterized by UV-Vis, Fourier transform infrared spectroscopy FTIR spectroscopy, Atomic force microscopy (AFM, Scanning Electron Microscopy (SEM, and X-ray diffractometry (XRD. These surfactant capped Cu nanostructures have been used as a heterogeneous catalyst for the comparative reductive degradation of methyl orange (MO in the presence of sodium borohydride (NaBH4 used as a potential reductant. Copper nanoparticles (Cu NPs were found to be more efficient compared to copper nanorods (Cu NRds with the degradation reaction obeying pseudofirst order reaction kinetics. Shape dependent catalytic efficiency was further evaluated from activation energy (EA of reductive degradation reaction. The more efficient Cu NPs were further employed for reductive degradation of real waste water samples containing dyes collected from the drain of different local textile industries situated in Hyderabad region, Pakistan.

  17. 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.

  18. Selective catalytic reduction of NO by ammonia over oil shale ash and fly ash catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Changtao Yue; Shuyuan Li [University of Petroleum, Beijing (China). State Key Lab of Heavy Oil Processing

    2003-07-01

    Acid rain and urban air pollution, produced mainly by pollutants such as SOX and NOX and other volatile organic compounds, has become the most serious environmental problem. The selective catalytic reduction (SCR) of NO with NH{sub 3} in the presence of oxygen is a wellproven method to limit the NOX emissions. The work in this field has been the subject of much research in recent years. In this paper, NO reduction with NH{sub 3} over oil shale ash or fly ash catalysts was studied. Fe, Cu, V or Ni as active elements was loaded by adding aqueous solutions of the metal nitrate over the oil shale ash or fly ash support. The activities of the catalysts for NO removal were measured in a fixed-bed reactor. According to the results, oil shale ash or fly ash, after pre-treatment, can be reasonably used as the SCR catalyst support to remove NO from flue gas. Cu gave the highest catalytic activity and NO conversion for fly ash while V for oil shale ash. As the support, fly ash is more feasible than oil shale ash. Because of their low cost and high efficiency, the catalysts should be used in the SCR process. Further research on this subject is necessary in the future to understand more details of the SCR system and issue of pollution control. 9 refs., 2 figs., 2 tabs.

  19. Life cycle assessment of the selective catalytic reduction; Oekobilanzierung des selektiven katalytischen Reduktionsverfahrens

    Energy Technology Data Exchange (ETDEWEB)

    Barzaga-Castellanos, L.; Kayser, G.; Markert, B. [Lehrstuhl Umweltverfahrenstechnik, Internationales Hochschulinstitut Zittau (Germany); Neufert, R. [Siemens AG, Bereich Energieerzeugung (KWU), Keramik- und Porzellanwerk Redwitz, Bereich Katalysatoren (Germany)

    1998-07-01

    This paper describes the overall reduction of the environmental impact by the use of selective catalytic reduction (SCR) determined by a investigation of the life cycle assessment of SCR systems for power plants. The overall reduction of the environmental impact by the use of SCR was determined under consideration of the total product life cycle from manufacture of the starting materials through catalyst production and use in the power plant to processing for recycling. Following clear specification of the overall system limits and definition of the goals for the analysis to be performed, the inventory analyses were determined for the individual process steps and in summary for the overall process cycle/sequence under consideration of basic SCR application variants in the power plant. The inventory analysis was used to generate the impact assessment and improvement assessment. This work was performed using the concept given by Braunschweig, A., and Mueller-Wenk, R. [5]. Other tools of environmental management of products and processes used were the methods of process cycle/sequence analysis, process input-output analysis and cumulative energy consumption or expenditure [14]. (orig.) [Deutsch] Zur Ermittlung der Brutto-Umweltbelastung durch Einsatz des selektiven katalytischen Reduktionsverfahrens (selective catalytic reduction, SCR) unter Beruecksichtigung des gesamten Produktlebenszyklus von der Herstellung der Vorprodukte ueber die Produktion der Katalysatoren und den Einsatz im Kraftwerk bis zur Aufbereitung zur Wiederverwertung wurde das Instrumentarium Oekobilanz angewandt. Nach einer eindeutigen Festlegung der gesamten Systemgrenzen und Definition der Ziele fuer die durchzufuehrende Analyse wurden die Sachbilanzen fuer die einzelnen Prozessschritte und zusammenfassend die Sachbilanz fuer die gesamte Prozesskette unter Beruecksichtigung grundsaetzlicher Anwendungsvarianten des SCR-Verfahrens im Kraftwerk erstellt. Auf der Sachbilanz aufbauend erfolgte die

  20. Remediation of actual groundwater polluted with nitrate by the catalytic reduction over copper-palladium supported on active carbon

    OpenAIRE

    Wang, Yi; Sakamoto, Yoshinori; Kamiya, Yuichi

    2009-01-01

    Catalytic reduction of nitrate (NO3-) in groundwater over a Cu-Pd catalyst supported on active carbon was investigated in a gas-liquid co-current flow system at 298 K. Although Cu-Pd/active carbon, in which the Cu/Pd molar ratio was more than 0.66, showed high activity, high selectivity for the formation of N2 and N2O (98%), and high durability for the reduction of 100 ppm NO3- in distilled water, the catalytic performance decreased during the reduction of NO3- in groundwater. The catalyst al...

  1. Confirmation of Isolated Cu2+ Ions in SSZ-13 Zeolite as Active Sites in NH3-Selective Catalytic Reduction

    NARCIS (Netherlands)

    Deka, U.; Juhin, A.F.; Eilertsen, E.A.; Emerich, H.; Green, M.A.; Korhonen, S.T.; Weckhuysen, B.M.; Beale, A.M.

    2012-01-01

    NH3-Selective Catalytic Reduction (NH3-SCR) is a widely used technology for NOx reduction in the emission control systems of heavy duty diesel vehicles. Copper-based ion exchanged zeolites and in particular Cu-SSZ-13 (CHA framework) catalysts show both exceptional activity and hydrothermal stability

  2. PILLARED CLAYS AS SUPERIOR CATALYSTS FOR SELECTIVE CATALYTIC REDUCTION OF NITRIC OXIDE

    Energy Technology Data Exchange (ETDEWEB)

    R.Q. Long; N. Tharappiwattananon; W.B. Li; R.T. Yang

    2000-09-01

    Removal of NO{sub x} (NO + NO{sub 2}) from exhaust gases is a challenging subject. V{sub 2}O{sub 5}-based catalysts are commercial catalysts for selective catalytic reduction (SCR) with NH{sub 3} for stationary sources. However, for diesel and lean-burn gasoline engines in vehicles, hydrocarbons would be the preferred reducing agents over NH{sub 3} because of the practical problems associated with the use of NH{sub 3} (i.e., handling and slippage through the reactor). The noble-metal three-way catalysts are not effective under these conditions. The first catalyst found to be active for selective catalytic reduction of NO by hydrocarbons in the presence of excess oxygen was copper exchanged ZSM-5 and other zeolites, reported in 1990 by Iwamoto in Japan and Held et al. in Germany. Although Cu-ZSM-5 is very active and the most intensively studied catalyst, it suffers from severe deactivation in engine tests, mainly due to H{sub 2}O and SO{sub 2}. In this project, we found that ion-exchanged pillared clays and MCM-41 catalysts showed superior SCR activities of NO with hydrocarbon. All Cu{sup 2+}-exchanged pillared clays showed higher SCR activities than Cu-ZSM-5 reported in the literature. In particular, H{sub 2}O and SO{sub 2} only slightly deactivated the SCR activity of Cu-TiO{sub 2}-PILC, whereas severe deactivation was observed for Cu-ZSM-5. Moreover, Pt/MCM-41 provided the highest specific NO reduction rates as compared with other Pt doped catalysts, i.e., Pt/Al{sub 2}O{sub 3}, Pt/SiO{sub 2} and Pt/ZSM-5. The Pt/MCM-41 catalyst also showed a good stability in the presence of H{sub 2}O and SO{sub 2}.

  3. Ammonia-treated Ordered Mesoporous Carbons as Catalytic Materials for Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiqing; Lee, Je Seung; Zhu, Qing; Liu, Jun; Wang, Yong; Dai, Sheng

    2010-04-13

    Polymer electrolyte membrane fuel cells (PEMFCs) have been considered as promising alternative power sources for many mobile and stationary applications. Compared to the fast hydrogen oxidation at the anode, the sluggish oxygen reduction reaction (ORR) at the cathode requires high-performance catalysts. Currently, platium (Pt) nanoparticles supported on high surface area carbons remain the best catalysts for ORR. However, both instability and high cost of Pt-based catalysts represent two main obstacles limiting the commercial applications of PEMFCs. The instability of supported Pt catalysts is mainly due to the corrosion of carbon support under operation conditions and the agglomation and detachment of Pt particles, leading to a decrease in catalytic surface areas. Development of corrosion resistant supports and enhancement of the interactions between Pt and supports are two strategies to improve the cathode long-term activity.

  4. Co$_9$S$_8$ nanotubes: facile synthesis and application in the catalytic reduction of 4-nitrophenol

    Indian Academy of Sciences (India)

    TAO GENG; YONGHONG NI; HONGYAN WANG; XIA ZHOU

    2016-10-01

    Co$_9$S$_8$ nanotubes have been successfully synthesized via a facile two-step solvothermal method without the assistance of any template or surfactant, using cobalt sulphate (CoSO$_4$·7H$_2$O), urea and sodium sulphide (Na$_2$S·9H$_2$O) as starting reactants, and deionized water and glycol as the reactive medium. The phase and the morphologyof the as-obtained product were characterized by means of powder X-ray diffraction, energy dispersive spectrometry and scanning electron microscopy. The result displays that the Co9S8 nanotubes have hexagonal crosssections,the diameter of the nanotubes is about 200 nm and the wall thickness is of 50 nm. The experiments showed that the Co$_9$S$_8$ nanotubes could be used as new-type catalysts for the reduction of 4-nitrophenol. It was found thatthe as-obtained Co$_9$S$_8$ nanotubes contributed to the best catalytic activity.

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

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

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

  6. The Origin of the Catalytic Activity of a Metal Hydride in CO2 Reduction.

    Science.gov (United States)

    Kato, Shunsuke; Matam, Santhosh Kumar; Kerger, Philipp; Bernard, Laetitia; Battaglia, Corsin; Vogel, Dirk; Rohwerder, Michael; Züttel, Andreas

    2016-05-10

    Atomic hydrogen on the surface of a metal with high hydrogen solubility is of particular interest for the hydrogenation of carbon dioxide. In a mixture of hydrogen and carbon dioxide, methane was markedly formed on the metal hydride ZrCoHx in the course of the hydrogen desorption and not on the pristine intermetallic. The surface analysis was performed by means of time-of-flight secondary ion mass spectroscopy and near-ambient pressure X-ray photoelectron spectroscopy, for the in situ analysis. The aim was to elucidate the origin of the catalytic activity of the metal hydride. Since at the initial stage the dissociation of impinging hydrogen molecules is hindered by a high activation barrier of the oxidised surface, the atomic hydrogen flux from the metal hydride is crucial for the reduction of carbon dioxide and surface oxides at interfacial sites.

  7. A study on the indirect urea dosing method in the Selective Catalytic Reduction system

    Science.gov (United States)

    Brzeżański, M.; Sala, R.

    2016-09-01

    This article presents the results of studies on concept solution of dosing urea in a gas phase in a selective catalytic reduction system. The idea of the concept was to heat-up and evaporate the water urea solution before introducing it into the exhaust gas stream. The aim was to enhance the processes of urea converting into ammonia, what is the target reductant for nitrogen oxides treatment. The study was conducted on a medium-duty Euro 5 diesel engine with exhaust line consisting of DOC catalyst, DPF filter and an SCR system with a changeable setup allowing to dose the urea in liquid phase (regular solution) and to dose it in a gas phase (concept solution). The main criteria was to assess the effect of physical state of urea dosed on the NOx conversion ratio in the SCR catalyst. In order to compare both urea dosing methods a special test procedure was developed which consisted of six test steps covering a wide temperature range of exhaust gas generated at steady state engine operation condition. Tests were conducted for different urea dosing quantities defined by the a equivalence ratio. Based on the obtained results, a remarkable improvement in NOx reduction was found for gas urea application in comparison to the standard liquid urea dosing. Measured results indicate a high potential to increase an efficiency of the SCR catalyst by using a gas phase urea and provide the basis for further scientific research on this type of concept.

  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. Nitrogen oxides from waste incineration: control by selective non-catalytic reduction.

    Science.gov (United States)

    Zandaryaa, S; Gavasci, R; Lombardi, F; Fiore, A

    2001-01-01

    An experimental study of the selective non-catalytic reduction (SNCR) process was carried out to determine the efficiency of NOx removal and NH3 mass balance, the NOx reducing reagent used. Experimental tests were conducted on a full-scale SNCR system installed in a hospital waste incineration plant. Anhydrous NH3 was injected at the boiler entrance for NOx removal. Ammonia was analyzed after each flue-gas treatment unit in order to establish its mass balance and NH3 slip in the stack gas was monitored as well. The effective fraction of NH3 for the thermal NOx reduction was calculated from measured values of injected and residual NH3. Results show that a NOx reduction efficiency in the range of 46.7-76.7% is possible at a NH3/NO molar ratio of 0.9-1.5. The fraction of NH3 used in NOx removal was found to decrease with rising NH3/NO molar ratio. The NH3 slip in the stack gas was very low, below permitted limits, even at the higher NH3 dosages used. No direct correlation was found between the NH3/NO molar ratio and the NH3 slip in the stack gas since the major part of the residual NH3 was converted into ammonium salts in the dry scrubbing reactor and subsequently collected in the fabric filter. Moreover, another fraction of NH3 was dissolved in the scrubbing liquor.

  10. Sub-micron Cu/SSZ-13: Synthesis and application as selective catalytic reduction (SCR) catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Prodinger, Sebastian; Derewinski, Miroslaw A.; Wang, Yilin; Washton, Nancy M.; Walter, Eric D.; Szanyi, János; Gao, Feng; Wang, Yong; Peden, Charles H. F.

    2017-02-01

    For the first time, sub-micron Cu/SSZ-13, obtained by modifying an existing synthesis procedure, was shown to be an effective and stable catalyst for selective catalytic reduction reactions, such as NO reduction. Characterization of the materials with X-ray diffraction, N2-physisorption and 27Al MAS NMR shows that hydrothermal aging, simulating SCR reaction conditions, is more destructive in respect to dealumination for smaller particles prior to Cu-exchange. However, the catalytic performance and hydrothermal stability for Cu/SSZ-13 is independent of the particle size. In particular, the stability of tetrahedral framework Al is improved in the sub-micron Cu/SSZ-13 catalysts of comparable Cu loading. This indicates that variations in the Al distribution for different SSZ-13 synthesis procedures have a more critical influence on stabilizing isolated Cu-ions during harsh hydrothermal aging than the particle size. This study is of high interest for applications in vehicular DeNOx technologies where high loadings of active species on wash coats can be achieved by using sub-micron Cu/SSZ-13. The authors would like to thank B. W. Arey and J. J. Ditto for performing electron microscope imaging. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. S. P and M. A. D also acknowledge support by the Materials Synthesis and Simulation Across Scales (MS3 Initiative) conducted under the Laboratory Directed Research & Development Program at PNNL. 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.

  11. 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

  12. Dynamic control of chirality in phosphine ligands for enantioselective catalysis

    NARCIS (Netherlands)

    Zhao, Depeng; Neubauer, Thomas M; Feringa, Ben L

    2015-01-01

    Chirality plays a fundamental role in biology and chemistry and the precise control of chirality in a catalytic conversion is a key to modern synthesis most prominently seen in the production of pharmaceuticals. In enantioselective metal-based catalysis, access to each product enantiomer is commonly

  13. Catalytic Asymmetric Synthesis of Phosphine Boronates

    NARCIS (Netherlands)

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

    2015-01-01

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

  14. Catalytic activity of various pepsin reduced Au nanostructures towards reduction of nitroarenes and resazurin

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Bhagwati; Mandani, Sonam; Sarma, Tridib K., E-mail: tridib@iiti.ac.in [Indian Institute of Technology Indore, Discipline of Chemistry, School of Basic Sciences (India)

    2015-01-15

    Pepsin, a digestive protease enzyme, could function as a reducing as well as stabilizing agent for the synthesis of Au nanostructures of various size and shape under different reaction conditions. The simple tuning of the pH of the reaction medium led to the formation of spherical Au nanoparticles, anisotropic Au nanostructures such as triangles, hexagons, etc., as well as ultra small fluorescent Au nanoclusters. The activity of the enzyme was significantly inhibited after its participation in the formation of Au nanoparticles due to conformational changes in the native structure of the enzyme which was studied by fluorescence, circular dichroism (CD), and infra red spectroscopy. However, the Au nanoparticle-enzyme composites served as excellent catalyst for the reduction of p-nitrophenol and resazurin, with the catalytic activity varying with size and shape of the nanoparticles. The presence of pepsin as the surface stabilizer played a crucial role in the activity of the Au nanoparticles as reduction catalysts, as the approach of the reacting molecules to the nanoparticle surface was actively controlled by the stabilizing enzyme.

  15. Selective Catalytic Reduction over Cu/SSZ-13: Linking Homo- and Heterogeneous Catalysis.

    Science.gov (United States)

    Gao, Feng; Mei, Donghai; Wang, Yilin; Szanyi, János; Peden, Charles H F

    2017-03-21

    Active centers in Cu/SSZ-13 selective catalytic reduction (SCR) catalysts have been recently identified as isolated Cu(2+) and [Cu(II)(OH)](+) ions. A redox reaction mechanism has also been established, where Cu ions cycle between Cu(I) and Cu(II) oxidation states during SCR reaction. While the mechanism for the reduction half-cycle (Cu(II) → Cu(I)) is reasonably well-understood, that for the oxidation half-cycle (Cu(I) → Cu(II)) remains an unsettled debate. Herein we report detailed reaction kinetics on low-temperature standard NH3-SCR, supplemented by DFT calculations, as strong evidence that the low-temperature oxidation half-cycle occurs with the participation of two isolated Cu(I) ions via formation of a transient [Cu(I)(NH3)2](+)-O2-[Cu(I)(NH3)2](+) intermediate. The feasibility of this reaction mechanism is confirmed from DFT calculations, and the simulated energy barrier and rate constants are consistent with experimental findings. Significantly, the low-temperature standard SCR mechanism proposed here provides full consistency with low-temperature SCR kinetics.

  16. 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

    of the activation of NO by O2 with the fast SCR reaction, enabled by the release of NO2. According to the scheme, the SCR reaction can be divided in an oxidation of the catalyst by NO + O2 and a reduction by NO + NH3; these steps together constitute a complete catalytic cycle. Furthermore both NO and NH3...... are required in the reduction, and, nally, oxidation by NO + O2 or NO2 leads to the same state of the catalyst. These points are shown experimentally for a Cu-CHA catalyst, by combining in situ X-ray absorption spectrosocpy (XAS), electron paramagnetic resonance (EPR), and Fourier transform infrared...... 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....

  17. 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.

  18. Heterogeneous Au-Pt nanostructures with enhanced catalytic activity toward oxygen reduction.

    Science.gov (United States)

    Ye, Feng; Liu, Hui; Hu, Weiwei; Zhong, Junyu; Chen, Yingying; Cao, Hongbin; Yang, Jun

    2012-03-14

    Heterogeneous Au-Pt nanostructures have been synthesized using a sacrificial template-based approach. Typically, monodispersed Au nanoparticles are prepared first, followed by Ag coating to form core-shell Au-Ag nanoparticles. Next, the galvanic replacement reaction between Ag shells and an aqueous H(2)PtCl(6) solution, whose chemical reaction can be described as 4Ag + PtCl(6)(2-)→ Pt + 4AgCl + 2Cl(-), is carried out at room temperature. Pure Ag shell is transformed into a shell made of Ag/Pt alloy by galvanic replacement. The AgCl formed simultaneously roughens the surface of alloy Ag-Pt shells, which can be manipulated to create a porous Pt surface for oxygen reduction reaction. Finally, Ag and AgCl are removed from core-shell Au-Ag/Pt nanoparticles using bis(p-sulfonatophenyl)phenylphosphane dihydrate dipotassium salt to produce heterogeneous Au-Pt nanostructures. The heterogeneous Au-Pt nanostructures have displayed superior catalytic activity towards oxygen reduction in direct methanol fuel cells because of the electronic coupling effect between the inner-placed Au core and the Pt shell.

  19. 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)

  20. 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...

  1. One-step selective synthesis of branched 1-O-alkyl-glycerol/diglycerol monoethers by catalytic reductive alkylation of ketones

    Institute of Scientific and Technical Information of China (English)

    DAYOUB; Wissam; LEMAIRE; Marc

    2010-01-01

    Branched 1-O-alkyl glycerol and diglycerol monoethers were obtained in good yields and high selectivity by a straightforward catalytic reductive alkylation of glycerol with relevant ketones in the presence of 0.5 mol% of Pd/C under 10 bar of hydrogen pressure using a Brφnsted acid as the co-catalyst.

  2. MERCURY OXIDATION PROMOTED BY A SELECTIVE CATALYTIC REDUCTION CATALYST UNDER SIMULATED POWDER RIVER BASIN COAL COMBUSTION CONDITIONS

    Science.gov (United States)

    A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury oxidation under SCR conditions. A low sulfur Power River Basin (PRB) coal combustion ...

  3. Selective catalytic reduction of NOx by hydrocarbons over Fe/ZSM5 prepared by sublimation of FeCl3

    NARCIS (Netherlands)

    Battiston, A.A.

    2003-01-01

    Selective Catalytic Reduction of NOx by Hydrocarbons over Fe/ZSM5 Prepared by Sublimation of FeCl3. Characterization and Catalysis Nitrogen oxides (NOx) are unwanted by-products of combustion. They are generated primarily from motor vehicles and stationary sources, like power stations and indust

  4. Promotional Effect of Ce on Iron-Based Catalysts for Selective Catalytic Reduction of NO with NH3

    OpenAIRE

    Xiaobo Wang; Lei Zhang; Shiguo Wu; Weixin Zou; Shuohan Yu; Ye Shao; Lin Dong

    2016-01-01

    A series of Fe–Ce–Ti catalysts were prepared via co-precipitation method to investigate the effect of doping Ce into Fe–Ti catalysts for selective catalytic reduction of NO with NH3. The NO conversion over Fe–Ce–Ti catalysts was considerably improved after Ce doping compared to that of Fe–Ti catalysts. The Fe(0.2)–Ce(0.4)–Ti catalysts exhibited superior catalytic activity to that of Fe(0.2)–Ti catalysts. The obtained catalysts were characterized by N2 adsorption (BET), X-ray diffraction (XRD)...

  5. Photo-catalytic reduction of oxygenated graphene dispersions for supercapacitor applications

    Science.gov (United States)

    Soni, Mahesh; Kumar, Pawan; Kumar, Rudra; Sharma, Satinder Kumar; Soni, Ajay

    2017-03-01

    Reduced graphene oxide (rGO) obtained from aqueous graphene oxide (GO) tends to agglomerate with time and hinders the commercial scale applications for high-density energy storage. Here, we report a photo-catalytic reduction of GO dispersions in N-Methyl-2-Pyrrolidone (NMP) under deep UV light (λ ~ 253 nm) for 60 min. The obtained hydrophobic rGO dispersions are electrochemically stable for more than 160 d and exhibit a high Brunauer–Emmet–Teller (BET) surface area of ~260 m2 g‑1. The NMP being a dipolar aprotic solvent serves as an electron donor and its high dipole moment enhances the electrochemical stability of rGO. Furthermore, the fabricated supercapacitor exhibits a high specific capacitance, charge retention, energy and power density of ~220 F g‑1 (current density of 0.5 A g‑1), up to 1000 charging/discharging cycles, 7.32 Wh kg‑1 and 130 W kg‑1, respectively. The high stability of dispersion and electrochemical performance of synthesized rGO is envisaged for potential applications in high density energy storage and conductive inks for flexible electronics.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-10-01

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

  7. Optimization of internals for Selective Catalytic Reduction (SCR) for NO removal.

    Science.gov (United States)

    Lei, Zhigang; Wen, Cuiping; Chen, Biaohua

    2011-04-15

    This work tried to identify the relationship between the internals of selective catalytic reduction (SCR) system and mixing performance for controlling ammonia (NH(3)) slip. In the SCR flow section, arranging the flow-guided internals can improve the uniformity of velocity distribution but is unfavorable for the uniformity of NH(3) concentration distribution. The ammonia injection grids (AIG) with four kinds of nozzle diameters (i.e., 1.0 mm, 1.5 mm, 2.0 mm, and mixed diameters) were investigated, and it was found that the AIG with mixed nozzle diameters in which A3, A4, B3, and B4 nozzles' diameters are 1.0 mm and other nozzles' diameters are 1.5 mm is the most favorable for the uniformity of NH(3) concentration distribution. In the SCR reactor section, the appropriate space length between two catalyst layers, which serves as gas mixing in order to prevent maldistribution of gas concentrations into the second catalyst layer, under the investigated conditions is about 100, 1000, and 12 mm for honeycomb-like cordierite catalyst, plate-type catalysts with parallel channel arrangement, and with cross channel arrangement, respectively. Therefore, the cross channel arrangement is superior to the parallel channel arrangement in saving the SCR reactor volume.

  8. 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.

  9. 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.

  10. 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.

  11. Characterization of systems active in selective catalytic reduction of NO{sub x}

    Energy Technology Data Exchange (ETDEWEB)

    Biglino, Daniele

    1998-06-01

    This thesis is in the field of gas emission control from automobile and stationary sources. Out of the possible approaches to the elimination of pollutant gases, such as nitrogen oxides (NO{sub x}), one consists in the selective catalytic reduction (SCR) of these NO{sub x} on a suitable heterogeneous catalyst. Ammonia or hydrocarbons are employed as reducing agents. The most important catalysts active in the SCR of NO{sub x} are based on ions of transition metal either supported on several oxides or dispersed in zeolites. The catalysts have been characterized by electron magnetic resonance techniques (EPR, ENDOR, ESEEM) and the interaction of catalysts with nitrogen oxides, with reducing and poisoned agents have been followed with the same techniques. Copper dispersed on alumina and its interaction with both NO and ammonia has been investigated. Also the interaction between both water and ammonia with copper dispersed in zeolite ZSM-5 has been investigated. The diffusion of NO{sub 2} in zeolites has been monitored 4 refs, 5 figs

  12. Impact of selective catalytic reduction on exhaust particle formation over excess ammonia events.

    Science.gov (United States)

    Amanatidis, Stavros; Ntziachristos, Leonidas; Giechaskiel, Barouch; Bergmann, Alexander; Samaras, Zissis

    2014-10-01

    The introduction of selective catalytic reduction (SCR) aftertreatment to meet stringent diesel NOx emission standards around the world increases exhaust ammonia. Further to the direct air quality and health implications of ammonia, this may also lead to particle formation in the exhaust. In this study, an ammonia SCR system was examined with respect to its impact on both solid and total exhaust particle number and size distribution, downstream of a diesel particulate filter (DPF). Fuel post-injection was conducted in some tests to investigate the effect of ammonia during active DPF regeneration. On average, the post-DPF solid >23 nm and total <23 nm particle number emissions were increased by 129% (range 80-193%) and by 67% (range 26-136%), respectively, when 100 ppm ammonia level was induced downstream of the SCR catalyst. This is a typical level during ammonia overdosing, often practiced for efficient NOx control. Ammonia did not have a significant additional effect on the high particle concentrations measured during DPF regeneration. Based on species availability and formation conditions, sulfate, nitrate, and chloride salts with ammonium are possible sources of the new particles formed. Ammonia-induced particle formation corresponds to an environmental problem which is not adequately addressed by current regulations.

  13. Catalytic enantioselective synthesis of vicinal dialkyl arrays

    NARCIS (Netherlands)

    van Zijl, Anthoni W.; Szymanski, Wiktor; Lopez, Ferrnando; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    With a consecutive "asymmetric allylic alkylation (AAA)/cross-metathesis (CM)/conjugate addition (CA)" protocol it is possible to synthesize either stereoisomer of compounds containing a vicinal dialkyl array with excellent stereoselectivity. The versatility of this protocol in natural product synth

  14. DEVELOPMENT OF HIGH ACTIVITY, COAL DERIVED, PROMOTED CATALYTIC SYSTEMS FOR NOx REDUCTION AT LOW TEMPERATURES

    Energy Technology Data Exchange (ETDEWEB)

    Joseph M. Calo

    1998-12-31

    This project is directed at an investigation of catalytic NO{sub x} reduction mechanisms on coal-derived, activated carbon supports at low temperatures. Promoted carbon systems offer some potentially significant advantages for heterogeneous NO{sub x} reduction. These include: low cost; high activity at low temperatures, which minimizes carbon loss; oxygen resistance; and a support material which can be engineered with respect to porosity, transport and catalyst dispersion characteristics. During the reporting period, the following has been accomplished: (1) A MS-TGA (mass spectrometric-thermogravimetric analysis) apparatus, which is one of the primary instruments that will be used in these studies, has been refurbished and modified to meet the requirements of this project. A NO{sub x} chemiluminescence analyzer (ThermoElectron, Model 10) has been added to the instrument to monitor NO{sub x} concentrations in the feed and product streams. Computer control and data acquisition system has been updated and modified to accommodate the requirements of the specific types of experiments planned. The diffusion pumps used to maintain vacuum for the mass spectrometer system have been replaced with turbomolecular pumps (Varian 300 HT). (2) A packed bed reactor/gas flow system has been assembled for performing reactivity studies. This system employs a Kin-Tek gas calibration/mixing system for varying NO and CO concentrations in the feed gas to the packed bed, a NO{sub x} chemiluminescence analyzer (ThermoElectron, Model 10), and a quadrupole mass spectrometer (Dycor). This system is required for steady-state reactivity studies, as well as mechanistic studies on the effects of NO and CO in the gas phase on intermediate oxygen surface complex populations on the carbon substrates. (3) Work has continued on the application of contrast matching, small angle neutron scattering to the characterization and development of char porosity. Contrast matching with perdeuterated toluene has

  15. Isothiourea-catalysed enantioselective pyrrolizine synthesis: synthetic and computational studies.

    Science.gov (United States)

    Stark, Daniel G; Williamson, Patrick; Gayner, Emma R; Musolino, Stefania F; Kerr, Ryan W F; Taylor, James E; Slawin, Alexandra M Z; O'Riordan, Timothy J C; Macgregor, Stuart A; Smith, Andrew D

    2016-10-14

    The catalytic enantioselective synthesis of a range of cis-pyrrolizine carboxylate derivatives with outstanding stereocontrol (14 examples, >95 : 5 dr, >98 : 2 er) through an isothiourea-catalyzed intramolecular Michael addition-lactonisation and ring-opening approach from the corresponding enone acid is reported. An optimised and straightforward three-step synthetic route to the enone acid starting materials from readily available pyrrole-2-carboxaldehydes is delineated, with benzotetramisole (5 mol%) proving the optimal catalyst for the enantioselective process. Ring-opening of the pyrrolizine dihydropyranone products with either MeOH or a range of amines leads to the desired products in excellent yield and enantioselectivity. Computation has been used to probe the factors leading to high stereocontrol, with the formation of the observed cis-steroisomer predicted to be kinetically and thermodynamically favoured.

  16. A study of different supports for the catalytic reduction of nitrates from natural water with a continuous reactor

    OpenAIRE

    Palomares, A.E.; Franch, C.; Corma,A.

    2011-01-01

    The aim of this work is to study the activity for the nitrate catalytic reduction in natural water, using a continuous stirred tank reactor, of Pd/Cu and Pd/Sn catalysts supported on different materials. The studied supports are: -Al2O3 (commercial), active carbon, graphite, hydrotalcite and alumina synthesized in our laboratory with a high surface area. The activity and selectivity of the catalysts supported on these materials have been compared. The best results have been obtain...

  17. Design and Enantioselective Construction of Axially Chiral Naphthyl-Indole Skeletons.

    Science.gov (United States)

    Zhang, Hong-Hao; Wang, Cong-Shuai; Li, Can; Mei, Guang-Jian; Li, Yuxue; Shi, Feng

    2017-01-02

    The first enantioselective construction of a new class of axially chiral naphthyl-indole skeletons has been established by organocatalytic asymmetric coupling reactions of 2-naphthols with 2-indolylmethanols (up to 99 % yield, 97:3 e.r.). This approach not only affords a new type of axially chiral heterobiaryl backbone, but also provides a new catalytic enantioselective strategy for constructing axially chiral biaryl scaffolds by making use of the C3-electrophilicity of 2-indolylmethanols.

  18. 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.

  19. 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)

  20. A new protocol for the in situ generation of aromatic, heteroaromatic, and unsaturated diazo compounds and its application in catalytic and asymmetric epoxidation of carbonyl compounds. Extensive studies to map out scope and limitations, and rationalization of diastereo- and enantioselectivities.

    Science.gov (United States)

    Aggarwal, Varinder K; Alonso, Emma; Bae, Imhyuck; Hynd, George; Lydon, Kevin M; Palmer, Matthew J; Patel, Mamta; Porcelloni, Marina; Richardson, Jeffery; Stenson, Rachel A; Studley, John R; Vasse, Jean-Luc; Winn, Caroline L

    2003-09-10

    A variety of metalated tosylhydrazone salts derived from benzaldehyde have been prepared and were reacted with benzaldehyde in the presence of tetrahydrothiophene (THT) (20 mol %) and Rh(2)(OAc)(4) (1 mol %) to give stilbene oxide. Of the lithium, sodium, and potassium salts tested, the sodium salt was found to give the highest yield and selectivity. This study was extended to a wide variety of aromatic, heteroaromatic, aliphatic, alpha,beta-unsaturated, and acetylenic aldehydes and to ketones. On the whole, high yields of epoxides with moderate to very high diastereoselectivities were observed. A broad range of tosylhydrazone salts derived from aromatic, heteroaromatic, and alpha,beta-unsaturated aldehydes was also examined using the same protocol in reactions with benzaldehyde, and again, good yields and high diastereoselectivities were observed in most cases. Thus, a general process for the in situ generation of diazo compounds from tosylhydrazone sodium salts has been established and applied in sulfur-ylide mediated epoxidation reactions. The chiral, camphor-derived, [2.2.1] bicyclic sulfide 7 was employed (at 5-20 mol % loading) to render the above processes asymmetric with a range of carbonyl compounds and tosylhydrazone sodium salts. Benzaldehyde tosylhydrazone sodium salt gave enantioselectivities of 91 +/- 3% ee and high levels of diastereoselectivity with a range of aldehydes. However, tosylhydrazone salts derived from a range of carbonyl compounds gave more variable selectivities. Although those salts derived from electron-rich or neutral aldehydes gave high enantioselectivities, those derived from electron-deficient or hindered aromatic aldehydes gave somewhat reduced enantioselectivities. Using alpha,beta-unsaturated hydrazones, chiral sulfide 7 gave epoxides with high diastereoselectivities, but only moderate yields were achieved (12-56%) with varying degrees of enantioselectivity. A study of solvent effects showed that, while the impact on

  1. Novel Catalytic Reactor for CO2 Reduction via Sabatier Process Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Precision Combustion, Inc. (PCI) proposes to develop a novel, efficient, and lightweight catalytic Sabatier CO2 methanation unit, capable of converting a mixture of...

  2. Low Temperature Performance of Selective Catalytic Reduction of NO with NH3 under a Concentrated CO2 Atmosphere

    OpenAIRE

    Xiang Gou; Chunfei Wu; Kai Zhang; Guoyou Xu; Meng Si; Yating Wang; Enyu Wang; Liansheng Liu; Jinxiang Wu

    2015-01-01

    Selective catalytic reduction of NOx with NH3 (NH3-SCR) has been widely investigated to reduce NOx emissions from combustion processes, which cause environmental challenges. However, most of the current work on NOx reduction has focused on using feed gas without CO2 or containing small amounts of CO2. In the future, oxy-fuel combustion will play an important role for power generation, and this process generates high concentrations of CO2 in flue gas. Therefore, studies on the SCR process unde...

  3. Isolation of the copper redox steps in the standard selective catalytic reduction on Cu-SSZ-13.

    Science.gov (United States)

    Paolucci, Christopher; Verma, Anuj A; Bates, Shane A; Kispersky, Vincent F; Miller, Jeffrey T; Gounder, Rajamani; Delgass, W Nicholas; Ribeiro, Fabio H; Schneider, William F

    2014-10-27

    Operando X-ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu-exchanged SSZ-13. Catalysts prepared to contain only isolated, exchanged Cu(II) ions evidence both Cu(II) and Cu(I) ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for Cu(II) reduction to Cu(I). DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed Cu(II) reduction. The calculations predict in situ generation of Brønsted sites proximal to Cu(I) upon reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of Cu(I) to Cu(II), which DFT suggests to occur by a NO2 intermediate. Reaction of Cu-bound NO2 with proximal NH4(+) completes the catalytic cycle. N2 is produced in both reduction and oxidation half-cycles.

  4. Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13

    Energy Technology Data Exchange (ETDEWEB)

    Paolucci, Christopher; Verma, Anuj A.; Bates, Shane A.; Kispersky, Vincent F.; Miller, Jeffrey T.; Gounder, Rajmani; Delgass, Nick; Ribeiro, Fabio; Schneider, William F.

    2014-10-27

    Operando X-ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu-exchanged SSZ-13. Catalysts prepared to contain only isolated, exchanged CuII ions evidence both CuII and CuI ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for CuII reduction to CuI. DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed CuII reduction. The calculations predict in situ generation of Brønsted sites proximal to CuI upon reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of CuI to CuII, which DFT suggests to occur by a NO2 intermediate. Reaction of Cu-bound NO2 with proximal NH4 + completes the catalytic cycle. N2 is produced in both reduction and oxidation half-cycles.

  5. Enantioselective Hydrolysis of Amino Acid Esters Promoted by Bis(β-cyclodextrin) Copper Complexes

    Science.gov (United States)

    Xue, Shan-Shan; Zhao, Meng; Ke, Zhuo-Feng; Cheng, Bei-Chen; Su, Hua; Cao, Qian; Cao, Zhen-Kun; Wang, Jun; Ji, Liang-Nian; Mao, Zong-Wan

    2016-02-01

    It is challenging to create artificial catalysts that approach enzymes with regard to catalytic efficiency and selectivity. The enantioselective catalysis ranks the privileged characteristic of enzymatic transformations. Here, we report two pyridine-linked bis(β-cyclodextrin) (bisCD) copper(II) complexes that enantioselectively hydrolyse chiral esters. Hydrolytic kinetic resolution of three pairs of amino acid ester enantiomers (S1–S3) at neutral pH indicated that the “back-to-back” bisCD complex CuL1 favoured higher catalytic efficiency and more pronounced enantioselectivity than the “face-to-face” complex CuL2. The best enantioselectivity was observed for N-Boc-phenylalanine 4-nitrophenyl ester (S2) enantiomers promoted by CuL1, which exhibited an enantiomer selectivity of 15.7. We observed preferential hydrolysis of L-S2 by CuL1, even in racemic S2, through chiral high-performance liquid chromatography (HPLC). We demonstrated that the enantioselective hydrolysis was related to the cooperative roles of the intramolecular flanking chiral CD cavities with the coordinated copper ion, according to the results of electrospray ionization mass spectrometry (ESI-MS), inhibition experiments, rotating-frame nuclear Overhauser effect spectroscopy (ROESY), and theoretical calculations. Although the catalytic parameters lag behind the level of enzymatic transformation, this study confirms the cooperative effect of the first and second coordination spheres of artificial catalysts in enantioselectivity and provides hints that may guide future explorations of enzyme mimics.

  6. Enantioselective Hydrolysis of Amino Acid Esters Promoted by Bis(β-cyclodextrin) Copper Complexes.

    Science.gov (United States)

    Xue, Shan-Shan; Zhao, Meng; Ke, Zhuo-Feng; Cheng, Bei-Chen; Su, Hua; Cao, Qian; Cao, Zhen-Kun; Wang, Jun; Ji, Liang-Nian; Mao, Zong-Wan

    2016-02-26

    It is challenging to create artificial catalysts that approach enzymes with regard to catalytic efficiency and selectivity. The enantioselective catalysis ranks the privileged characteristic of enzymatic transformations. Here, we report two pyridine-linked bis(β-cyclodextrin) (bisCD) copper(II) complexes that enantioselectively hydrolyse chiral esters. Hydrolytic kinetic resolution of three pairs of amino acid ester enantiomers (S1-S3) at neutral pH indicated that the "back-to-back" bisCD complex CuL(1) favoured higher catalytic efficiency and more pronounced enantioselectivity than the "face-to-face" complex CuL(2). The best enantioselectivity was observed for N-Boc-phenylalanine 4-nitrophenyl ester (S2) enantiomers promoted by CuL(1), which exhibited an enantiomer selectivity of 15.7. We observed preferential hydrolysis of L-S2 by CuL(1), even in racemic S2, through chiral high-performance liquid chromatography (HPLC). We demonstrated that the enantioselective hydrolysis was related to the cooperative roles of the intramolecular flanking chiral CD cavities with the coordinated copper ion, according to the results of electrospray ionization mass spectrometry (ESI-MS), inhibition experiments, rotating-frame nuclear Overhauser effect spectroscopy (ROESY), and theoretical calculations. Although the catalytic parameters lag behind the level of enzymatic transformation, this study confirms the cooperative effect of the first and second coordination spheres of artificial catalysts in enantioselectivity and provides hints that may guide future explorations of enzyme mimics.

  7. Promotional Effect of Ce on Iron-Based Catalysts for Selective Catalytic Reduction of NO with NH3

    Directory of Open Access Journals (Sweden)

    Xiaobo Wang

    2016-07-01

    Full Text Available A series of Fe–Ce–Ti catalysts were prepared via co-precipitation method to investigate the effect of doping Ce into Fe–Ti catalysts for selective catalytic reduction of NO with NH3. The NO conversion over Fe–Ce–Ti catalysts was considerably improved after Ce doping compared to that of Fe–Ti catalysts. The Fe(0.2–Ce(0.4–Ti catalysts exhibited superior catalytic activity to that of Fe(0.2–Ti catalysts. The obtained catalysts were characterized by N2 adsorption (BET, X-ray diffraction (XRD, temperature programmed reduction (H2-TPR, temperature programmed desorption (NH3-TPD, Fourier transform infrared (FT-IR spectrophotometry, thermogravimetric analysis (TGA, and X-ray photoelectron spectroscopy (XPS. The data showed that the introduction of Ce results in higher surface area and better dispersion of active components on the catalyst surface and enhances the amount of surface acid sites. The interactions between Fe and Ce species were found to improve the redox ability of the catalyst, which promotes catalytic performance at low temperature. The XPS results revealed that Fe3+/Fe2+ and Ce4+/Ce3+ coexisted on the catalyst surface and that Ti was in 4+ oxidation state on catalyst surface. Ce doping increased the atomic ratio of Fe/Ti and Ce/Ti and enhanced the surface adsorbed oxygen species. In addition, Fe(0.2–Ce(0.4–Ti catalyst also showed better tolerance to H2O and SO2 and up to 92% NO conversion at 270 °C with 200 ppm SO2 added over 25 h, which suggests that it is a promising industrial catalyst for mid-low temperature NH3–selective catalytic reduction (SCR reaction.

  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. Conversion of chicken feather waste to N-doped carbon nanotubes for the catalytic reduction of 4-nitrophenol.

    Science.gov (United States)

    Gao, Lei; Li, Ran; Sui, Xuelin; Li, Ren; Chen, Changle; Chen, Qianwang

    2014-09-02

    Poultry feather is renewable, inexpensive and abundantly available. It holds great business potentials if poultry feather can be converted into valuable functional materials. Herein, we describe a strategy for the catalytic conversion of chicken feather waste to Ni3S2-carbon coaxial nanofibers (Ni3S2@C) which can be further converted to nitrogen doped carbon nanotubes (N-CNTs). Both Ni3S2@C and N-CNTs exhibit high catalytic activity and good reusability in the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by NaBH4 with a first-order rate constant (k) of 0.9 × 10(-3) s(-1) and 2.1 × 10(-3) s(-1), respectively. The catalytic activity of N-CNTs is better than that of N-doped graphene and comparable to commonly used noble metal catalysts. The N content in N-CNTs reaches as high as 6.43%, which is responsible for the excellent catalytic performance. This strategy provides an efficient and low-cost method for the comprehensive utilization of chicken feathers. Moreover, this study provides a new direction for the application of N-CNTs.

  10. Robust, Chiral, and Porous BINAP-Based Metal–Organic Frameworks for Highly Enantioselective Cyclization Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Thacker, Nathan C.; Lin, Zekai; McIsaac, Alexandra R.; Lin, Wenbin (UC)

    2016-05-06

    We report here the design of BINAP-based metal–organic frameworks and their postsynthetic metalation with Rh complexes to afford highly active and enantioselective single-site solid catalysts for the asymmetric cyclization reactions of 1,6-enynes. Robust, chiral, and porous Zr-MOFs of UiO topology, BINAP-MOF (I) or BINAP-dMOF (II), were prepared using purely BINAP-derived dicarboxylate linkers or by mixing BINAP-derived linkers with unfunctionalized dicarboxylate linkers, respectively. Upon metalation with Rh(nbd)2BF4 and [Rh(nbd)Cl]2/AgSbF6, the MOF precatalysts I·Rh(BF4) and I·Rh(SbF6) efficiently catalyzed highly enantioselective (up to 99% ee) reductive cyclization and Alder-ene cycloisomerization of 1,6-enynes, respectively. I·Rh catalysts afforded cyclization products at comparable enantiomeric excesses (ee’s) and 4–7 times higher catalytic activity than the homogeneous controls, likely a result of catalytic site isolation in the MOF which prevents bimolecular catalyst deactivation pathways. However, I·Rh is inactive in the more sterically encumbered Pauson–Khand reactions between 1,6-enynes and carbon monoxide. In contrast, with a more open structure, Rh-functionalized BINAP-dMOF, II·Rh, effectively catalyzed Pauson–Khand cyclization reactions between 1,6-enynes and carbon monoxide at 10 times higher activity than the homogeneous control. II·Rh was readily recovered and used three times in Pauson–Khand cyclization reactions without deterioration of yields or ee’s. Our work has expanded the scope of MOF-catalyzed asymmetric reactions and showed that the mixed linker strategy can effectively enlarge the open space around the catalytic active site to accommodate highly sterically demanding polycyclic metallocycle transition states/intermediates in asymmetric intramolecular cyclization reactions.

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

    Institute of Scientific and Technical Information of China (English)

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

    2003-01-01

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

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

    Institute of Scientific and Technical Information of China (English)

    Shicheng XU; Junhua LI; Dong YANG; Jiming HAO

    2009-01-01

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

  13. Low-temperature selective catalytic reduction of NO with propylene in excess oxygen over the Pt/ZSM-5 catalyst.

    Science.gov (United States)

    Zhang, Zhixiang; Chen, Mingxia; Jiang, Zhi; Shangguan, Wenfeng

    2011-10-15

    A 0.5 wt% Pt/ZSM-5 catalyst was used for the low-temperature selective catalytic reduction (SCR) of NO with C(3)H(6) in the presence of excess oxygen. Under an atmosphere of 150 ppm NO, 150 ppm C(3)H(6) and 18 vol% O(2) (GHSV 72,000 h(-1)), Pt/ZSM-5 showed remarkably high catalytic performance giving 77.1% NO reduction to N(2) + N(2)O and 79.7% C(3)H(6) conversion to CO(2) simultaneously at 140 °C. The samples were characterized by means of NO temperature programmed desorption (TPD), NO/C(3)H(6) temperature programmed oxidation (TPO), BET surface area, XRD and TEM. The catalytic activities of C(3)H(6) combustion and NO oxidation are improved by well-dispersed platinum significantly. It is found that the enhanced activity of Pt/ZSM-5 for the low-temperature SCR is associated with its outstanding activities in the TPO processes of NO to NO(2) and C(3)H(6) to CO(2) in low temperature range.

  14. Chitosan based polymer matrix with silver nanoparticles decorated multiwalled carbon nanotubes for catalytic reduction of 4-nitrophenol.

    Science.gov (United States)

    Alshehri, Saad M; Almuqati, Turki; Almuqati, Naif; Al-Farraj, Eida; Alhokbany, Norah; Ahamad, Tansir

    2016-10-20

    A novel catalyst for the reduction of 4-nitrophenol (4-NP) was prepared using carboxyl group-functionalized multiwalled carbon nanotubes (MWCNTs), polymer matrix, and silver nanoparticles (AgNPs). The AgNPs were prepared by the reduction of silver nitrate by trisodium citrate in the MWCNTs-polymer nanocomposite; the size of the synthesized AgNPs was found to be 3nm (average diameter). The synthesized nanocomposites were characterized using several analytical techniques. Ag@MWCNTs-polymer composite in the presence of sodium borohydride (NaBH4) in aqueous solution is an effective catalyst for the reduction of 4-NP. The apparent kinetics of reduction has a pseudo-first-order kinetics, and the rate constant and catalytic activity parameter were found to be respectively 7.88×10(-3)s(-1)and 11.64s(-1)g(-1). The MWCNTs-polymer nanocomposite renders stability to AgNPs against the environment and the reaction medium, which means that the Ag@MWCNTs-polymer composite can be re-used for many catalytic cycles.

  15. Uniform Ni/SiO2@Au magnetic hollow microspheres: rational design and excellent catalytic performance in 4-nitrophenol reduction

    Science.gov (United States)

    Zhang, Shenghuan; Gai, Shili; He, Fei; Dai, Yunlu; Gao, Peng; Li, Lei; Chen, Yujin; Yang, Piaoping

    2014-05-01

    A unique and rational design was presented to fabricate Ni/SiO2@Au magnetic hollow microspheres (MHMs) with interesting structures and well-dispersed metal nanoparticles. Hierarchical nickel silicate hollow microspheres were synthesized using silica colloidal spheres as a chemical template. Then, Ni/SiO2 MHMs with well-dispersed Ni nanoparticles were prepared via an in situ reduction approach. Ni/SiO2@Au MHMs were finally obtained by immobilizing uniform Au nanoparticles onto Ni/SiO2 support through a low-temperature chemical reduction process. It was found that Ni/SiO2@Au MHMs inherit the shape and uniformity of the original silica scaffold, and Ni NPs and Au NPs, which were less than 5 nm in size, were well dispersed on the mesoporous silica shell with narrow size distribution. Both Ni/SiO2 and Ni/SiO2@Au MHMs showed excellent catalytic activity in the 4-nitrophenol reduction reaction. Importantly, introduction of a small amount of Au NPs onto Ni/SiO2 MHMs markedly improved the catalytic activity. In particular, Ni/SiO2@Au MHMs showed high conversion even after re-use for several cycles with magnetic separation. The unique structure, high catalytic performance, and ease of separation make Ni/SiO2@Au MHMs highly promising candidates for diverse applications.A unique and rational design was presented to fabricate Ni/SiO2@Au magnetic hollow microspheres (MHMs) with interesting structures and well-dispersed metal nanoparticles. Hierarchical nickel silicate hollow microspheres were synthesized using silica colloidal spheres as a chemical template. Then, Ni/SiO2 MHMs with well-dispersed Ni nanoparticles were prepared via an in situ reduction approach. Ni/SiO2@Au MHMs were finally obtained by immobilizing uniform Au nanoparticles onto Ni/SiO2 support through a low-temperature chemical reduction process. It was found that Ni/SiO2@Au MHMs inherit the shape and uniformity of the original silica scaffold, and Ni NPs and Au NPs, which were less than 5 nm in size, were well

  16. Aqueous-Phase Catalytic Chemical Reduction of p-Nitrophenol Employing Soluble Gold Nanoparticles with Different Shapes

    Directory of Open Access Journals (Sweden)

    Francyelle Moura de Oliveira

    2016-12-01

    Full Text Available Gold nanoparticles with different shapes were prepared and used as catalysts in the reduction of p-nitrophenol (PNP in the aqueous phase and in the presence of sodium borohydride (NaBH4. Parameters such as the reaction temperature, substrate/NaBH4 molar ratio, and substrate/gold molar ratio were tested and evaluated. In this paper, we compare the catalytic reactivities of gold nanorods (AuNRs and gold nanospheres (AuNSs, both synthesized by the seed-mediated method in the presence of cetyltrimethyl ammonium bromide (CTAB. Physical-chemical parameters such as the apparent rate constant (kapp and activation energy (Ea of the reactions were obtained for both systems. We observed that the catalytic system based on AuNRs is the most active. These colloidal dispersions were investigated and fully characterized by ultraviolet-visible absorption spectroscopy (UV–Vis and transmission electron microscopy (TEM.

  17. Plasma-catalytic Selective Reduction of NO with C2H4 in the Presence of Excess Oxygen

    Institute of Scientific and Technical Information of China (English)

    Qi SUN; Ai Min ZHU; Xue Feng YANG; Jin Hai NIU; Yong XU; Zhi Min SONG; Jing LIU

    2005-01-01

    This paper reports observations of significant synergistic effects between dielectric barrier discharge (DBD) plasmas and Cu-ZSM-5 catalysts for C2H4 selective reduction of NOx at250 ℃ in the presence of excess oxygen by using a one-stage plasma-over-catalyst (POC) reactor.With the reactant gas mixture of 530 ppm NO, 650 ppm C2H4, 5.8% O2 in N2and GHSV = 12000h-1, the pure catalytic, pure plasma-induced (discharges over fused silica pellets) and plasmacatalytic (in the POC reactor) NOx conversion are 39%, 1.5% and 79%, respectively. The in-situ optical emission spectra of the reactive systems imply some short-lived active species formed from plasma-induced and plasma-catalytic processes may be responsible to the observed synergistic effects in this one-stage POC system.

  18. Testing and design of selective catalytic reduction DENOX catalysts on the basis of titanium dioxide for flue gas cleaning plants

    Energy Technology Data Exchange (ETDEWEB)

    Neufert, R.; Zuerbig, J. (Siemens AG, Redwitz (Germany). Unternehmensbereich KWU, Keramik- und Porzellanwerk)

    1990-12-01

    Selective catalytic reduction catalysers based on titanium dioxide enjoy a commanding position in the market. Reasons for this are high catalytic activity with simultaneous high specificity, low SO{sub 2}/SO{sub 3} oxidation rates, chemical resistance against acid, flue gas constituents and mechanical stability. The principle of DENOX catalyser design is precise knowledge and analyses of the limiting conditions under which use in power station shall result. A suitable type of catalyser has to be selected in accordance with the conditions of application. Manufacture has to be supported by a complex system of quality assurance measures and tests, so that the catalyser characteristics specified in the design can be guaranteed. 4 figs.

  19. Low-Temperature Plasma-Catalytic Reduction of Nox by C2H2 in the Presence of Excess Oxygen

    Institute of Scientific and Technical Information of China (English)

    NIU Jinhai; ZHANG Zhihui; LIU Dongping; WANG Qi

    2008-01-01

    Synergistic effects of pulsed DC dielectric barrier discharge (DBD) plasma and In-dium modified HZSM-5 (In/HZSM-5) catalyst for C2H2 selective reduction of Nox at 200℃, in the presence of enriched oxygen by using a one-stage plasma-over-catalyst (POC) reactor, are reported. With a reactant gas mixture of 480 ppm NO, 500 ppm C2H2, 13.0% O2 in N2 and gas hourly space velocity (GHSV) = 10000 h-1, pure catalytic, pure plasma-induced (discharges over fused silica pellets) and plasma-catalytic Nox conversion percentages are 45.0%, 4.0% and 92.2%, respectively. Nox conversion rates and energy costs were also compared for pulsed DC DBD and AC DBD reactors.

  20. Effect of manufacturing methods of AgCl/Al2O3 catalyst on selective catalytic reduction of NOx

    Institute of Scientific and Technical Information of China (English)

    Satoshi Kishida; Dong-Ying Ju; Hirofumi Aritani

    2011-01-01

    The AgCl/Al2O3 catalyst has potential for use in the selective catalytic reduction (SCR) of NOx. A compound hydrocarbon, following oxygenation is used as a type of reducing agent. In this experiment, the AgCl/Al2O3 catalyst was produced by four different methods,and the differences among their reduction catalysis of NOx were compared. Ethanol was used as a type of reducing agent. X-ray diffraction analysis was performed to study the crystalline structure and scanning electron microscope and transmission electron microscope (TEM) were applied to determine the microindentation. The results indicated that, in the range of 350-400℃, there was no significant difference on the NOx reduction rate; however, there was dispersion at high and low temperature ranges. The size of the AgCl particles was about 20-100 nm.

  1. Highly active Ag clusters stabilized on TiO{sub 2} nanocrystals for catalytic reduction of p-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xin [Division of Fuel Cells, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 (China); University of Chinese Academy of Sciences, Beijing, 100049 (China); Zhao, Zhe; Ou, Dingrong; Tu, Baofeng; Cui, Daan [Division of Fuel Cells, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 (China); Wei, Xuming [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Cheng, Mojie, E-mail: mjcheng@dicp.ac.cn [Division of Fuel Cells, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 (China)

    2016-11-01

    Graphical abstract: Ag/TiO{sub 2} nanocomposites have been synthesized through the reduction of silver-dodecylamine complexes by CH{sub 3}CHO in the presence of TiO{sub 2} nanocrystals and have shown excellent catalytic activity for the reduction of 4-NP into 4-AP by NaBH{sub 4}. Display Omitted - Highlights: • Ag/TiO{sub 2} nanocomposites with Ag clusters under 2 nm are synthesized through a silver mirror reaction in toluene. • The silver mirror reaction refers to the reduction of silver-dodecylamine complexes by acetaldehyde in toluene. • The Ag/TiO{sub 2} nanocomposites show a good ability of resistant against poisoning by the product in reduction of 4-NP. • TOFs of Ag/TiO{sub 2} nanocomposites obtained in this work are the highest among Ag based catalysts previously reported. - Abstract: Ag/TiO{sub 2} nanocomposites comprising of Ag clusters on TiO{sub 2} nanocrystal surfaces are of great significance in catalysts and advanced functional materials. Herein a novel method to synthesize Ag/TiO{sub 2} nanocomposites with Ag clusters under 2 nm on TiO{sub 2} nanocrystal surfaces have been developed. The success of this method relies on a silver mirror reaction in toluene, which refers to the reduction of silver-dodecylamine complexes by acetaldehyde in the presence of mono-dispersed TiO{sub 2} nanocrystals. The prepared Ag/TiO{sub 2} nanocomposites have been characterized by FT-IR spectra, UV–vis absorption spectra, X-ray diffraction (XRD) analysis, ultra high resolution scanning electron microscope (Ultra-HRSEM), high resolution transmission electron microscope (HRTEM) and X-ray photoelectron spectra (XPS). Catalytic activity of Ag/TiO{sub 2} nanocomposites is evaluated for the reduction of p-nitrophenol (4-NP) into p-aminophenol (4-AP) by NaBH{sub 4}. Results demonstrate that Ag/TiO{sub 2} nanocomposites have shown an outstanding catalytic activity as well as a good stability in successive reduction of 4-NP. Noticeably, TOF of Ag/TiO{sub 2

  2. Anodic aluminium oxide catalytic membranes for asymmetric epoxidation.

    Science.gov (United States)

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

    2005-11-14

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

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

    Directory of Open Access Journals (Sweden)

    Burkhard König

    2003-05-01

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

  4. Green synthesis of Au-rGO nanocomposite and its catalytic activity in nitro-reduction and degradation of dyes

    Science.gov (United States)

    Saikia, Indranirekha; Hazarika, Moushumi; Tamuly, Chandan

    2016-10-01

    An eco-friendly, very simple method for synthesis of gold-reduced graphene oxide nanocomposite was developed using leaf extract of Piper pedicellatum C.DC. Its characterization was done by UV-visible, FT-IR, XRD, XPS, Raman, TGA, EDX, TEM analysis. The nanocomposite was very efficiently utilized as catalyst for reduction reaction of 3-nitroaniline and 4-nitrophenol. The kinetic and rate constant of nitro-reduction also reported in this study. The nanocomposite showed excellent catalytic activity for reduction of nitro aromatic compound within very short period of time. The dye which are used in industries such as rhodamine B, methyl red, methyl orange, methylene blue and bromocresol green were degraded rapidly and efficiently in a photocatalytic pathway by the as-synthesized Au-rGO nanocomposite with only 6% activity loss in degradation after the 10th cycle. So, Au-rGO composite has significant catalytic activity in nitroreduction and photocatalytic degradation of dye molecules under sunlight.

  5. Highly active Ag clusters stabilized on TiO2 nanocrystals for catalytic reduction of p-nitrophenol

    Science.gov (United States)

    Wang, Xin; Zhao, Zhe; Ou, Dingrong; Tu, Baofeng; Cui, Daan; Wei, Xuming; Cheng, Mojie

    2016-11-01

    Ag/TiO2 nanocomposites comprising of Ag clusters on TiO2 nanocrystal surfaces are of great significance in catalysts and advanced functional materials. Herein a novel method to synthesize Ag/TiO2 nanocomposites with Ag clusters under 2 nm on TiO2 nanocrystal surfaces have been developed. The success of this method relies on a silver mirror reaction in toluene, which refers to the reduction of silver-dodecylamine complexes by acetaldehyde in the presence of mono-dispersed TiO2 nanocrystals. The prepared Ag/TiO2 nanocomposites have been characterized by FT-IR spectra, UV-vis absorption spectra, X-ray diffraction (XRD) analysis, ultra high resolution scanning electron microscope (Ultra-HRSEM), high resolution transmission electron microscope (HRTEM) and X-ray photoelectron spectra (XPS). Catalytic activity of Ag/TiO2 nanocomposites is evaluated for the reduction of p-nitrophenol (4-NP) into p-aminophenol (4-AP) by NaBH4. Results demonstrate that Ag/TiO2 nanocomposites have shown an outstanding catalytic activity as well as a good stability in successive reduction of 4-NP. Noticeably, TOF of Ag/TiO2-0.75 nanocomposites obtained in this work is the highest among Ag based catalysts previously reported.

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

    Energy Technology Data Exchange (ETDEWEB)

    Sun, MIn; Perry, Kevin L.

    2015-11-20

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

  7. 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.

  8. Substitution of Val72 residue alters the enantioselectivity and activity of Penicillium expansum lipase.

    Science.gov (United States)

    Tang, Lianghua; Su, Min; Zhu, Ling; Chi, Liying; Zhang, Junling; Zhou, Qiong

    2013-01-01

    Error-prone PCR was used to create more active or enantioselective variants of Penicillium expansum lipase (PEL). A variant with a valine to glycine substitution at residue 72 in the lid structure exhibited higher activity and enantioselectivity than those of wild-type PEL. Site-directed saturation mutagenesis was used to explore the sequence-function relationship and the substitution of Val72 of P. expansum lipase changed both catalytic activity and enantioselectivity greatly. The variant V72A, displayed a highest enantioselectivity enhanced to about twofold for the resolution of (R, S)-naproxen (E value increased from 104 to 200.7 for wild-type PEL and V72A variant, respectively). In comparison to PEL, the variant V72A showed a remarkable increase in specific activity towards p-nitrophenyl palmitate (11- and 4-fold increase at 25 and 35 °C, respectively) whereas it had a decreased thermostability. The results suggest that the enantioselective variant V72A could be used for the production of pharmaceutical drugs such as enantiomerically pure (S)-naproxen and the residue Val 72 of P. expansum lipase plays a significant role in the enantioselectivity and activity of this enantioselective lipase.

  9. Organocatalytic Enantioselective Henry Reactions

    Directory of Open Access Journals (Sweden)

    Raquel P. Herrera

    2011-05-01

    Full Text Available A large number of interesting organocatalytic enantioselective protocols have been explored and successfully applied in the last decade. Among them, the Henry (nitroaldol reaction represents a powerful carbon-carbon bond-forming procedure for the preparation of valuable synthetic intermediates, such as enantioenriched nitro alcohols, which can be further transformed in a number of important nitrogen and oxygen-containing compounds. This area of research is still in expansion and a more complex version of this useful process has recently emerged, the domino Michael/Henry protocol, affording highly functionalized cycles with multiple stereogenic centers.

  10. MOF-74 as an Efficient Catalyst for the Low-Temperature Selective Catalytic Reduction of NOx with NH3.

    Science.gov (United States)

    Jiang, Haoxi; Wang, Qianyun; Wang, Huiqin; Chen, Yifei; Zhang, Minhua

    2016-10-12

    In this work, Mn-MOF-74 with hollow spherical structure and Co-MOF-74 with petal-like shape have been prepared successfully via the hydrothermal method. The catalysts were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetry-mass spectrum analysis (TG-MS), N2 adsorption/desorption, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). It is found that MOF-74(Mn, Co) exhibits the capability for selective catalytic reduction (SCR) of NOx at low temperatures. Both experimental (temperature-programmed desorption, TPD) and computational methods have shown that Co-MOF-74 and Mn-MOF-74 owned high adsorption and activation abilities for NO and NH3. The catalytic activities of Mn-MOF-74 and Co-MOF-74 for low-temperature denitrification (deNOx) in the presence of NH3 were 99% at 220 °C and 70% at 210 °C, respectively. It is found that the coordinatively unsaturated metal sites (CUSs) in M-MOF-74 (M = Mn and Co) played important roles in SCR reaction. M-MOF-74 (M = Mn and Co), especially Mn-MOF-74, showed excellent catalytic performance for low-temperature SCR. In addition, in the reaction process, NO conversion on Mn-MOF-74 decreased with the introduction of H2O and SO2 and almost recovered when gas was cut off. However, for Co-MOF-74, SO2 almost has no effect on the catalytic activity. This work showed that MOF-74 could be used prospectively as deNOx catalyst.

  11. Bisguanidinium dinuclear oxodiperoxomolybdosulfate ion pair-catalyzed enantioselective sulfoxidation

    OpenAIRE

    Zong, Lili; Wang, Chao; Moeljadi, Adhitya Mangala Putra; Ye, Xinyi; Ganguly, Rakesh; Li, Yongxin; Hirao, Hajime; Tan, Choon-Hong

    2016-01-01

    Catalytic use of peroxomolybdate for asymmetric transformations has attracted increasing attention due to its catalytic properties and application in catalysis. Herein, we report chiral bisguanidinium dinuclear oxodiperoxomolybdosulfate [BG]2+[(μ-SO4)Mo2O2(μ-O2)2(O2)2]2− ion pair, as a catalyst for enantioselective sulfoxidation using aqueous H2O2 as the terminal oxidant. The ion pair catalyst is isolatable, stable and useful for the oxidation of a range of dialkyl sulfides. The practical uti...

  12. 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

    2014-11-01

    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.

  13. Operation and uphold of area of liquid ammonia in Selective Catalytic Reduction%SCR氨区的运行维护

    Institute of Scientific and Technical Information of China (English)

    陈建明

    2014-01-01

    液氨是选择性催化还原脱硝法( SCR)工艺首选的脱硝反应剂,它属于危险化学品。氨区的安全运行是SCR系统安全运行的基础保障。从氨区的运行、维护、人员防护和事故处理等方面阐述了SCR系统运行维护中需要注意的一些关键点。%Liquid ammonia is the first choice of reductant in selective catalytic reduction,it is a sort of dangerous chemical. The safe operation in the area of liquid ammonia is foundation of SCR. lt describes take notice of SCR from the operation,uphold,physical protection and accident handling in the area of liquid ammonia.

  14. CoMn2O4 hierarchical microspheres with high catalytic activity towards p-nitrophenol reduction.

    Science.gov (United States)

    Shi, Xiaohui; Zheng, Fangcai; Yan, Nan; Chen, Qianwang

    2014-10-07

    The CoMn2O4 hierarchical microspheres assembled by nanosheets through thermal decomposition of the precursor at different temperatures were first used as catalysts in the reduction of p-nitrophenol to p-aminophenol. The sample prepared at 500 °C shows the highest catalytic activity (kapp 14.95 × 10(-3) s(-1)), which is even higher than some results reported for noble metal particles (Au, Ag and Pd). It is suggested that the presence of metal oxide with 'd(7)' (Co element) and 'd(5)' (Mn element) electronic configurations and the special morphology of CoMn2O4 hierarchical microspheres are beneficial to the reduction of p-nitrophenol to p-aminophenol.

  15. [Experimental studies on low-temperature selective catalytic reduction of NO on magnetic iron-based catalysts].

    Science.gov (United States)

    Yao, Gui-huan; Zhang, Qi; Qin, Ye; Wang, Fang; Lu, Fang; Gui, Ke-ting

    2009-10-15

    Low-temperature selective catalytic reduction (SCR) of NO is a new technique needing urgent development in flue gas cleaning. Elementary studies were done about selective catalytic reduction of NO from flue gas on magnetic iron oxides with ammonia at low and medium temperatures in a fluidized bed, such as Fe3O4 and gamma-Fe2O3. Magnetic field effects for NO removal on gamma-Fe2O3 were also researched with low assisted magnetic fileds. X-ray diffraction spectroscopy was used to identify and characterize the iron oxides catalysts. Results show that gamma-Fe2O3 is active in SCR at low temperatures, and Fe3O4 is apparently less active in SCR than gamma-Fe2O3, but Fe2O3 is also active in ammonia oxidation by O2 above 25 degrees C. Therefore, the optimal catalytic temperature zone in SCR on gamma-Fe2O3 includes 250 degrees C and adjacent temperature zone below it. Furthermore, a better NO conversion, which is 90%, is obtained at 250 degrees C on the gamma-Fe2O3 particle catalyst. In addition, chemisorption of NO on gamma-Fe2O3 is accelerated by assisted magnetic fields at 150-290 degrees C, thus the NO conversion is improved and higher NO removal efficiency of 95% is obtained at 250 degrees C. But the efficiency of NO removal decreases above 290 degrees C with the magnetic field. It is concluded that gamma-FeO3 catalyst is fit to be used in low-temperature SCR of NO with ammonia at 200-250 degrees C, which may suppress oxidation of ammonia and take advantage of positive effects by external magnetic fields.

  16. Effect of Pt promotion on Ni/Al2O3 for the selective catalytic reduction of NO with hydrogen

    Science.gov (United States)

    Mihet, Maria; Lazar, Mihaela D.; Borodi, G.; Almasan, V.

    2013-11-01

    Ni/Al2O3 (10 wt.% Ni) and Ni-Pt/Al2O3 (10 wt.% Ni, 0.5 wt.% Pt) were comparatively tested in the hydrogen selective catalytic reduction process (H2-SCR), at reaction temperatures below 350°C. Catalytic activity tests consisted in temperature programmed reactions (TPRea) under plug flow conditions from 50 to 350°C, with a temperature rate of 5°C/min, using a feed stream with a reactant ratio NO:H2 = 1:1.3 and a GHSV of 4500 h-1. Promotion with Pt increases the catalytic performances of the Ni based catalyst, in respect to NO conversion, N2 selectivity and N2 yield. The reaction temperatures for NO conversion above 95% decrease significantly due to Pt addition, from 250°C for Ni/Al2O3 to 125°C for Ni-Pt/Al2O3. Characterization of catalysts was performed by: X ray powder diffraction (XRD) for the estimation of Ni crystallite size, temperature programmed reduction (TPR) for the catalyst reducibility, temperature programmed desorption of hydrogen (H2-TPD) for the investigation of active sites and metal dispersion on the support, N2 adsorption-desorption isotherms at -196°C for the determination of total specific surface area and pore size distribution, and H/D isotopic exchange on the catalyst surface. At the request of the Proceedings Editor, and all authors of the paper, an updated version of this article was published on 14 January 2014. Data presented in Table 1 of the original paper contained errors which have been corrected in the updated and re-published article. The Corrigendum attached to the corrected article PDF file explains the errors in more detail.

  17. Cation exchanged and impregnated Ti-pillared clays for selective catalytic reduction of NO{sub x} by propylene

    Energy Technology Data Exchange (ETDEWEB)

    Valverde, J.L.; De Lucas, A.; Sanchez, P.; Dorado, F.; Romero, A. [Facultad de Quimicas, Departamento de Ingenieria Quimica, Universidad Castilla-La Mancha, 13004 Ciudad Real (Spain)

    2003-06-20

    Ti-pillared interlayer clay (PILC)-based catalysts ion exchanged with Cu, Ni and Fe were prepared and used for the selective catalytic reduction of NO{sub x} using propylene as the reducing agent. The influence of the metal loading in the SCR activity was studied. Likewise, catalytic activity of Cu-ion exchanged samples was compared to that of Cu-ones. In both cases, the catalytic activity increased with increasing metal loading, reaching a maximum of NO{sub x} conversion, and then decreased at higher loading. The maximum of NO{sub x} conversion was achieved in each set of catalysts for the samples NiTi-3.4, FeTi-8.0 and CuTi-7.4. Ti-PILCs-ion exchanged with Cu was the most active catalyst for the SCR of NO{sub x} by propylene. H{sub 2}-TPR results showed that Ni{sup 2+} in Ti-PILC-based catalysts was harder to reduce than Cu{sup 2+} in the same material. It was observed that, as the Cu content is increased, CuO and isolated Cu{sup 2+} species became easier to reduce in ion exchanged samples. Likewise, it was also noted that the relative H{sub 2} consumption decreased with the Cu content, due to a lower accessibility of H{sub 2} to the metal. It can be verified a correlation between NO{sub x} conversion and the H{sub 2} consumption for the Cu{sup 2+} -> Cu{sup +} reduction process, reaching the maximum for the sample CuTi-7.4. Finally, it was observed that the presence of 10% water in the feed inhibited the SCR of NO activity of this catalyst. However, this effect was completely reversible following the removal of water from the gas stream.

  18. 油包水微乳液中抗体酶催化布洛芬酯选择性水解的酶学特性%Enzymological Characteristics of Catalytic Antibody-catalyzed enantioselective Hydrolysis of Ibuprofen Ester in Water-in-oil microemulsion

    Institute of Scientific and Technical Information of China (English)

    杨根生; 戚映丹; 欧志敏; 姚善泾

    2009-01-01

    The asymmetric hydrolyzation of racemic ibuprofen ester is one of the most important methods for chiral separation of ibuprofen. A catalytic antibody that accelerates the rate of enantioselective hydrolysis of ibuprofen methyl ester was successfully elicited against an immunogen consisting of tetrahedral sulfate hapten attached to bovine serum albumin (BSA). The rate constant enhancement factor Kcat/Kuncat was about 1.6x104. The catalytic activity of the catalytic antibody in a reverse micelle reaction system based on sodium b/s (2-ethylhexyl) sodium sulfosuccinate (AOT) in isooctane was studied. Kinetic analysis of the catalytic antibody-catalyzed reaction was found to be possible in this system. Kinetic studies showed that hydrolysis in the microemulsion system follow Michaelis-Menten kinetics. The catalytic antibody can also accelerate catalysis of S-ibuprofen methyl ester in the microemulsion system. Temperature effects, the pH profile, Km,app and Kcat were determined. The dependence of the catalytic antibody hydrolytic activity on the Wo (molar ratio of water to surfactant) showed a bell-shaped curve, presenting a maximum at about wo = 21.%根据过渡态理论设计和合成了能诱导产生催化选择性水解布洛芬甲酯的催化抗体的四面体硫酸盐半抗原,并与牛血清白蛋白(BSA)偶联制备成免疫源,通过免疫手段成功筛选出具有加速选择性水解生成S-布洛芬的特异性催化抗体.其Kcat,app/Kuncat,app达1.6x104.进一步地将催化抗体运用到W/O微乳体系(反胶束)中进行布洛芬酯的选择性水解研究,其动力学研究证明其催化过程同样遵循Michaelis.Menten方程.考察了pH值和温度对催化初速度影响,Wo(体系中水和琥珀酸二辛酯磺酸钠(AOT)的摩尔比)对催化初速度影响呈现为钟罩型,最适的Wo.为21.

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

    Science.gov (United States)

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

    2016-09-19

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

  20. 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.

  1. Enantioselective Vinylogous Organocascade Reactions.

    Science.gov (United States)

    Hepburn, Hamish B; Dell'Amico, Luca; Melchiorre, Paolo

    2016-08-01

    Cascade reactions are powerful tools for rapidly assembling complex molecular architectures from readily available starting materials in a single synthetic operation. Their marriage with asymmetric organocatalysis has led to the development of novel techniques, which are now recognized as reliable strategies for the one-pot enantioselective synthesis of stereochemically dense molecules. In recent years, even more complex synthetic challenges have been addressed by applying the principle of vinylogy to the realm of organocascade catalysis. The key to the success of vinylogous organocascade reactions is the unique ability of the chiral organocatalyst to transfer reactivity to a distal position without losing control on the stereo-determining events. This approach has greatly expanded the synthetic horizons of the field by providing the possibility of forging multiple stereocenters in remote positions from the catalyst's point of action with high selectivity, while simultaneously constructing multiple new bonds. This article critically describes the developments achieved in the field of enantioselective vinylogous organocascade reactions, charting the ideas, the conceptual advances, and the milestone reactions that have been essential for reaching highly practical levels of synthetic efficiency.

  2. Tungsten-catalyzed regio- and enantioselective aminolysis of trans-2,3-epoxy alcohols: an entry to virtually enantiopure amino alcohols.

    Science.gov (United States)

    Wang, Chuan; Yamamoto, Hisashi

    2014-12-08

    The first catalytic enantioselective aminolysis of trans-2,3-epoxy alcohols has been accomplished. This stereospecific ring-opening process was efficiently promoted by a tungsten/bis(hydroxamic acid) catalytic system, furnishing various anti-3-amino-1,2-diols with excellent regiocontrol and high enantioselectivities (up to 95% ee). Moreover, virtually enantiopure 3-amino-1,2-diols could be obtained by the sequential combination of two reactions that both involve the use of a chiral catalyst.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-03-01

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

  4. Impact of Substituents Attached to N-Heterocyclic Carbenes on the Catalytic Activity of Copper Complexes in the Reduction of Carbonyl Compounds with Triethoxysilane

    Institute of Scientific and Technical Information of China (English)

    PENG, Jiajian; CHEN, Lingzhen; XU, Zheng; HU, Yingqian; LI, Jiayun; BAI, Ying; QIU, Huayu; LAI, Guoqiao

    2009-01-01

    By using functionalized imidazolium salts such as 1-allyl-3-alkylimidazolium or 1-alkyi-3-vinylimidazolium salts as carbene ligand precursors, the reduction of aryl ketones with triethoxysilane may be catalyzed by copper salt/imidazolium salt/KO~tBu systems. The functional substituents attached to the N-heterocyclic carbene (NHC) serve to enhance the catalytic activity. Different copper salts also have an effect on the catalytic activity, with copper(Ⅱ) acetate monohydrate being superior to copper(I) chloride.

  5. A Tethered Ru-S Complex with an Axial Chiral Thiolate Ligand for Cooperative Si-H Bond Activation: Application to Enantioselective Imine Reduction.

    Science.gov (United States)

    Wübbolt, Simon; Maji, Modhu Sudan; Irran, Elisabeth; Oestreich, Martin

    2017-02-13

    An axial chiral version of the 2,6-dimesitylphenyl group attached to sulfur is reported. Its multistep preparation starts from (S)-binol, and the thiol group is established by a racemization-free thermal Newman-Kwart rearrangement. The new chiral thiolate ligand decorated with one mesityl group is used in the synthesis of a tethered ruthenium chloride complex. Its spectroscopic characterization revealed solvent-dependent epimerization at the ruthenium center. The major diastereomer is crystallographically characterized. Chloride abstraction with tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF4) yields the corresponding coordinatively unsaturated ruthenium complex with the Ru-S bond exposed. Si-H bond activation at this Ru-S bond proceeds in syn fashion but with moderate facial selectivity (d.r. = 70:30), generating diastereomeric chiral-at-ruthenium hydrosilane adducts. Their application to catalytic imine hydrosilylation led to promising enantioinduction (40% ee), thereby providing proof of concept for asymmetric catalysis involving cooperative Si-H bond activation.

  6. Novel Catalytic Reactor for CO2 Reduction via Sabatier Process Project

    Data.gov (United States)

    National Aeronautics and Space Administration — A novel short contact time Microlith Sabatier reactor system for CO2 reduction offers a significant advance in support of manned spaceflight. Compared to current and...

  7. The Effect of Copper Loading on the Selective Catalytic Reduction of Nitric Oxide by Ammonia Over Cu-SSZ-13

    Energy Technology Data Exchange (ETDEWEB)

    Kwak, Ja Hun; Tran, Diana N.; Szanyi, Janos; Peden, Charles HF; Lee, Jong H.

    2012-03-01

    The effect of Cu loading on the selective catalytic reduction of NOx by NH3 was examined over 20-80% ion-exchanged Cu-SSZ-13 zeolite catalysts. High NO reduction efficiency (80-95%) was obtained over all catalyst samples between 250 and 500°C, and the gas hourly space velocity of 200,000 h-1. Both NO reduction and NH3 oxidation activities under these conditions were found to increase slightly with increasing Cu loading at low temperatures. However, NO reduction activity was suppressed with increasing Cu loadings at high temperatures (>500oC) due to excess NH3 oxidation. The optimum Cu ion exchange level appears to be ~40-60% as higher than 80% NO reduction efficiency was obtained over 50% Cu ion-exchanged SSZ-13 up to 600oC. The NO oxidation activity of Cu-SSZ-13 was found to be low regardless of Cu loading, although it was somewhat improved with increasing Cu ion exchange level at high temperatures. During the “fast” SCR (i.e., NO/NO2 =1), only a slight improvement in NOx reduction activity was obtained for Cu-SSZ-13. Regardless of Cu loading, near 100% selectivity to N2 was observed; only a very small amount of N2O was produced even in the presence of NO2. Based on the Cu loading, the apparent activation energies for NO oxidation and NO SCR were estimated to be ~58 kJ/mol and ~41 kJ/mol, respectively.

  8. Mercury Oxidation over Selective Catalytic Reduction (SCR) Catalysts - Ph.d. thesis Karin Madsen

    DEFF Research Database (Denmark)

    Madsen, Karin

    The vanadium-based SCR catalyst used for NOx-control promotes the oxidation of elemental mercury Hg0 to Hg2+ in flue gases from coal-fired power plants. Hg2+ is water soluble and can effectively be captured in a wet scrubber. This means that the combination of an SCR with a wet FGD can offer....... For T=250-375oC, the DeNOx reaction will inhibit the kinetics of reaction R1 by consuming active Lewis sites that must be oxidized to regain activity for Hg0 oxidation. The experimental data obtained in this study indicate that vanadia Lewis sites on SCR catalysts are active in the catalytic Hg0...... in the experimental investigations is incorporated in the model. The resulting model successfully reproduces the variations in Hg0 oxidation over the SCR that have been experimentally observed for different gas compositions and testing conditions. This verifies that the relevant mercury chemistry has been taken...

  9. Reduction of the Variety of Phenolic Compounds in Bio-oil via the Catalytic Pyrolysis of Pine Sawdust

    Directory of Open Access Journals (Sweden)

    Duo Wang

    2014-05-01

    Full Text Available The objective of this study was to evaluate phenolic compounds produced from the catalytic pyrolysis of pine sawdust by commercial catalysts. Eight types of commercial catalysts consisting of SiO2, montmorillonite, α-Fe2O3, HZSM-5 (Si:Al = 25:1, ZnO, γ-Fe2O3, HZSM-5 (Si:Al = 50:1, and nano-HZSM-5 (Si:Al = 50:1 were screened in a fixed bed reactor at a reaction temperature of 500 °C and a vapor residence time of 3 s. All the tested commercial catalysts exhibited different catalytic performances for the adjustment of the composition of the bio-oil. HZSM-5 (Si:Al = 25:1 significantly increased hydrocarbon production in the bio-oil, which is helpful for improving its heating value. The different types of phenols were reduced significantly from 17 to 7 with nano-HZSM-5 (Si:Al = 50:1; however, the phenols content also decreased from 32.6% to 23.28% compared with non-catalytic pyrolysis. Meanwhile, the addition of nano-HZSM-5 (Si:Al = 50:1 to the raw material provided the highest amount of furans (up to 38.8% among the tested commercial catalysts. The inexpensive ZnO and γ-Fe2O3 also were surprisingly effective for the reduction of the variety of phenolic compounds detected by GC/MS, reducing that number from 17 to 10.

  10. Controllable formation of graphene and graphene oxide sheets using photo-catalytic reduction and oxygen plasma treatment

    Science.gov (United States)

    Ostovari, Fatemeh; Abdi, Yaser; Ghasemi, Foad

    2012-12-01

    Au/SiO2/Si interdigital electrodes with thickness of 1 μm were created on silicon substrate. Graphene oxide (GO) sheets hanging from these electrodes were obtained by spin coating of chemically synthesized GO dispersed in water. We used UV-light-induced photo-catalytic activity of titanium oxide nanoparticles to reduce the GO layer. Effects of the photo-induced chemical reduction on the conductivity of the GO were investigated. Also, low power DC plasma was used for oxidation of the sheets. Oxygen bombardment leads to sheets with low electrical conductivity. Measurements show that graphene and GO sheets with the controlled electrical conductivity were obtained by these processes. Scanning electron and atomic force microscopy were used to study the morphology of the TiO2/GO and graphene structures. X-ray diffraction and Raman scattering analysis were used to verify the structural characteristics of the prepared sheets. Analysis showed a gradual increase in the number of C-O bonds on the surface of the graphene layer as a result of increasing the time of plasma bombardment. Based on the Raman spectroscopy, the photo-catalytic activity of TiO2 nanoparticles resulted in a decrease in the number of C-O bonds.

  11. Oxygen reduction at carbon supported ruthenium-selenium catalysts: Selenium as promoter and stabilizer of catalytic activity

    Science.gov (United States)

    Schulenburg, Hendrik; Hilgendorff, Marcus; Dorbandt, Iris; Radnik, Jörg; Bogdanoff, Peter; Fiechter, Sebastian; Bron, Michael; Tributsch, Helmut

    Carbon supported ruthenium-based catalysts (Ru/C) for the oxygen reduction in acid electrolytes were investigated. A treatment of Ru/C catalysts with selenious acid had a beneficial effect on catalytic activity but no influence on intrinsic kinetic properties, like Tafel slope and hydrogen peroxide generation. Reasons for the increased activity of RuSe x/C catalysts are discussed. Potential step measurements suggest that at potentials around 0.8 V (NHE) a selenium or selenium-oxygen species protects the catalyst from formation of inactive RuO 2-films. This protective effect leads to an enhanced activity of RuSe x/C compared to Ru/C. No evidence was found for a catalytically active stoichiometric selenium compound. The active phase may be described as a ruthenium suboxide RuO x (x RuSe y phase or RuSe yO v (y < 2, v < 2) layer at the particle surface.

  12. 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.

  13. Low temperature selective catalytic reduction of NOx with NH3 over Mn-based catalyst: A review

    Directory of Open Access Journals (Sweden)

    TsungYu Lee

    2016-05-01

    Full Text Available The removals of NOx by catalytic technology at low temperatures (100–300 °C for industrial flue gas treatment have received increasing attention. However, the development of low temperature catalysts for selective catalytic reduction (SCR of NOx with ammonia is still a challenge especially in the presence of SO2. The current status of using Mn-based catalysts for low temperature SCR of NOx with ammonia (NH3-SCR is reviewed. Reaction mechanisms and effects of operating factors on low temperature NH3-SCR are addressed, and the SCR efficiencies of Mn-based metal oxides with and without SO2 poisoning have also been discussed with different supports and co-metals. The key factors for enhancing low temperature NH3-SCR efficiency and SO2 resistance with Mn-based catalysts are identified to be (1 high specific surface area; (2 high surface acidity; (3 oxidation states of manganese; (4 well dispersion of manganese oxide metals; (5 more surface adsorbed oxygen; (6 more absorbed NO3− on the catalyst surface; (7 easier decomposition of ammonium sulfates. Moreover, the regenerative methods such as water washing, acid and/or alkali washing and heat treatment to the poisoned catalysts could help to recover the low temperature SCR efficiency to its initial level.

  14. Highly efficient catalytic reductive degradation of various organic dyes by Au/CeO₂-TiO₂ nano-hybrid

    Indian Academy of Sciences (India)

    PRANJAL SAIKIA; ABU T MIAH; PARTHA P DAS

    2017-01-01

    Highly improved catalytic reductive degradation of different organic dyes, in the presence of excess NaBH₄ over Au/CeO₂-TiO₂ nano-hybrid as the catalyst is reported in this study. CeO₂-TiO₂ nanocomposite was prepared by a facile co-precipitation method using ultra-high dilute aqueous solutions. Small amount of Au (only 1 wt%) was loaded onto the nanocomposite material by deposition-precipitation with urea (DPU) method to fabricate the ternary Au/CeO₂-TiO₂ nano-hybrid. The catalysts were characterized by the representative techniques like XRD, BET surface area, ICP-AES, UV-Vis diffuse reflectance spectroscopy, TEM and XPS. The Au/CeO₂-TiO₂ nano-hybrid along with NaBH₄ exhibited remarkable catalytic activities towards all the probed dyes, namely Methylene Blue, Methyl Orange, Congo Red, Rhodamine B and Malachite Green, with a degradation efficiency of ~100% in a short reaction time. The degradation reaction followed pseudo-first-order kinetics with respect to the concentration of the dye. Different parameters that affect the rate of the reaction are discussed. A plausible mechanism for methylene blue degradation has also been proposed.

  15. 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.

  16. A novel catalyst of silicon cerium complex oxides for selective catalytic reduction of NO by NH_3

    Institute of Scientific and Technical Information of China (English)

    徐海涛; 沈岳松; 邵成华; 林福文; 祝社民; 丘泰

    2010-01-01

    A series of CeO2/SiO2 and SixCe1-xO2 complex oxides supported on an activated Al2TiO5-TiO2-SiO2 complex phase (ATS) ceramics were prepared by step impregnation and co-impregnation methods, and characterized by N2-BET, XRD, SEM and NH3-TPD techniques. The effects of reaction temperature, CeO2/SiO2 loadings and Si/Ce molar ratio on the granular catalysts for NO selective catalytic reduction with ammonia (NH3-SCR) were studied. Results indicated that both CeO2/SiO2/ATS and CeO2/ATS catalysts showed the same ac...

  17. 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.

  18. Selective catalytic reduction of NO over commercial DeNO{sub x} catalysts: Comparison of the measured and calculated performance

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-02-01

    The performance of selective catalytic reduction monolithic catalysts may best be characterized by plotting the ammonia slip as a function of the percentage of NO{sub x} conversion achieved. Experimental results obtained on a Diesel engine test stand have been compared with predicted values obtained by model calculations. In this way the possibilities and limits of such calculations could be shown. The model has no adjustable parameters. An exact prediction of performance is not possible under all conditions due to minor differences in composition between the real exhaust and the test gas mixtures used in the determination of the intrinsic catalyst properties. The value of such a model therefore lies in the prediction of the performance of new catalysts (e.g., layer catalysts) or under changed operating conditions (other temperature or GHSV).

  19. Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3

    Energy Technology Data Exchange (ETDEWEB)

    Kwak, Ja Hun; Tonkyn, Russell G.; Kim, Do Heui; Szanyi, Janos; Peden, Charles HF

    2010-10-21

    Superior activity and selectivity of a Cu ion-exchanged SSZ-13 zeolite in the selective catalytic reduction (SCR) of NOx with NH3 were observed, in comparison to Cu-beta and Cu-ZSM-5 zeolites. Cu-SSZ-13 was not only more active in the NOx SCR reaction over the entire temperature range studied (up to 550 °C), but also more selective toward nitrogen formation, resulting in significantly lower amounts of NOx by-products (i.e., NO2 and N2O) than the other two zeolites. In addition, Cu-SSZ-13 demonstrated the highest activity and N2 formation selectivity in the oxidation of NH3. The results of this study strongly suggest that Cu-SSZ-13 is a promising candidate as a catalyst for NOx SCR with great potential in after-treatment systems for either mobile or stationary sources.

  20. Low-temperature selective catalytic reduction of NO on MnO(x)/TiO(2) prepared by different methods.

    Science.gov (United States)

    Jiang, Boqiong; Liu, Yue; Wu, Zhongbiao

    2009-03-15

    Catalysts based on MnO(x)/TiO(2) were prepared by sol-gel, impregnation, and coprecipitation methods for low-temperature selective catalytic reduction (SCR) of NO with NH(3). Among the catalysts, the sample prepared by sol-gel method had the best performance on both activity and SO(2) resistance. From the results of thermo gravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectrum (XPS), it was known that manganese oxides and titania existed in different phase in the samples prepared by three methods. Strong interaction, large surface area, high concentration of hydroxyl groups, high concentration of amorphous Mn on the surface might be the main reasons for the excellent performance of the catalysts.

  1. Laboratory test reactor for the investigation of liquid reducing agents in the selective catalytic reduction of NOx

    Science.gov (United States)

    Peitz, D.; Bernhard, A.; Elsener, M.; Kröcher, O.

    2011-08-01

    A test reactor was designed and built for investigating liquid reducing agents in the selective catalytic reduction (SCR) process in the laboratory. The design of the experimental setup is described in detail and its performance was evaluated. Using a glass nebulizer, liquid reducing agents were sprayed directly onto a catalyst positioned in a heated glass reactor with a length of 250 mm and an internal diameter of 20.4 mm or 40 mm. Model exhaust gases were mixed from individual gas components and were heated up to 450 °C in a heat exchanger before entering the reactor. The off-gas was analyzed using two complimentary techniques, a multi-component online FTIR gas analysis and a liquid quench gas absorption setup, to detect higher molecular compounds and aerosols. Due to the versatility of construction, processes not related to SCR, but involving three-phase reactions with gases, liquids and a catalyst, can also be investigated.

  2. Low Temperature Performance of Selective Catalytic Reduction of NO with NH3 under a Concentrated CO2 Atmosphere

    Directory of Open Access Journals (Sweden)

    Xiang Gou

    2015-10-01

    Full Text Available Selective catalytic reduction of NOx with NH3 (NH3-SCR has been widely investigated to reduce NOx emissions from combustion processes, which cause environmental challenges. However, most of the current work on NOx reduction has focused on using feed gas without CO2 or containing small amounts of CO2. In the future, oxy-fuel combustion will play an important role for power generation, and this process generates high concentrations of CO2 in flue gas. Therefore, studies on the SCR process under concentrated CO2 atmosphere conditions are important for future SCR deployment in oxy-fuel combustion processes. In this work, Mn- and Ce-based catalysts using activated carbon as support were used to investigate the effect of CO2 on NO conversion. A N2 atmosphere was used for comparison. Different process conditions such as temperature, SO2 concentration, H2O content in the feed gas and space velocity were studied. Under Mn-Ce/AC conditions, the results suggested that Mn metal could reduce the inhibition effect of CO2 on the NO conversion, while Ce metal increased the inhibition effect of CO2. High space velocity also resulted in a reduction of CO2 inhibition on the NO conversion, although the overall performance of SCR was greatly reduced at high space velocity. Future investigations to design novel Mn-based catalysts are suggested to enhance the SCR performance under concentrated CO2 atmosphere conditions.

  3. Species active in the selective catalytic reduction of no with iso-butane on iron-exchanged ZSM-5 zeolites

    Directory of Open Access Journals (Sweden)

    M. S. Batista

    2005-09-01

    Full Text Available Fe-ZSM-5 catalysts were prepared by ion exchange in aqueous medium or in the solid state and tested in the catalytic reduction of NO with iso-butane. X-ray powder diffraction (XRD, atomic absorption spectroscopy (AAS, electron paramagnetic resonance spectroscopy (EPR, X-ray absorption spectroscopy (XANES, EXAFS, temperature-programmed reduction by H2 (H2-TPR and Mössbauer spectroscopy (MÖS-S were used for sample characterisation. Irrespective of the method used in catalyst preparation, EPR, XANES and MÖS-S showed Fe atoms in the oxidation state of 3+. MÖS-S and H2-TPR data on Fe-ZSM-5 prepared by ion exchange in the solid state allowed quantification of a lower hematite (Fe2O3 concentration and a higher proportion of Fe cations than samples prepared in an aqueous medium. In all the catalysts studied these Fe cations were the active sites in the reduction of NO to N2 and in the oxidation of iso-butane. It is further suggested that coordination of Fe species is another important aspect to be considered in their behaviour.

  4. One-Pot Synthesis of Bi/Fe3O4 and Its Catalytic Performances for 4-Nitrophenol Reduction

    Directory of Open Access Journals (Sweden)

    Ke-ying Cai

    2017-04-01

    Full Text Available A novel approach was successfully developed for the catalyst Bi-deposited Fe3O4 magnetic nanoparticles, which was used in the degradation of 4-nitrophenol (4-NP. The Bi/Fe3O4 composite was prepared via a one-pot process from ferrous sulfate and bismuth chloride using hydrazine hydrate as a reducing agent. The catalyst was characterized by X-ray diffraction (XRD and Fourier transform infrared (FTIR spectroscopy. In the composite pure Fe3O4 particles were synthesized and bismuth particles were well dispersed. The catalytic performances were investigated for the reduction of 4-NP with sodium borohydride. The catalyst has higher activity when Bi/Fe molar ratio is 1:4 in the composite and the rate constant k is about 0.611 min-1. The catalyst has good reusability which can be used 10 cycles without obvious deactivation. Furthermore, the catalyst can be easily separated by an external magnetic field. Copyright © 2017 BCREC GROUP. All rights reserved Received: 11st August 2016; Revised: 20th December 2016; Accepted: 21st December 2016 How to Cite: Cai, K.Y., Liu, Y.S., Xu, Y., Zhou, H., Zhang, L., Cui., Y. (2017. One-Pot Synthesis of Bi/Fe3O4 and Its Catalytic Performances for 4-Nitrophenol Reduction. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (1: 89-95 (doi:10.9767/bcrec.12.1.621.89-95 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.1.621.89-95

  5. Cooperative catalysis by palladium and a chiral phosphoric acid: enantioselective amination of racemic allylic alcohols.

    Science.gov (United States)

    Banerjee, Debasis; Junge, Kathrin; Beller, Matthias

    2014-11-24

    Cooperative catalysis by [Pd(dba)2] and the chiral phosphoric acid BA1 in combination with the phosphoramidite ligand L8 enabled the efficient enantioselective amination of racemic allylic alcohols with a variety of functionalized amines. This catalytic protocol is highly regio- and stereoselective (up to e.r. 96:4) and furnishes valuable chiral amines in almost quantitative yield.

  6. 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...

  7. Zeolite catalysts and their use in selective catalytic reduction of NOx

    NARCIS (Netherlands)

    Seijger, G.B.F.; Van den Bleek, C.M.; Calis, H.P.A.

    2003-01-01

    The invention is directed to catalyst compositions comprising a zeolite, as well as to processes for the reduction of nitrogen oxides (NOx) employing these catalyst compositions. The catalyst compositions of the invention comprise a zeolite of the ferrierite type (FER), which zeolite is ion exchange

  8. 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

    are required in the reduction, and, nally, oxidation by NO + O2 or NO2 leads to the same state of the catalyst. These points are shown experimentally for a Cu-CHA catalyst, by combining in situ X-ray absorption spectrosocpy (XAS), electron paramagnetic resonance (EPR), and Fourier transform infrared...

  9. Formation of catalytically active gold-polymer microgel hybrids via a controlled in situ reductive process

    NARCIS (Netherlands)

    Agrawal, Garima; Schuerings, Marco Philipp; van Rijn, Patrick; Pich, Andrij

    2013-01-01

    A newly developed N-vinylcaprolactam/acetoacetoxyethyl methacrylate/acrylic acid based microgel displays in situ reductive reactivity towards HAuCl4, forming hybrid polymer-gold nanostructures at ambient temperature without additional reducing agents. The colloidal gold nanostructure is selectively

  10. Understanding ammonia selective catalytic reduction kinetics over Cu-SSZ-13 from motion of the Cu ions

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Feng; Walter, Eric D.; Kollar, Marton; Wang, Yilin; Szanyi, Janos; Peden, Charles HF

    2014-11-01

    Cu-SSZ-13 catalysts with three Si/Al ratios, at 6, 12 and 35, are synthesized with solution ion exchange. Catalysts are characterized with surface area/pore volume measurements, temperature programmed reduction (TPR), and electron paramagnetic resonance (EPR) spectroscopy. Catalytic properties are examined using NO oxidation, ammonia oxidation, and standard ammonia selective catalytic reduction (NH3-SCR) reactions. By varying Si/Al ratios and Cu loadings, it is possible to synthesize catalysts with one dominant type of isolated Cu2+ ion species. Prior to full dehydration of the zeolite catalyst, hydrated Cu2+ ions are found to be very mobile as judged from EPR. NO oxidation is catalyzed by O-bridged Cu-dimer species that form at relatively high Cu loadings and in the presence of O2. For NH3 oxidation and standard SCR reactions, transient Cu-dimers even form at much lower Cu loadings; and these are proposed to be the active sites for reaction temperatures ≤ 350 °C. These dimer species can be viewed as in equilibrium with monomeric Cu ion complexes. Between ~250 and 350 °C, these moieties become less stable causing SCR reaction rates to decrease. At temperatures above 350 °C and at low Cu loadings, Cu-dimers completely dissociate to regenerate isolated Cu2+ monomers that then locate at ion-exchange sites of the zeolite lattice. At low Cu loadings, these Cu species are the high-temperature active SCR catalytic centers. At high Cu loadings, on the other hand, both Cu-dimers and monomers are highly active in the high temperature kinetic regime, yet Cu-dimers are less selective in SCR. Brönsted acidity is also very important for SCR reactivity in the high-temperature regime. The authors 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 at the Environmental Molecular Sciences Laboratory (EMSL), a national

  11. Importance of interatomic spacing in catalytic reduction of oxygen in phosphoric acid

    Science.gov (United States)

    Jalan, V.; Taylor, E. J.

    1983-01-01

    A correlation between the nearest-neighbor distance and the oxygen reduction activity of various platinum alloys is reported. It is proposed that the distance between nearest-neighbor Pt atoms on the surface of a supported catalyst is not ideal for dual site absorption of O2 or 'HO2' and that the introduction of foreign atoms which reduce the Pt nearest-neighbor spacing would result in higher oxygen reduction activity. This may allow the critical 0-0 bond interatomic distance and hence the optimum Pt-Pt separation for bond rupture to be determined from quantum chemical calculations. A composite analysis shows that the data on supported Pt alloys are consistent with Appleby's (1970) data on bulk metals with respect to specific activity, activation energy, preexponential factor, and percent d-band character.

  12. 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.

  13. 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.

  14. Kinetic Study of Co-β-Zeolite for Selective Catalytic Reduction of NOx with Propane

    Institute of Scientific and Technical Information of China (English)

    毛树红; 王润平; 池永庆; 王艳; 张清华; 丛燕青

    2011-01-01

    The effects of grain size, space velocity, temperature and reactant concentration on the kinetics of NOx reduction with propane over Co-β-zeolite catalyst were investigated. The external mass transfer phenomenon was examined by varying the space velocity. The results show that the transfer can be negligible when the space velocity is greater than 60000 h-1 in low temperature range. However, the transfer exists at high temperatures even when the space velocity reaches a high level.Variation of the catalyst grain size from 0.05 to 0.125 mm does not change the conversion rate of NOx. The concentrations of components, NOx, C3H8 and O2, were also investigated to have a better understanding of mechanism. Based on the experimental data, the selectivity formula was proposed. The results shows that lower temperature is helpful to get higher selectivity as the activation energy of hydrocarbon oxidation, Ea,2, is greater than that of NOx reduction, Ea,1, (Ea,2>Ea,l). High NOx concentration and low C3H8 concentration are beneficial to high selectivity. However in order to maintain high activity simultaneously, the temperature and C3H8 concentration should be high enough to promote NOx reduction. 10%(φ) H2O and 75×i0-6(φ) SO2 were introduced into the reaction system, and Co-β-zeolite shows strong resistance to water and SO2.

  15. Task 2.6 - Catalyst for Utilization of Methane in Selective Catalytic Reduction of NOx: Topical report, July 1, 1995

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-31

    Selective catalytic reduction (SCR) of nitrogen oxides (NO{sub x}) in flue gas or engine exhaust gas with hydrocarbons as the reductant has great potential for less expense, less pollution, and easier operation than SCR with ammonia. Methane is the preferred reducing gas because of its low cost and low toxicity. Stable, low-cost catalysts for SCR with methane are required to demonstrate this technology for controlling NO{sub x} emissions. Several cobalt and nickel catalysts on synthetic clay and uranium oxide supports were investigated for their activities in reducing NO{sub x} with methane in the presence of air. The efficiency of the synthetic clay-supported nickel and cobalt catalysts for nitric oxide (NO) reduction with methane as the reducing gas was poor. The nickel oxide-uranium oxide catalyst, which was chosen for its high stability, was also ineffective. Results from the two-step experiments conducted at two temperatures produced some interesting information on the reactions of methane with the catalysts and the reactivity of the carbonaceous intermediate. The carbonaceous material formed from methane dissociation at 450{degrees}C not only reduces NO to N{sub 2}O at lower temperatures, but also prevents oxidation of NO to NO{sub 2}. Unfortunately, the carbonaceous forms that reduce the NO are not available for reactions at 400{degrees}C in the presence of oxygen. A two-step process employing this chemistry would be difficult because the catalyst would have to be cycled between the two temperatures. Also the desired reduction to nitrogen is not very efficient.

  16. Enhancement of the enantioselectivity of carboxylesterase A by structure-based mutagenesis.

    Science.gov (United States)

    Godinho, Luis F; Reis, Carlos R; Rozeboom, Henriëtte J; Dekker, Frank J; Dijkstra, Bauke W; Poelarends, Gerrit J; Quax, Wim J

    2012-03-31

    Previously studied Bacillus subtilis carboxylesterases (CesA and CesB) have potential for the kinetic resolution of racemic esters of 1,2-O-isopropylideneglycerol (IPG). CesA exhibits high activity but low enantioselectivity towards IPG-butyrate and IPG-caprylate, while the more enantioselective CesB does not process IPG-butyrate and exhibits several-fold lower activity than CesA towards IPG-caprylate. A sequence and structure comparison allowed us to identify active site residues that may cause the difference in (enantio)selectivities of CesA and CesB towards these IPG esters. This structure-based approach led to the identification of two active site residues in CesA (F166 and F182), as promising candidates for mutagenesis in order to enhance its enantioselectivity. Mutagenesis of positions 166 and 182 in CesA yielded novel variants with enhanced enantioselectivity and without significant loss of catalytic activity. For IPG-butyrate, a CesA double mutant F166V/F182C (ER=13) was generated showing a ∼13-fold increased enantioselectivity as compared to wild-type CesA (E=1). For IPG-caprylate, we designed a CesA double mutant F166V/F182Y (ER=9) displaying a ∼5-fold increased enantioselectivity as compared to the wild-type enzyme (ER=2). These findings, combined with the results of molecular docking experiments, demonstrate the importance of residues at positions 166 and 182 for the enantioselectivity of CesA, and may contribute to the development of efficient biocatalysts.

  17. Biologically active Phytophthora mating hormone prepared by catalytic asymmetric total synthesis

    NARCIS (Netherlands)

    Harutyunyan, S.R.; Zhao, Z.; Hartog, den T.; Bouwmeester, K.; Minnaard, A.J.; Feringa, B.L.; Govers, F.

    2008-01-01

    A Phytophthora mating hormone with an array of 1,5-stereogenic centers has been synthesized by using our recently developed methodology of catalytic enantioselective conjugate addition of Grignard reagents. We applied this methodology in a diastereo- and enantioselective iterative route and obtained

  18. Biologically active Phytophthora mating hormone prepared by catalytic asymmetric total synthesis

    NARCIS (Netherlands)

    Harutyunyan, Syuzanna R.; Zhao, Zhijian; den Hartog, Tim; Bouwmeester, Klaas; Minnaard, Adriaan J.; Feringa, Ben L.; Govers, Francine

    2008-01-01

    A Phytophthora mating hormone with an array of 11,5-stereogenic centers has been synthesized by using our recently developed methodology of catalytic enantioselective conjugate addition of Grignard reagents. We applied this methodology in a diastereo-and enantioselective iterative route and obtained

  19. Modification of Cu/ZSM-5 catalyst with CeO2for selective catalytic reduction of NOxwith ammonia

    Institute of Scientific and Technical Information of China (English)

    刘雪松; 吴晓东; 翁端; 石磊

    2016-01-01

    Cu/ZSM-5 and CeO2-modified Cu/ZSM-5 catalysts were prepared by a wetness impregnation method. The addition of CeO2was found to enhance the NOxselective catalytic reduction (SCR) activity of the catalyst atlow temperatures, but the high-temperature activitywas weakened. The catalysts were characterized by X-ray diffraction (XRD), nitrogen physisorption, induc-tively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), H2temperature-programmed reduction (TPR) and NH3temperature-programmed desorption (TPD). The results showedthat more CuO clusters instead of isolated Cu2+specieswere obtained on the modified catalyst. These active CuO clusters, as well as the Cu-Ce synergistic effect, improvedthe redox property of the catalyst and low-temperatures SCR activity via promoting the oxidation of NO to NO2and fast SCR reaction. The loss in high-temperatures activitywas attributedto the enhanced competitive ox-idation of NH3by O2and decreased surface acidity of the catalyst.

  20. Selective catalytic reduction of nitric oxide by methane over cerium and silver ion-exchanged ZSM-5 zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zhijiang; Flytzani-Stephanopoulos, Maria [Department of Chemical Engineering, Tufts University, Medford, MA (United States)

    1997-12-31

    A new catalyst comprising cerium and silver ion-exchanged ZSM-5 zeolite is reported in this paper, for the reduction of nitric oxide by methane in the presence of excess oxygen. The bi-cation exchanged Ce-Ag-ZSM-5 catalyst was very active for this reaction, while either Ce-ZSM-5 or Ag-ZSM-5 alone showed low activity. The presence of oxygen in the feed gas mixture enhanced the activity of the catalyst and the NO conversion to N{sub 2} increased with the CH{sub 4}/NO ratio and Ag loading of the zeolite. The presence of water vapor had a small adverse effect on the catalyst activity. The coexistence of Ce and Ag ions in the zeolite is crucial for achieving high NO conversion to N{sub 2}. A small amount of cerium is adequate to promote the selective catalytic reduction of NO. The two main functions of Ce ions are (1) to provide the Ag ion sites with NO{sub 2} by catalyzing the oxidation of NO to NO{sub 2} and (2) to suppress the direct CH{sub 4} oxidation to CO{sub 2}. The Ag sites are the active centers where the reaction of NO{sub 2} with CH{sub 4} takes place

  1. Fabrication of silver nanoparticles in pH responsive polymer microgel dispersion for catalytic reduction of nitrobenzene in aqueous medium

    Science.gov (United States)

    Farooqi, Zahoor H.; Begum, Robina; Naseem, Khalida; Rubab, Uma; Usman, Muhammad; Khan, Abbas; Ijaz, Aysha

    2016-12-01

    Copolymer microgels based on N-isopropylacrylamide (NIPAM) and methacrylic acid (MAA) have been synthesized by free radical emulsion polymerization using N, N-methylenebisacrylamide (BIS) as a cross-linker. Synthesized microgels were characterized by Fourier transform infrared spectroscopy (FTIR). Then silver nanoparticles were fabricated in the synthesized microgels by in-situ reduction of AgNO3 with NaBH4. The formation of silver nanoparticles was confirmed by UV-Vis spectroscopy. The pH sensitivity of the copolymer microgels was investigated using dynamic light scattering technique (DLS). Hydrodynamic radius of P (NIPAM-MAA) microgels increases with increase in pH of the medium at 25°C. Surface plasmon resonance wavelength (λSPR) of silver nanoparticles increases with increase in hydrodynamic radius due to change in pH of the medium. The catalytic activity for the reduction of nitrobenzene (NB), an environmental pollutant, into aniline was investigated by UV-Vis spectroscopy in excess of NaBH4 using hybrid microgels as catalyst. The value of apparent rate constant ( k app) of the reaction was calculated using pseudo first order kinetic model and it was found to be linearly related to the amount of catalyst. The results were compared with literature data. The system was found to be an effective catalyst for conversion of NB into aniline.

  2. Mn-CeOx/Ti-PILCs for selective catalytic reduction of NO with NH3 at low temperature.

    Science.gov (United States)

    Shen, Boxiong; Ma, Hongqing; Yao, Yan

    2012-01-01

    Titanium-pillared clays (Ti-PILCs) were obtained by different ways from TiCl4, Ti(OC3H7)4 and TiOSO4, respectively. Mn-CeO(x)/)Ti-PILCs were then prepared and their activities of selective catalytic reduction (SCR) of NO with NH3 at low-temperature were evaluated. Mn-CeO(x)/Ti-PILCs were characterized by X-ray diffraction, N2 adsorption, Fourier transform infrared spectroscopy, thermal analysis, temperature-programmed desorption of ammonia and H2-temperature-programmed reduction. It was found that Ti-pillar tend to be helpful for the enlargement of surface area, pore volume, acidity and the enhancement of thermal stability for Mn-CeO(x)/Ti-PILCs. Mn-CeO(x)/Ti-PILCs catalysts were active for the SCR of NO. Among three resultant Mn-CeO(x)/Ti-PILCs, the catalyst from TiOSO4 showed the highest activity with 98% NO conversion at 220 degrees C, it also exhibited good resistance to H2O and SO2 in flue gas. The catalyst from TiCl4 exhibited the lowest activity due to the unsuccessful pillaring process.

  3. Catalytic reduction of methylene blue and Congo red dyes using green synthesized gold nanoparticles capped by salmalia malabarica gum

    Science.gov (United States)

    Ganapuram, Bhagavanth Reddy; Alle, Madhusudhan; Dadigala, Ramakrishna; Dasari, Ayodhya; Maragoni, Venkatesham; Guttena, Veerabhadram

    2015-08-01

    Stable gold nanoparticles (AuNPs) were synthesized using salmalia malabarica gum as both reducing and capping agent. It is a simple and eco-friendly green synthesis. The successful formation of AuNPs was confirmed by UV-visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction and transmission electron microscopy (TEM). The synthesized AuNPs were characterized by a peak at 520-535 nm in the UV-Vis spectrum. The X-ray diffraction studies indicated that the resulting AuNPs were highly crystalline with face-centred cubic geometry. TEM studies showed that the average particle size of the synthesized AuNPs was 12 ± 2 nm. FTIR analysis revealed that -OH groups present in the gum matrix might be responsible for the reduction of Au+3 into AuNPs. The synthesized AuNPs exhibited good catalytic properties in the reduction of methylene blue and Congo red.

  4. Green synthesis of silver nanoparticles using Terminalia cuneata and its catalytic action in reduction of direct yellow-12 dye

    Science.gov (United States)

    Edison, Thomas Nesakumar Jebakumar Immanuel; Lee, Yong Rok; Sethuraman, Mathur Gopalakrishnan

    2016-05-01

    Facile green synthesis of silver nanoparticles (AgNPs) using aqueous bark extract of Terminalia cuneata has been reported in this article. The effects of concentration of the extract, reaction time and pH were studied by UV-Vis spectroscopy. Appearance of yellow color with λmax around ~ 420 nm suggested the formation of AgNPs. The stable AgNPs were further characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), dynamic light scattering (DLS) with zeta potential and high resolution transmission electron microscopy (HR-TEM) with energy dispersive X-ray spectroscopy (EDS) analysis. The synthesized AgNPs were in the size range of 25-50 nm with a distorted spherical shape identified from HR-TEM analysis. The catalytic activity of AgNPs on the reduction of direct yellow-12 using NaBH4 was analyzed using a UV-Vis spectrophotometer. This study showed the efficacy of biogenic AgNPs in catalyzing the reduction of direct yellow-12.

  5. Morphology-controllable synthesis of CuO nanostructures and their catalytic activity for the reduction of 4-nitrophenol

    Science.gov (United States)

    Che, Wei; Ni, Yonghong; Zhang, Yuxing; Ma, Yue

    2015-02-01

    The investigation on the correlation between properties and shapes of nanomaterials always draws increased interest. However, the correlation between properties and shapes of CuO nanostructures was rarely reported in the previous works. The shape-controlled preparation of CuO nanostructures was successfully realized in the present work via a simple oil-bath route in air at 170 °;C for 30 min, employing CuCl2•2H2O and NaOH as the reactants. It was found that CuO nanocrystals with leaf-like, dumbbell-like and flowerlike structures were obtained through introducing various additives. At the same time, the correlation between properties and shapes was investigated. It was found that the catalytic performances of the as-prepared CuO nanostructures for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in NaBH4 aqueous solution were dependent on its morphologies. Experiments showed that the first-order rate constants for CuO nanostructures with various shapes were in turn 35.5‧ 10-3 s-1 (leaf-like nanosheets), 4.77‧ 10-3 s-1 (dumbbell-like architectures), 10.6‧ 10-3 s-1 (flowerlike nanostructures). The present research provides a new catalyst selection for the reduction of 4-NP to 4-AP in excess NaBH4 aqueous solution, which has potential application in industrial production.

  6. Selective catalytic reduction of sulfur dioxide by carbon monoxide over iron oxide supported on activated carbon

    OpenAIRE

    2014-01-01

    The selective reduction of sulfur dioxide with carbon monoxide to elemental sulfur was studied over AC-supported transition-metal oxide catalysts. According to the study, Fe2O3/AC was the most active catalyst among the 4 AC-supported catalysts tested. By using Fe2O3/AC, the best catalyst, when the feed conditions were properly optimized (CO/SO2 molar ratio = 2:1; sulfidation temperature, 400 °C; Fe content, 20 wt%; GHSV = 7000 mL g-1 h-1), 95.43% sulfur dioxide conversion and 86.59% sulfur yi...

  7. Study on Simultaneous Catalytic Reduction of Sulfur Dioxide and Nitric Oxide on Rare Earth Mixed Compounds

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    CeO2/γ-Al2O3, La2O3/γ-Al2O3, CeO2-La2O3/γ-Al2O3 and CeO2-La2O3, which were prepared by impregnating in certain ratio, were used as the catalysts for the reduction of SO2 and NO by CO. Separate and simultaneous removal of SO2 and NO over La2O3/γ-Al2O3, CeO2/γ-Al2O3, CeO2-La2O3/γ-Al2O3 were investigated. The phase characteristics of catalysts were also analyzed by X-ray diffraction. The result shows that the conversions of SO2 and NO are above 98% over CeO2/γ-Al2O3 and CeO2-La2O3/γ-Al2O3. After SO2 is added in the NO-CO-N2 system (NO∶SO2=1∶2~1∶3), the conversions of SO2 and NO are both above 98%. Furthermore, it is found that CeO2-La2O3 with various ratios has different activity for the simultaneous reduction of SO2 and NO.

  8. Formic acid as an alternative reducing agent for the catalytic nitrate reduction in aqueous media.

    Science.gov (United States)

    Choi, Eun-Kyoung; Park, Kuy-Hyun; Lee, Ho-Bin; Cho, Misun; Ahn, Samyoung

    2013-08-01

    Formic acid was used for the nitrate reduction as a reductant in the presence of Pd:Cu/gamma-alumina catalysts. The surface characteristics of the bimetallic catalyst synthesized by wet impregnation were investigated by SEM, TEM-EDS. The metals were not distributed homogeneously on the surface of catalyst, although the total contents of both metals in particles agreed well with the theoretical values. Formic acid decomposition on the catalyst surface, its influence on solution pH and nitrate removal efficacy was investigated. The best removal of nitrate (50 ppm) was obtained under the condition of 0.75 g/L catalyst with Pd:Cu ratio (4:1) and two fold excess of formic acid. Formic acid decay patterns resembled those of nitrate removal, showing a linear relationship between k(f) (formic acid decay) and k (nitrate removal). Negligible amount of ammonia was detected, and no nitrite was detected, possibly due to buffering effect of bicarbonate that is in situ produced by the decomposition of formic acid, and due to the sustained release of H2 gas.

  9. Formic acid as an alternative reducing agent for the catalytic nitrate reduction in aqueous media

    Institute of Scientific and Technical Information of China (English)

    Eun-kyoung Choi; Kuy-hyun Park; Ho-bin Lee; Misun Cho; Samyoung Ahn

    2013-01-01

    Formic acid was used for the nitrate reduction as a reductant in the presence of Pd∶Cu/γ-alumina catalysts.The surfatce characteristics of the bimetallic catalyst synthesized by wet impregnation were investigated by SEM,TEM-EDS.The metals were not distributed homogeneously on the surface of catalyst,although the total contents of both metals in particles agreed well with the theoretical values.Formic acid decomposition on the catalyst surface,its influence on solution pH and nitrate removal efficacy was investigated.The best removal of nitrate (50 ppm) was obtained under the condition of 0.75 g/L catalyst with Pd∶Cu ratio (4∶1) and two fold excess of formic acid.Formic acid decay patterns resembled those of nitrate removal,showing a linear relationship between kf (formic acid decay) and k (nitrate removal).Negligible amount of ammonia was detected,and no nitrite was detected,possibly due to buffering effect of bicarbonate that is in situ produced by the decomposition of formic acid,and due to the sustained release of H2 gas.

  10. Copper nanoparticles supported on permeable monolith with carboxylic acid surface functionality: Stability and catalytic properties under reductive conditions

    Energy Technology Data Exchange (ETDEWEB)

    Poupart, Romain; Le Droumaguet, Benjamin, E-mail: ledroumaguet@icmpe.cnrs.fr; Guerrouache, Mohamed; Carbonnier, Benjamin, E-mail: carbonnier@icmpe.cnrs.fr

    2015-08-01

    This work reported on the immobilization of copper metallic nanoparticles at the interface of mercaptosuccinic acid-functionalized N-acryloxysuccinimide-based monoliths. Upon photochemically-mediated free radical copolymerization of N-acryloxysuccinimide reactive monomer with ethylene glycol dimethacrylate cross-linker, reactive monoliths were obtained. Nucleophilic substitution of the N-hydroxysuccinimide moieties with allylamine, allowed for the synthesis of an olefin-functionalized monolith, as demonstrated by Raman spectroscopy. Mercaptosuccinic acid was anchored at the surface of the porous polymeric material through photochemically-driven thiol-ene “click” addition. In a final step, adsorption of copper nanoparticles at the surface of the resulting carboxylic acid functionalized monolith was achieved via two distinct pathways. It was either realized by percolation of a suspension of pre-formed copper nanoparticles through the capillary or by in situ reduction of Cu{sup (II)}Br{sub 2} salt solution preliminary flown through the monolith. After characterization of the resulting hybrids by scanning electron microscopy and energy-dispersive X-ray spectroscopy, investigations were further pursued regarding the catalytic behavior of such hybrid materials. The possibility to reduce 2-nitrophenol into the corresponding 2-aminophenol within a few minutes via a flow-through process inside the hybrid monolithic capillary was notably successfully demonstrated. - Graphical abstract: Display Omitted - Highlights: • Monolithic micro-reactors with surface immobilized copper nanoparticle for flow through catalytic processes. • Porous polymer-stabilized copper nanoparticles. • Photothiol-ene click chemistry for the effective surface functionalization of porous monolithic polymers. • Surface adsorption of copper nanoparticles through in-situ and ex-situ strategies.

  11. 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......-removal in flue-gas cleaning from waste incineration....

  12. 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 X-ra

  13. PILOT-SCALE STUDY OF THE EFFECT OF SELECTIVE CATALYTIC REDUCTION CATALYST ON MERCURY SPECIATION IN ILLINOIS AND POWDER RIVER BASIN COAL COMBUSTION FLUE GASES

    Science.gov (United States)

    A study was conducted to investigate the effect of selective catalytic reduction (SCR) catalyst on mercury (Hg) speciation in bituminous and subbituminous coal combustion flue gases. Three different Illinois Basin bituminous coals (from high to low sulfur and chlorine) and one Po...

  14. 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...

  15. Wet chemical method for synthesizing 3D graphene/gold nanocomposite: catalytic reduction of methylene blue

    Science.gov (United States)

    Xie, Jiliang; Yang, Xujie; Xu, Xingyou

    2017-04-01

    In this paper, a simple and environmentally-friendly approach was reported to synthesize a novel 3D composite of graphene/gold nanoparticles (3DG/Au NPs) in one step. A 3D interlaced framework of graphene, which exhibited hierarchically porous structures, generated directly through the distinct driving force during the hydrothermal growth. Meanwhile, Au NPs with high dispersity, which displayed tunable morphologies, were immobilized on the framework, where the as-prepared graphene was employed as the endogenous reducing agent. Compared with AuNPs, the obtained 3DG/Au NPs exhibited remarkably convenient recyclability and high activity for the reduction of methylene blue which is a kind of organic dye.

  16. Experimental and modeling study of the effect of CH(4) and pulverized coal on selective non-catalytic reduction process.

    Science.gov (United States)

    Zhang, Yanwen; Cai, Ningsheng; Yang, Jingbiao; Xu, Bo

    2008-10-01

    The reduction of nitric oxide using ammonia combined with methane and pulverized coal additives has been studied in a drop tube furnace reactor. Simulated flue gas with 1000 ppm NO(x) and 3.4% excess oxygen was generated by cylinder gas. Experiments were performed in the temperature range of 700-1200 degrees C to investigate the effects of additives on the DeNO(x) performance. Subsequently, a kinetic mechanism was modified and validated based on experimental results, and a computational kinetic modeling with CHEMKIN was conducted to analyze the secondary pollutants. For both methane and pulverized coal additives, the temperature window is shifted towards lower temperatures. The appropriate reaction temperature is shifted to about 900 and 800 degrees C, respectively with 1000 ppm methane and 0.051 g min(-1) pulverized lignite coal. The addition of methane and pulverized coal widens the temperature window towards lower temperature suggesting a low temperature application of the process. Furthermore, selective non-catalytic reduction (SNCR) reaction rate is accelerated evidently with additives and the residence time to complete the reaction is shortened distinctly. NO(x) reduction efficiency with 80% is achieved in about 0.3s without additive at 1000 degrees C. However, it is achieved in only about 0.2s with 100 ppm methane as additive, and only 0.07 and 0.05s are needed respectively for the cases of 500 and 1000 ppm methane. The modified kinetic modeling agrees well with the experimental results and reveals additional information about the process. Investigation on the byproducts where NO(2) and N(2)O were analyzed by modeling and the others were investigated by experimental means indicates that emissions would not increase with methane and pulverized coal additions in SNCR process and the efficacious temperature range of SNCR reaction is widened approximately with 100 degrees C.

  17. Induced axial chirality in biocatalytic asymmetric ketone reduction.

    Science.gov (United States)

    Agudo, Rubén; Roiban, Gheorghe-Doru; Reetz, Manfred T

    2013-02-06

    Catalytic asymmetric reduction of prochiral ketones of type 4-alkylidene cyclohexanone with formation of the corresponding axially chiral R-configurated alcohols (up to 99% ee) was achieved using alcohol dehydrogenases, whereas chiral transition-metal catalysts fail. Reversal of enantioselectivity proved to be possible by directed evolution based on saturation mutagenesis (up to 98% ee (S)). Utilization of ketone with a vinyl bromide moiety allows respective R- and S-alcohols to be exploited as key compounds in Pd-catalyzed cascade reactions.

  18. 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

  19. One-pot hydrothermal synthesis of CuBi co-doped mesoporous zeolite Beta for the removal of NOx by selective catalytic reduction with ammonia

    Science.gov (United States)

    Xie, Zhiguo; Zhou, Xiaoxia; Wu, Huixia; Chen, Lisong; Zhao, Han; Liu, Yan; Pan, Linyu; Chen, Hangrong

    2016-07-01

    A series of CuBi co-doped mesoporous zeolite Beta (CuxBiy-mBeta) were prepared by a facile one-pot hydrothermal treatment approach and were characterized by XRD, N2 adsorption-desorption, TEM/SEM, XPS, H2-TPR, NH3-TPD and in situ DRIFTS. The catalysts CuxBiy-mBeta were applied to the removal of NOx by selective catalytic reduction with ammonia (NH3-SCR), especially the optimized Cu1Bi1-mBeta achieved the high efficiency for the removal of NOx and N2 selectivity, superior water and sulfur resistance as well as good durability. The excellent catalytic performance could be attributed to the acid sites of the support and the synergistic effect between copper and bismuth species. Moreover, in situ DRIFTS results showed that amides NH2 and NH4+ generated from NH3 adsorption could be responsible for the high selective catalytic reduction of NOx to N2. In addition, a possible catalytic reaction mechanism on Cu1Bi1-mBeta for the removal of NOx by NH3-SCR was proposed for explaining this catalytic process.

  20. Selective catalytic reduction of NO and NO{sub 2} at low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Koebel, Manfred; Madia, Giuseppe; Elsener, Martin [Paul Scherrer Institute, CH-5232 PSI Villigen (Switzerland)

    2002-04-15

    The fast SCR reaction using equimolar amounts of NO and NO{sub 2} is a powerful means to enhance the NO{sub x} conversion over a given SCR catalyst. NO{sub 2} fractions in excess of 50% of total NO{sub x} should be avoided because the reaction with NO{sub 2} only is slower than the standard SCR reaction. At temperatures below 200C, due to its negative temperature coefficient, the ammonium nitrate reaction gets increasingly important. Half of each NH{sub 3} and NO{sub 2} react to form dinitrogen and water in analogy to a typical SCR reaction. The other half of NH{sub 3} and NO{sub 2} form ammonium nitrate in close analogy to a NO{sub x} storage-reduction catalyst. Ammonium nitrate tends to deposit in solid or liquid form in the pores of the catalyst and this will lead to its temporary deactivation.The various reactions have been studied experimentally in the temperature range 150-450C for various NO{sub 2}/NO{sub x} ratios. The fate of the deposited ammonium nitrate during a later reheating of the catalyst has also been investigated. In the absence of NO, the thermal decomposition yields mainly ammonia and nitric acid. If NO is present, its reaction with nitric acid on the catalyst will cause the formation of NO{sub 2}.

  1. Mercury Oxidation over Selective Catalytic Reduction (SCR) Catalysts - Ph.d. thesis Karin Madsen

    DEFF Research Database (Denmark)

    Madsen, Karin

    for the mercury chemistry over the SCR: R1. 2 HCl + Hg0 + 1/2 O2 ↔ HgCl2 + H2O R2. 2 NH3 + 3 HgCl2 ↔ N2 + 3 Hg0 + 6 HCl R3. 2 NO + 2 NH3 + 1/2 O2 ↔ 2 N2 + 3 H2O where reaction R1 is the oxidation of Hg0 by HCl, reaction R2 is the reduction of HgCl2 by NH3 and reaction R3 is the DeNOx reaction. The importance...... oxidation - possibly as Hg0 adsorption sites. A kinetic model for the steady-state Hg0 oxidation over monolithic SCR reactors has been developed taking both external mass transfer, pore diffusion and reaction on the catalyst wall into account. The mercury chemistry that has been identified and quantified...... in the experimental investigations is incorporated in the model. The resulting model successfully reproduces the variations in Hg0 oxidation over the SCR that have been experimentally observed for different gas compositions and testing conditions. This verifies that the relevant mercury chemistry has been taken...

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

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Xin, E-mail: chenxin830107@pku.edu.cn; Chen, Shuangjing; Wang, Jinyu

    2016-08-30

    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.

  3. 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.

  4. Low temperature selective catalytic reduction of NOx with NH3 over Mn-based catalyst: A review

    OpenAIRE

    TsungYu Lee; Hsunling Bai

    2016-01-01

    The removals of NOx by catalytic technology at low temperatures (100–300 °C) for industrial flue gas treatment have received increasing attention. However, the development of low temperature catalysts for selective catalytic reduction (SCR) of NOx with ammonia is still a challenge especially in the presence of SO2. The current status of using Mn-based catalysts for low temperature SCR of NOx with ammonia (NH3-SCR) is reviewed. Reaction mechanisms and effects of operating factors on low temper...

  5. Fabrication of doped Titania (TiO2) nanofibers to serve as catalysts in NH3-Selective CatalyticReduction (SCR)

    DEFF Research Database (Denmark)

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

    2016-01-01

    of the NOx in exhausts via the NH3 SelectiveCatalytic Reduction (SCR) method. By combining electrospinning and sol-gel chemistry, materials areprocessed as nanofibers with the catalytic components (e. g. V2O5-WO3) incorporated as dopants into thesupporting anatase phase (e. g TiO2). Remarkable high NOx...... conversion efficiencies are obtained andassociated with the unique features deriving from the synergism among the doping approach, the nanoscaleconfinement, and the nano-fibrous texture. A novel concept of self-supported, lightweight and ultra-compactdesign SCR reactor is defined....

  6. Development of catalysts and ligands for enantioselective gold catalysis.

    Science.gov (United States)

    Wang, Yi-Ming; Lackner, Aaron D; Toste, F Dean

    2014-03-18

    During the past decade, the use of Au(I) complexes for the catalytic activation of C-C π-bonds has been investigated intensely. Over this time period, the development of homogeneous gold catalysis has been extraordinarily rapid and has yielded a host of mild and selective methods for the formation of carbon-carbon and carbon-heteroatom bonds. The facile formation of new bonds facilitated by gold naturally led to efforts toward rendering these transformations enantioselective. In this Account, we survey the development of catalysts and ligands for enantioselective gold catalysis by our research group as well as related work by others. We also discuss some of our strategies to address the challenges of enantioselective gold(I) catalysis. Early on, our work with enantioselective gold-catalyzed transformations focused on bis(phosphinegold) complexes derived from axially chiral scaffolds. Although these complexes were highly successful in some reactions like cyclopropanation, the careful choice of the weakly coordinating ligand (or counterion) was necessary to obtain high levels of enantioselectivity for the case of allene hydroamination. These counterion effects led us to use the anion itself as a source of chirality, which was successful in the case of allene hydroalkoxylation. In general, these tactics enhance the steric influence around the reactive gold center beyond the two-coordinate ligand environment. The use of binuclear complexes allowed us to use the second gold center and its associated ligand (or counterion) to exert a further steric influence. In a similar vein, we employed a chiral anion (in place of or in addition to a chiral ligand) to move the chiral information closer to the reactive center. In order to expand the scope of reactions amenable to enantioselective gold catalysis to cycloadditions and other carbocyclization processes, we also developed a new class of mononuclear phosphite and phosphoramidite ligands to supplement the previously widely

  7. Catalytic Asymmetric Synthesis of Phosphine Boronates.

    Science.gov (United States)

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

    2015-06-26

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

  8. Rh nanoparticles supported on ultrathin carbon nanosheets for high-performance oxygen reduction reaction and catalytic hydrogenation.

    Science.gov (United States)

    Lin, Chong; Wu, Guanghao; Li, Huiqin; Geng, Yanmin; Xie, Gang; Yang, Jianhui; Liu, Bin; Jin, Jian

    2017-02-02

    We reported a facile and scalable salt-templated approach to produce monodisperse Rh nanoparticles (NPs) on ultrathin carbon nanosheets with the assistance of calcination under inert gas. More importantly, in spite of the essentially poor ORR activity of Rh/C, the acquired Rh/C hybrid nanosheets display a comparable ORR activity to the optimal commercial Pt/C catalyst, which may be due to the extra-small size of Rh NPs and the 2D defect-rich amorphous carbon nanosheets that can facilitate the charge transfer and reactive surface exposure. Moreover, Rh/C nanosheets present the optimal current density and best durability with the minimum decline during the entire test, so that ∼93% activity after 20 000 s is achieved, indicating a good lifetime for ORR. In contrast, commercial Pt/C and commercial Rh/C exhibited worse durability, so that ∼74% and ∼85% activities after 20 000 s are maintained. What's more, in the model system of reduction of 4-nitrophenol (4-NP), the kinetic constant k for Rh/C nanosheets is 3.1 × 10(-3), which is 4.5 times than that of the commercial Rh/C catalyst, revealing that our Rh/C hybrid nanosheets can be potentially applied in industrial catalytic hydrogenation. This work opens a novel and facile way for the rest of the precious metal NPs to be supported on ultrathin carbon nanosheets for heterogeneous catalysis.

  9. Simultaneous removal of NO x and SO2 by low-temperature selective catalytic reduction over modified activated carbon catalysts

    Science.gov (United States)

    Liu, Ye; Ning, Ping; Li, Kai; Tang, Lihong; Hao, Jiming; Song, Xin; Zhang, Guijian; Wang, Chi

    2017-03-01

    A series of modified porous activated carbon (AC) catalysts prepared by impregnation were investigated for the low-temperature (≤250°C) selective catalytic reduction (SCR) of NO x with NH3 with simultaneous removal of SO2. The effects of various preparation conditions and reaction conditions on NO and SO2 conversions were observed, such as support type, active components, copper loading, calcination temperature and presence of H2O and O2. The modified AC catalysts were characterized by BET, XRD, TG and TPX methods. The activity test results showed that the optimal catalyst is 15% Cu/WCSAC which can provide 52% NO conversion and 68% SO2 conversion simultaneously at 175°C with a space velocity of 30000 h‒1, and the optimal calcination temperature was 500°C. The presence of H2O could inhibit NO conversion and promote the SO2 conversion. The effect of O2 (0-5%) was evaluated, and the NO and SO2 conversions were best when the concentration of O2 was 3%. Research demonstrated that Cu/WCSAC catalyst was a kind of potential catalysts due to the amorphous phase, high specific areas and high active ability.

  10. Hierarchical plasmonic-metal/semiconductor micro/nanostructures: green synthesis and application in catalytic reduction of p-nitrophenol

    Science.gov (United States)

    Gao, Shuyan; Jia, Xiaoxia; Li, Zhengdao; Chen, Yanli

    2012-03-01

    Hierarchical micro/nano arrays can offer both the advantages of nano-sized building blocks and micro- or submicrometer-sized ordered arrays, therefore representing one kind of potential functional materials and having received enormous attention for a wealth of applications. In this study, four-dimensionally flower-like CuO micro/nanostructures decorated by Au nanoparticles are synthesized via an environmentally friendly route assisted by polyethylene glycol. Experiments reveal that the product demonstrates high catalytic performance for the reduction of 4-nitrophenol using NaBH4 as the reducing agent, which could be attributed to the rich Au/CuO interfaces in the samples. Compared to the pure noble metal catalysts, the obtained sample is quite economic. In terms of methodology and cost-effectiveness, this study proposes an economically useful and green method to produce a highly efficient metal-based catalyst. It is also a good example for the organic combination of green chemistry and functional materials.

  11. Performance of selective catalytic reduction of NO with NH3 over natural manganese ore catalysts at low temperature.

    Science.gov (United States)

    Wang, Tao; Zhu, Chengzhu; Liu, Haibo; Xu, Yongpeng; Zou, Xuehua; Xu, Bin; Chen, Tianhu

    2017-03-16

    Natural manganese ore catalysts for selective catalytic reduction (SCR) of NO with NH3 at low temperature in the presence and absence of SO2 and H2O were systematically investigated. The physical and chemical properties of catalysts were characterized by X-ray diffraction, Brunauer-Emmett-Teller (BET) specific surface area, NH3 temperature-programmed desorption (NH3-TPD) and NO-TPD methods. The results showed that natural manganese ore from Qingyang of Anhui Province had a good low-temperature activity and N2 selectivity, and it could be a novel catalyst in terms of stability, good efficiency, good reusability and lower cost. The NO conversion exceeded 85% between 150°C and 300°C when the initial NO concentration was 1000 ppm. The activity was suppressed by adding H2O (10%) or SO2 (100 or 200 ppm), respectively, and its activity could recover while the SO2 supply is cut off. The simultaneous addition of H2O and SO2 led to the increase of about 100% in SCR activity than bare addition of SO2. The formation of the amorphous MnOx, high concentration of lattice oxygen and surface-adsorbed oxygen groups and a lot of reducible species as well as adsorption of the reactants brought about excellent SCR performance and exhibited good SO2 and H2O resistance.

  12. Fabrication of Bi-Fe3O4@RGO hybrids and their catalytic performance for the reduction of 4-nitrophenol

    Science.gov (United States)

    Wang, Xuefang; Xia, Fengling; Li, Xichuan; Xu, Xiaoyang; Wang, Huan; Yang, Nian; Gao, Jianping

    2015-11-01

    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 Fe3O4 nanoparticles loaded on reduced graphene oxide magnetic hybrids (Bi-Fe3O4@RGO) using soluble starch as a dispersant is demonstrated. The magnetic Fe3O4 nanoparticles were synthesized by the co-precipitation of Fe2+ and Fe3+ 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 Fe3O4 nanoparticles is about 5 nm and the diameters of Bi nanoparticles range from 10 to 20 nm. The magnetic Bi-Fe3O4@RGO hybrids exhibit high catalytic activity in the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by NaBH4 with a first-order rate constant (K) of 0.00808 s-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.

  13. Selective catalytic reduction of NO by NH3 on Cu-faujasite catalysts: an experimental and quantum chemical approach.

    Science.gov (United States)

    Delahay, Gérard; Villagomez, Enrique Ayala; Ducere, Jean-Marie; Berthomieu, Dorothée; Goursot, Annick; Coq, Bernard

    2002-08-16

    The selective catalytic reduction (SCR) of NO by NH3 in the presence of O2 on Cu-faujasite (Cu-FAU) has been studied. Substitution of some Cu2+ with H+ and Na+ cations, compensating for the negative charge of the zeolite framework, forms the various CuHNa-FAU studied. The amount of Cu was held constant and the proportion of H+ and Na+ varied in the sample. The substitution of Na+ for H+ increases sharply the SCR rate by lowering the temperature of reaction by about 150 K. It is proposed that the rate increase mainly comes from an unhindered migration of Cu from hidden to active sites and a modification of the redox properties of Cu species. The former was demonstrated by diffuse reflectance IR spectroscopy of adsorbed CO. The change in redox properties was demonstrated by a faster oxidation of Cu+ to Cu2+ (rate-determining step). Quantum chemical calculations on model clusters of CuHNa-FAU indicate that the faster rate of oxidation can be explained by a higher lability of protons in the absence of Na, which can be then removed from the catalyst more easily to yield H2O during the oxidation process.

  14. Selective catalytic reduction of nitric oxide with ethanol/gasoline blends over a silver/alumina catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Pihl, Josh A [ORNL; Toops, Todd J [ORNL; Fisher, Galen [University of Michigan; West, Brian H [ORNL

    2014-01-01

    Lean gasoline engines running on ethanol/gasoline blends and equipped with a silver/alumina catalyst for selective catalytic reduction (SCR) of NO by ethanol provide a pathway to reduced petroleum consumption through both increased biofuel utilization and improved engine efficiency relative to the current stoichiometric gasoline engines that dominate the U.S. light duty vehicle fleet. A pre-commercial silver/alumina catalyst demonstrated high NOx conversions over a moderate temperature window with both neat ethanol and ethanol/gasoline blends containing at least 50% ethanol. Selectivity to NH3 increases with HC dosing and ethanol content in gasoline blends, but appears to saturate at around 45%. NO2 and acetaldehyde behave like intermediates in the ethanol SCR of NO. NH3 SCR of NOx does not appear to play a major role in the ethanol SCR reaction mechanism. Ethanol is responsible for the low temperature SCR activity observed with the ethanol/gasoline blends. The gasoline HCs do not deactivate the catalyst ethanol SCR activity, but they also do not appear to be significantly activated by the presence of ethanol.

  15. Low-Temperature Selective Catalytic Reduction of NO with NH₃ over Mn₂O₃-Doped Fe₂O₃ Hexagonal Microsheets.

    Science.gov (United States)

    Li, Yi; Wan, Yuan; Li, Yanping; Zhan, Sihui; Guan, Qingxin; Tian, Yang

    2016-03-02

    Mn2O3-doped Fe2O3 hexagonal microsheets were prepared for the low-temperature selective catalytic reduction (SCR) of NO with NH3. These hexagonal microsheets were characterized by SEM, TEM, XRD, BET, XPS, NH3-TPD, H2-TPR, and in situ DRIFT and were shown to exhibit a considerable uniform hexagonal microsheet structure and excellent low temperature SCR efficiency. When doped with different Mn molar ratios, Mn2O3 was detected in the Fe2O3 hexagonal microsheets based on the XRD results without the presence of other MnOX species. In addition, the hexagonal microsheets with a Mn/Fe molar ratio of 0.2 showed the best SCR removal performance among the materials, where a 98% NO conversion ratio at 200 °C at a space velocity of 30,000 h(-1) was obtained. Meanwhile, excellent tolerances to H2O and SO2, as well as high thermal stability, were obtained in Mn2O3-doped Fe2O3 hexagonal microsheets. Moreover, on the basis of the XPS and in situ DRIFT results, it can be suggested that coupled Mn2O3 nanocrystals played a key role at low temperatures and produced a possible redox reaction mechanism in the SCR process.

  16. Determining the storage, availability and reactivity of NH3 within Cu-Chabazite-based Ammonia Selective Catalytic Reduction systems.

    Science.gov (United States)

    Lezcano-Gonzalez, I; Deka, U; Arstad, B; Van Yperen-De Deyne, A; Hemelsoet, K; Waroquier, M; Van Speybroeck, V; Weckhuysen, B M; Beale, A M

    2014-01-28

    Three different types of NH3 species can be simultaneously present on Cu(2+)-exchanged CHA-type zeolites, commonly used in Ammonia Selective Catalytic Reduction (NH3-SCR) systems. These include ammonium ions (NH4(+)), formed on the Brønsted acid sites, [Cu(NH3)4](2+) complexes, resulting from NH3 coordination with the Cu(2+) Lewis sites, and NH3 adsorbed on extra-framework Al (EFAl) species, in contrast to the only two reacting NH3 species recently reported on Cu-SSZ-13 zeolite. The NH4(+) ions react very slowly in comparison to NH3 coordinated to Cu(2+) ions and are likely to contribute little to the standard NH3-SCR process, with the Brønsted groups acting primarily as NH3 storage sites. The availability/reactivity of NH4(+) ions can be however, notably improved by submitting the zeolite to repeated exchanges with Cu(2+), accompanied by a remarkable enhancement in the low temperature activity. Moreover, the presence of EFAl species could also have a positive influence on the reaction rate of the available NH4(+) ions. These results have important implications for NH3 storage and availability in Cu-Chabazite-based NH3-SCR systems.

  17. [Low-temperature catalytic reduction of NO over Fe-MnOx-CeO2/ZrO2 catalyst].

    Science.gov (United States)

    Liu, Rong; Yang, Zhi-Qin

    2012-06-01

    Fe-MnOx-CeO2/ZrO2 catalysts were prepared through impregnation method with nanometer ZrO2 as a carrier and used in selective catalytic reduction of NO with NH3 at low temperature. Effects of active component ratio and loading of promoter on the catalyst activity were investigated. The catalysts were characterized by means of XRD, SEM, EDS and BET. The effects of temperature, SO2 and H2O on NO conversion were studied and the results showed that in the absence of SO2 and H2O, the catalyst of 8% Fe-10% MnOx-CeO2/ZrO2 had good activity and stability as well as the NOx removal efficiency reached 85.23% at 120 degrees C and 92.0% at 180 degrees C. The presence of SO2 and H2O results in the catalyst deactivated. Properties of the catalyst on different reaction stages were characterized by FT-IR to study the inactivation mechanism of the catalyst. The results showed that the catalyst deactivation was due to the deposition of ammonium sulfate on the catalyst and the sulphation of the catalyst.

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

    Science.gov (United States)

    Kong, Dewang; Yuan, Wenjing; Li, Cun; Song, Jiming; Xie, Anjian; Shen, Yuhua

    2017-01-01

    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 m2/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 addresses the disposal issue of waste biomass simultaneously for environment clean.

  19. DRIFT study of manganese/ titania-based catalysts for low-temperature selective catalytic reduction of NO with NH3.

    Science.gov (United States)

    Wu, Zhongbiao; Jiang, Boqiong; Liu, Yue; Wang, Haiqiang; Jin, Ruiben

    2007-08-15

    Manganese oxides and iron-manganese oxides supported on TiO2 were prepared by the sol-gel method and used for low-temperature selective catalytic reduction (SCR) of NO with NH3. Base on the previous study, Mn(0.4)/ TiO2 and Fe(0.1)-Mn(0.4)/TiO2 were then selected to carry out the in situ diffuse reflectance infrared transform spectroscopy (DRIFT) investigation for revealing the reaction mechanism. The DRIFT spectroscopy for the adsorption of NH3 indicated the presence of coordinated NH3 and NH4+ on both of the two catalysts. When NO was introduced, the coordinated NH3 on the catalyst surface was consumed rapidly, indicating these species could react with NO effectively. When NH3 was introduced into the sample preadsorbed with NO + O2, SCR reaction would not proceed on Mn(0.4)/TiO2. However, for Fe(0.1)-Mn(0.4)/ TiO2 the bands due to coordinated NH3 on Fe2O3 were formed. Simultaneously, the bidentate nitrates were transformed to monodentate nitrates and NH4+ was detected. And NO2 from the oxidation of NO on catalyst could react with NH4+ leading to the reduction of NO. Therefore, it was suggested that the SCR reaction on Fe(0.1)-Mn(0.4)/TiO2 could also take place in a different way from the reactions on Mn(0.4)/TiO2 proposed by other researchers. Furthermore, the SCR reaction steps for these two kinds of catalysts were proposed.

  20. Highly selective catalytic reduction of NO via SO2/H2O-tolerant spinel catalysts at low temperature.

    Science.gov (United States)

    Cai, Xuanxuan; Sun, Wei; Xu, Chaochao; Cao, Limei; Yang, Ji

    2016-09-01

    Selective catalytic reduction of NO X by hydrogen (H2-SCR) in the presence of oxygen has been investigated over the NiCo2O4 and Pd-doped NiCo2O4 catalysts under varying conditions. The catalysts were prepared by a sol-gel method in the presence of oxygen within 50-350 °C and were characterized using XRD, BET, EDS, XPS, Raman, H2-TPR, and NH3-TPD analysis. The results demonstrated that the doped Pd could improve the catalyst reducibility and change the surface acidity and redox properties, resulting in a higher catalytic performance. The performance of NiCo1.95Pd0.05O4 was consistently better than that of NiCo2O4 within the 150-350 °C range at a gas hourly space velocity (GHSV) of 4800 mL g(-1) h(-1), with a feed stream containing 1070 ppm NO, 10,700 ppm H2, 2 % O2, and N2 as balance gas. The effects of GHSV, NO/H2 ratios, and O2 feed concentration on the NO conversion over the NiCo2O4 and NiCo1.95Pd0.05O4 catalysts were also investigated. The two samples similarly showed that an increase in GHSV from 4800 to 9600 mL h(-1) g(-1), the NO/H2 ratio from 1:10 to 1:1, and the O2 content from 0 to 6 % would result in a decrease in NO conversion. In addition, 2 %, 5 %, and 8 % H2O into the feed gas had a slightly negative influence on SCR activity over the two catalysts. The effect of SO2 on the SCR activity indicated that the NiCo1.95Pd0.05O4 possesses better SO2 tolerance than NiCo2O4 catalyst does. Graphical abstract The NiCo1.95Pd0.05O4 catalyst achieved over 90 % NO conversion with N2 selectivity of 100 % in the 200∼250 °C range than the maximum 40.5 % NO conversion over NiCo2O4 with N2 selectivity of approximately 80 % in 350 °C.

  1. Catalytic reduction of nitrate in secondary effluent of wastewater treatment plants by Fe(0) and Pd-Cu/γ-Al2O3.

    Science.gov (United States)

    Yun, Yupan; Li, Zifu; Chen, Yi-Hung; Saino, Mayiani; Cheng, Shikun; Zheng, Lei

    2016-01-01

    Total nitrogen, in which NO3(-) is dominant in the effluent of most wastewater treatment plants, cannot meet the requirements of the Chinese wastewater discharge standard (nitrate (NO3(-)) elimination attract considerable attention. In this study, reductant iron (Fe(0)) and γ-Al2O3 supported palladium-copper bimetallic catalysts (Pd-Cu/γ-Al2O3) were innovatively used for the chemical catalytic reduction of nitrate in wastewater. A series of specific operational conditions (such as mass ratio of Pd:Cu, catalyst amounts, reaction time and pH of solution) were optimized for nitrate reduction in the artificial solution, and then the selected optimal conditions were further applied for investigating the nitrate elimination of secondary effluent of a wastewater treatment plant in Beijing, China. Results indicated that a better catalytic performance (74% of nitrate removal and 62% of N2 selectivity) could be obtained under the optimal condition: 5 g/L Fe(0), 3:1 mass ratio (Pd:Cu), 4 g/L catalyst, 2 h reaction time and pH 5.1. It is noteworthy to point out that nitrogen gas (N2) predominated in the byproducts without another system to treat ammonium and nitrite. Therefore, the chemical catalytic reduction combining Fe(0) with Pd-Cu/γ-Al2O3 could be regarded as a better alternative for nitrate removal in wastewater treatment.

  2. Enantioselective recognition at mesoporous chiral metal surfaces

    Science.gov (United States)

    Wattanakit, Chularat; Côme, Yémima Bon Saint; Lapeyre, Veronique; Bopp, Philippe A.; Heim, Matthias; Yadnum, Sudarat; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2014-02-01

    Chirality is widespread in natural systems, and artificial reproduction of chiral recognition is a major scientific challenge, especially owing to various potential applications ranging from catalysis to sensing and separation science. In this context, molecular imprinting is a well-known approach for generating materials with enantioselective properties, and it has been successfully employed using polymers. However, it is particularly difficult to synthesize chiral metal matrices by this method. Here we report the fabrication of a chirally imprinted mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and chiral template molecules. The porous platinum retains a chiral character after removal of the template molecules. A matrix obtained in this way exhibits a large active surface area due to its mesoporosity, and also shows a significant discrimination between two enantiomers, when they are probed using such materials as electrodes.

  3. Selective catalytic reduction (SCR) of NO by urea loaded on activated carbon fibre (ACF) and CeO2/ACF at 30 degrees C: the SCR mechanism.

    Science.gov (United States)

    Zeng, Zheng; Lu, Pei; Li, Caiting; Zeng, Guangming; Jiang, Xiao; Zhai, Yunbo; Fan, Xiaopeng

    2012-06-01

    Selective catalytic reduction (SCR) of NO by urea loaded on rayon-based activated carbon fibre (ACF) and CeO2/ACF (CA) was studied at ambient temperature (30 degrees C) to establish a basic scheme for its reduction. Nitric oxide was found to be reduced to N2 with urea deposited on the ACF and CA. When oxygen was present, the greater the amount of loaded urea (20-60%), the greater the NO(x) conversions, which were between 72.03% and 77.30%, whereas the NO(x) conversions were about 50% when oxygen was absent. Moreover, when the urea was loaded on CA, a catalyst containing 40% urea/ACF loaded with 10% CeO2 (UCA4) could yield a NO(x) conversion of about 80% for 24.5 h. Based on the experimental results, the catalytic mechanisms of SCR with and without oxygen are discussed. The enhancing effect of oxygen resulted from the oxidation of NO to NO2, and urea was the main reducing agent in the SCR of loaded catalysts. ACF-C was the catalytic centre in the SCR of NO of ACF, while CeO2 of urea-loaded CA was the catalytic centre.

  4. 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.

  5. Pt/YSZ electrochemical catalysts prepared by electrostatic spray deposition for selective catalytic reduction of NO by C{sub 3}H{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Lintanf, A.; Djurado, E. [Laboratoire d' Electrochimie et de Physico-Chimie des Materiaux et des Interfaces (LEPMI), ENSEEG/INPG/UJF/CNRS Institut National Polytechnique de Grenoble Domaine Universitaire, BP 75, 1130 rue de la Piscine, 38402 St Martin d' Heres Cedex (France); Vernoux, P. [Universite de Lyon, Institut de Recherches sur la Catalyse et l' Environnement de Lyon, UMR 5256, CNRS, Universite Claude Bernard Lyon 1, 2 avenue A. Einstein, 69626 Villeurbanne (France)

    2008-03-15

    Due to the great importance of automotive exhaust gas treatment, the catalytic activity was investigated in selective catalytic reduction of NO by propene on Pt films - with controlled microstructure - deposited on YSZ (8 mol% Y{sub 2}O{sub 3}-doped ZrO{sub 2}) by electrostatic spray deposition. This technique requires low Pt loadings in order to reduce costs and also to achieve high Pt particles dispersion with good reproducibility. This kind of electrochemical catalysts was found to be effective for NO reduction by propene in the presence of oxygen. A dense Pt film was found to be the most suitable. Furthermore, we have demonstrated that these electrochemical catalysts can implement the concept of electrochemical promotion of catalysis (EPOC). (author)

  6. Effect of promoter and noble metals and suspension pH on catalytic nitrate reduction by bimetallic nanoscale Fe(0) catalysts.

    Science.gov (United States)

    Bae, Sungjun; Hamid, Shanawar; Jung, Junyoung; Sihn, Youngho; Lee, Woojin

    2016-01-01

    Experiments were conducted to investigate the effect of experimental factors (types of promotor and noble metals, H2 injection, and suspension pH) on catalytic nitrate reduction by bimetallic catalysts supported by nanoscale zero-valent iron (NZVI). NZVI without H2 injection showed 71% of nitrate reduction in 1 h. Cu/NZVI showed the almost complete nitrate reduction (96%) in 1 h, while 67% of nitrate was reduced by Ni/NZVI. The presence of noble metals (Pd and Pt) on Cu/NZVI without H2 injection resulted in the decrease of removal efficiency to 89% and 84%, respectively, due probably to the electron loss of NZVI for formation of metallic Pd and Pt. H2 injection into Cu-Pd/NZVI suspension significantly improved both catalytic nitrate reduction (>97% in 30 min) and N2 selectivity (18%), indicating that adsorbed H on active Pd sites played an important role for the enhanced nitrate reduction and N2 selectivity. The rapid passivation of NZVI surface resulted in a dramatic decrease in nitrate reduction (79-28%) with an increase in N2 selectivity (8-66%) as the suspension pH increased from 8 to 10.

  7. Superior catalysts for selective catalytic reduction of nitric oxide. Final technical report, October 1, 1993--September 30, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Yang, R.T.; Li, W.B.; Chen, J.P.; Hausladen, M.C.; Cheng, L.S.; Kikkinides, E.S.

    1995-12-31

    The most advanced and proven technology for NO{sub x} control for stationary sources is Selective Catalytic Reduction (SCR). In SCR, NO{sub x} is reduced by NH{sub 3} to N{sub 2} and H{sub 2}O. The commercial catalysts are based on V{sub 2}O{sub 5}/TiO{sub 2}, and the vanadium-based catalysts are patented by the Japanese (Mitsubishi). However, there are three main advantages for the vanadium-based SCR catalyst: (a) a tendency to be poisoned in the flue gas; (b) oxidation of SO{sub 2} to SO{sub 3} by V{sub 2}O{sub 5}, this is a particularly severe problem due to the higher sulfur content of American coals compared with coals used in Japan (from Australia) and in Europe; (c) environmental problems involved in the disposal of the spent catalyst (due to the toxicity of vanadium). In order to overcome these problems, in addition to the undesirable dominance by the Japanese patent position, the authors have studied in this project a new type of catalyst for the SCR reaction; namely, pillared clays, which have adjustable, unique structures and acidity. Three types of catalysts were developed and tested for this reaction, i.e. Fe{sub 2}O{sub 3}-pillared clays, delaminated Fe{sub 2}O{sub 3}-pillared clays, and ion-exchanged pillared clays. The project was divided into sixteen tasks, and will be reported as such.

  8. Catalytic asymmetric alkylation of acylsilanes

    NARCIS (Netherlands)

    Rong, Jiawei; Oost, Rik; Desmarchelier, Alaric; Minnaard, Adriaan J; Harutyunyan, Syuzanna R

    2015-01-01

    The highly enantioselective addition of Grignard reagents to acylsilanes is catalyzed by copper diphosphine complexes. This transformation affords -silylated tertiary alcohols in up to 97% yield and 98:2 enantiomeric ratio. The competing Meerwein-Ponndorf-Verley reduction is suppressed by the use of

  9. Synthesis of palladium nanoparticles over graphite oxide and carbon nanotubes by reduction in ethylene glycol and their catalytic performance on the chemoselective hydrogenation of para-chloronitrobenzene

    OpenAIRE

    2016-01-01

    Pd nanoparticles have been synthesized over carbon nanotubes (CNT) and graphite oxide (GO) by reduction with ethylene glycol and by conventional impregnation method. The catalysts were tested on the chemoselective hydrogenation of p-chloronitrobenzene and the effect of the synthesis method and surface chemistry on their catalytic performance was evaluated. The catalysts were characterized by N2 adsorption/desorption isotherms at 77 K, TEM, powder X-ray diffraction, thermogravimetry, infrared ...

  10. The Experimental and Simulation Study of Selective Catalytic Reduction System in a Single Cylinder Diesel Engine Using NH3 as a Reducing Agent

    OpenAIRE

    Manoj Kumar Athrashalil Phaily; Sreekumar Jayachandra Sreekala; Padmanabha Mohanan

    2014-01-01

    Selective catalytic reduction (SCR) technology has been widely used in automotive applications in order to meet the stringent limits on emission standards. The maximum NOx conversion efficiency of an SCR depends on temperature and mass flow rate of an exhaust gas. In order to assess the suitability of Cordierite/Pt catalyst for low temperature application, an experimental work is carried out using single cylinder diesel engine for different load conditions by varying ammonia induction rate fr...

  11. FT-IR Spectroscopic characterization of the intermediates in the selective catalytic reduction of NO with methane on Pd/ZrO(formula)-WO(formula) catalyst

    OpenAIRE

    Çayırtepe, İlknur

    2004-01-01

    Cataloged from PDF version of article. This work involves in situ FT-IR spectroscopic study of the routes of formation, composition and thermal stability of strongly bound NOx complexes on the surface of Pd/tungstated zirconia, and transformation of the surface NOx complexes in the presence of methane in order to elucidate the mechanism of selective catalytic reduction of NO with methane. Sol-gel polymer-template synthesis was chosen to obtain high surface area in the prepar...

  12. Bisguanidinium dinuclear oxodiperoxomolybdosulfate ion pair-catalyzed enantioselective sulfoxidation

    Science.gov (United States)

    Zong, Lili; Wang, Chao; Moeljadi, Adhitya Mangala Putra; Ye, Xinyi; Ganguly, Rakesh; Li, Yongxin; Hirao, Hajime; Tan, Choon-Hong

    2016-11-01

    Catalytic use of peroxomolybdate for asymmetric transformations has attracted increasing attention due to its catalytic properties and application in catalysis. Herein, we report chiral bisguanidinium dinuclear oxodiperoxomolybdosulfate [BG]2+[(μ-SO4)Mo2O2(μ-O2)2(O2)2]2- ion pair, as a catalyst for enantioselective sulfoxidation using aqueous H2O2 as the terminal oxidant. The ion pair catalyst is isolatable, stable and useful for the oxidation of a range of dialkyl sulfides. The practical utility was illustrated using a gram-scale synthesis of armodafinil, a commercial drug, with the catalyst generated in situ from 0.25 mol% of bisguanidinium and 2.5 mol% of Na2MoO4.2H2O. Structural characterization of this ion pair catalyst has been successfully achieved using single-crystal X-ray crystallography.

  13. Synergistic chiral iminium and palladium catalysis: Highly regio- and enantioselective [3 + 2] annulation reaction of 2-vinylcyclopropanes with enals

    Science.gov (United States)

    Zhu, Haipan; Du, Peile; Li, Jianjun; Liao, Ziyang; Liu, Guohua

    2016-01-01

    Summary A cooperative catalytic strategy of chiral iminium catalysis by regioselective activation of the C=C bond in enals and a transition metal promoting to open the 2-vinylcyclopropanes for highly regio- and enantioselective [3 + 2] cycloaddition reaction of 2-vinylcyclopropanes with α,β-unsaturated aldehydes has been developed. PMID:27559383

  14. In situ FT-IR studies on the mechanism of selective catalytic reduction of NOx by propene over SnO2/Al2O3 catalyst.

    Science.gov (United States)

    Liu, Zhiming; Woo, Seong Ihl; Lee, Won Su

    2006-12-28

    The mechanism of the selective catalytic reduction (SCR) of NOx by propene over SnO2/Al2O3 catalyst in the presence of oxygen has been investigated using in situ Fourier transform infrared (FT-IR) spectroscopy. In situ IR measurements indicate that acetate and formate, which are the derivatives of the partial oxidation of propene, play a crucial role in the formation of NCO by reacting with the reactive monodentate nitrate species. The resulting NCO species subsequently reacts with NOx to form N2. The presence of oxygen substantially contributes to the partial oxidation of propene and thus shows a promoting effect for the NOx reduction.

  15. CARBOXYLESTERASES IN ENANTIOSELECTIVE SYNTHESIS OF ORGANIC COMPOUNDS

    Directory of Open Access Journals (Sweden)

    E. A. Shesterenko

    2013-02-01

    Full Text Available The classification, structure, and mechanism of catalytic action of carboxylesterase of different origin are presented in the review. The prospects of carboxylesterases application for metabolism and both several drugs and prodrugs activation investigation in vitro are shown. The enzyme usage as biocatalyst of stereoselective hydrolysis and synthesis of a wide range of acyclic, carbocyclic and heterocyclic compounds — esters are also urgent. It was established that enantiomers obtainable with the help of carboxylesterase are characterized by high chemical yields and optical purity; immobilization on different supports stabilizes the enzyme and allows the repeated usage of obtained biocatalysts. The own studies conducted and the enzymatic hydrolysis features of news 3-acylhydroxy-1,4-benzodiasepin-2-ones — potential anxiolytic and hypnotic means, with a help of pig liver microsomal fraction carboxylesterase have been established. For the first time the enantioselective hydrolysis of 3-acetoxy-7-bromo-1-methyl-5-phenyl-1,2-dihydro-3H-1,4-benzdiazepine-2-one was accomplished using free and immobilized in phyllophorine and alginate, stabilized by Ca2+ microsomal fraction. The S-enantiomer of substrate was isolated, which suggests the increased specificity of pig liver microsomal fraction carboxylesterase to its R-enantiomer.

  16. Effect of Mole Percentage of Crosslinker of Silver-poly(N-isopropylacrylamide-co-acrylic acid Hybrid Microgels on Catalytic Reduction of Nitrobenzene

    Directory of Open Access Journals (Sweden)

    Zahoor H. FAROOQI

    2015-02-01

    Full Text Available Poly(N-isopropylacrylamide-co-acrylic acid microgels [P(NIPAM-co-AAc] with 2, 4, 6 and 8 mole percentage of N,N-methylene-bis-acrylamide were used as micro-reactors for the fabrication of Ag nanoparticles using the in situ reduction method. The pure and hybrid microgels were characterized by Fourier transform infrared and Ultraviolet-Visible spectroscopies. Silver-poly(N-isopropylacrylamide-co-acrylic acid hybrid microgels [Ag-P(NIPAM-co-AAc] with different crosslinker contents were used as catalysts for reduction of nitrobenzene (NB in aqueous medium in order to investigate the effect of crosslinker content on the value of apparent rate constant (kapp. 0.041, 0.146, 0.2388 and 0.255 min-1 were found as values of kapp for catalytic reduction of NB using hybrid microgels with 2, 4, 6 and 8 mole percentage of crosslinker, respectively. The effect of crosslinker feed content of hybrid microgels on catalytic activity for reduction of NB was compared to that of reduction of p-nitrophenol in aqueous medium.

  17. Facile synthesis of SiO2@CuxO@TiO2 heterostructures for catalytic reductions of 4-nitrophenol and 2-nitroaniline organic pollutants

    Science.gov (United States)

    Zelekew, Osman Ahmed; Kuo, Dong-Hau

    2017-01-01

    Herein, we designed the p-type CuxO (x = 1 or 2) nanoparticles deposited on SiO2 spherical particle inside and coated with thin layered n-type TiO2 semiconductors outside for reduction purpose. The composite material, abbreviated as SiO2@CuxO@TiO2, 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 CuxO and n-type TiO2 and the built-in electric field. Moreover, the hydride ion and electrons released from NaBH4 together with outward electrons from n-type TiO2, 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.

  18. Enantioselective [4 + 1] Annulation Reactions of α-Substituted Ammonium Ylides To Construct Spirocyclic Oxindoles.

    Science.gov (United States)

    Zheng, Peng-Fei; Ouyang, Qin; Niu, Sheng-Li; Shuai, Li; Yuan, Yi; Jiang, Kun; Liu, Tian-Yu; Chen, Ying-Chun

    2015-07-29

    Ammonium ylides have a long history in organic synthesis, but their application in asymmetric catalysis is still underdeveloped in regard to both substrate scope and reaction pathways compared with phosphorus and sulfur ylides. Here a previously unreported asymmetric [4 + 1] annulation reaction of 3-bromooxindoles and electron-deficient 1-azadienes has been developed through ammonium ylide catalysis of a newly designed 2'-methyl α-isocupreine (α-MeIC), efficiently delivering spirocyclic oxindole compounds incorporating a dihydropyrrole motif in excellent enantioselectivity (up to 99% ee). To the best of our knowledge, this work represents the first example of asymmetric catalysis of ammonium ylides bearing α-substitutions, and the catalytic [4 + 1] annulation pathway of ammonium ylides is also unprecedented. Moreover, (1)H NMR, mass spectroscopy, and computational calculation studies were conducted, and the catalytic cycle and a tentative explanation of the enantioselective mechanism have been successfully elucidated.

  19. Enantioselective Transport by a Steroidal Guanidinium Receptor

    NARCIS (Netherlands)

    Baragaña, Beatriz; Blackburn, Adrian G.; Breccia, Perla; Davis, Anthony P.; Mendoza, Javier de; Padrón-Carrillo, José M.; Prados, Pilar; Riedner, Jens; Vries, Johannes G. de

    2002-01-01

    The cationic steroidal receptors 9 and 11 have been synthesized from cholic acid 3. Receptor 9 extracts N-acetyl-α-amino acids from aqueous media into chloroform with enantioselectivities (L:D) of 7-10:1. The lipophilic variant 11 has been employed for the enantioselective transport of N-acetylpheny

  20. In situ DRIFTS studies on MnOx nanowires supported by activated semi-coke for low temperature selective catalytic reduction of NOx with NH3

    Science.gov (United States)

    Chen, Yan; Zhang, Zuotai; Liu, Lili; Mi, Liang; Wang, Xidong

    2016-03-01

    To mitigate the threat of NOx on the environment, MnOx nanowires were fabricated on activated semi-coke (MnOx NW/ASC) for the first time. The prepared MnOx NW/ASC was used for the low temperature selective catalytic reduction (SCR) of NOx with NH3, which achieved an efficiency of over 90% with a low loading content of 1.64 wt% at 150-210 °C. This high performance could be ascribed to synergistic effect between MnOx and ASC. Specifically, the large specific surface area and reducible property of ASC facilitated the dispersion of MnOx and the formation of Mn3+, respectively. Meanwhile, MnOx nanowires provided more redox sites and lattice oxygen species due to the coexistence of Mn3+ and Mn4+, which accelerated the catalytic cycle. The in situ DRIFTS studies revealed that ASC was conducive to the adsorption of NO and NH3. Most importantly, the existence of Mn3+ favored the formation of amide species and the subsequent reduction reaction. Furthermore, the Langmuir-Hinshelwood (L-H) route between coordinated NH3 and bidentate nitrate was predominating in the SCR process and responsible for the high catalytic activity at low temperature.

  1. Mechanism of N2O formation during the low-temperature selective catalytic reduction of NO with NH3 over Mn-Fe spinel.

    Science.gov (United States)

    Yang, Shijian; Xiong, Shangchao; Liao, Yong; Xiao, Xin; Qi, Feihong; Peng, Yue; Fu, Yuwu; Shan, Wenpo; Li, Junhua

    2014-09-02

    The mechanism of N2O formation during the low-temperature selective catalytic reduction reaction (SCR) over Mn-Fe spinel was studied. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and transient reaction studies demonstrated that the Eley-Rideal mechanism (i.e., the reaction of adsorbed NH3 species with gaseous NO) and the Langmuir-Hinshelwood mechanism (i.e., the reaction of adsorbed NH3 species with adsorbed NOx species) both contributed to N2O formation. However, N2O selectivity of NO reduction over Mn-Fe spinel through the Langmuir-Hinshelwood mechanism was much less than that through the Eley-Rideal mechanism. The ratio of NO reduction over Mn-Fe spinel through the Langmuir-Hinshelwood mechanism remarkably increased; therefore, N2O selectivity of NO reduction over Mn-Fe spinel decreased with the decrease of the gas hourly space velocity (GHSV). As the gaseous NH3 concentration increased, N2O selectivity of NO reduction over Mn-Fe spinel increased because of the promotion of NO reduction through the Eley-Rideal mechanism. Meanwhile, N2O selectivity of NO reduction over Mn-Fe spinel decreased with the increase of the gaseous NO concentration because the formation of NH on Mn-Fe spinel was restrained. Therefore, N2O selectivity of NO reduction over Mn-Fe spinel was related to the GHSV and concentrations of reactants.

  2. Effects of natural water ions and humic acid on catalytic nitrate reduction kinetics using an alumina supported Pd-Cu catalyst.

    Science.gov (United States)

    Chaplin, Brian P; Roundy, Eric; Guy, Kathryn A; Shapley, John R; Werth, Charles J

    2006-05-01

    Catalytic nitrate reduction was evaluated for the purpose of drinking water treatment. Common anions present in natural waters and humic acid were evaluated for their effects on NO3(-) hydrogenation over a bimetallic supported catalyst (Pd-Cu/gamma-Al2O3). Groundwater samples, with and without powder activated carbon (PAC) pretreatment, were also evaluated. In the absence of inhibitors the NO3- reduction rate was 2.4 x 10(-01) L/min g cat. However, the addition of constituents (SO4(2-), SO3(2-), HS-, CI-, HCO3-, OH-, and humic acid) on the order of representative concentrations for drinking water decreased the NO3- reduction rate. Sulfite, sulfide, and elevated chloride decreased the NO3- reduction rate by over 2 orders of magnitude. Preferential adsorption of Cl- inhibited NO3- reduction to a greater extent than NO2- reduction. Partial regeneration of catalysts exposed to SO3(2-) was achieved by using a dilute hypochlorite solution, however Cu dissolution occurred. Dissolved constituents in the groundwater sample decreased the NO3- reduction rate to 3.7 x 10(-03) L/min g cat and increased ammonia production. Removal of dissolved organic matter from the groundwater using PAC increased the NO3- reduction rate to 5.06 x 10(-02) L/min g cat and decreased ammonia production. Elemental analyses of catalysts exposed to the natural groundwater suggest that mineral precipitation may also contribute to catalyst fouling.

  3. Green synthesis of Pd nanoparticles at Apricot kernel shell substrate using Salvia hydrangea extract: Catalytic activity for reduction of organic dyes.

    Science.gov (United States)

    Khodadadi, Bahar; Bordbar, Maryam; Nasrollahzadeh, Mahmoud

    2017-03-15

    For the first time the extract of the plant of Salvia hydrangea was used to green synthesis of Pd nanoparticles (NPs) supported on Apricot kernel shell as an environmentally benign support. The Pd NPs/Apricot kernel shell as an effective catalyst was prepared through reduction of Pd(2+) ions using Salvia hydrangea extract as the reducing and capping agent and Pd NPs immobilization on Apricot kernel shell surface in the absence of any stabilizer or surfactant. According to FT-IR analysis, the hydroxyl groups of phenolics in Salvia hydrangea extract as bioreductant agents are directly responsible for the reduction of Pd(2+) ions and formation of Pd NPs. The as-prepared catalyst was characterized by Fourier transform infrared (FT-IR) and UV-Vis spectroscopy, field emission scanning electron microscopy (FESEM) equipped with an energy dispersive X-ray spectroscopy (EDS), Elemental mapping, X-ray diffraction analysis (XRD) and transmittance electron microscopy (TEM). The synthesized catalyst was used in the reduction of 4-nitrophenol (4-NP), Methyl Orange (MO), Methylene Blue (MB), Rhodamine B (RhB), and Congo Red (CR) at room temperature. The Pd NPs/Apricot kernel shell showed excellent catalytic activity in the reduction of these organic dyes. In addition, it was found that Pd NPs/Apricot kernel shell can be recovered and reused several times without significant loss of catalytic activity.

  4. Effect of SO2 on the performance of Ag-Pd/Al2O3 for the selective catalytic reduction of NOx with C2H5OH

    Institute of Scientific and Technical Information of China (English)

    XIE Shu-xia; YU Yun-bo; WANG Jin; HE Hong

    2006-01-01

    The influence of SO2 on the performance of Ag-Pd/Al2O3 for the selective catalytic reduction (SCR) of NOx with C2H5OH was investigated experimentally. The activity test results suggest that Ag-Pd/Al2O3 shows a small activity loss in the presence of SO2 when using C2H5OH as a reductant. In situ DRIFTS spectra show that the activity loss originates from the formation of surface sulphate species on the Ag-Pd/Al2O3. The surface sulphate species formation inhibits the formation of nitrate, whereas hardly changes the partial oxidation of C2H5OH. Compared with the NOx reduction by C3H6, an obvious suppression of the surface sulphate species formation was observed by DRIFTS experiment when using C2H5OH as a reductant. This phenomenon reveals the better catalytic performance and strong SO2 tolerance of Ag-Pd/Al2O3-C2H5OH system.

  5. Mo-catalyzed asymmetric olefin metathesis in target-oriented synthesis: Enantioselective synthesis of (+)-africanol

    Science.gov (United States)

    Weatherhead, Gabriel S.; Cortez, G. A.; Schrock, Richard R.; Hoveyda, Amir H.

    2004-01-01

    Catalytic asymmetric ring-opening metathesis (AROM) provides an efficient method for the synthesis of a variety of optically enriched small organic molecules that cannot be easily prepared by alternative methods. The development of Mo-catalyzed AROM transformations that occur in tandem with ring-closing metathesis are described. The utility of the Mo-catalyzed AROM/ring-closing metathesis is demonstrated through an enantioselective approach to the synthesis of (+)-africanol. PMID:15056762

  6. 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.

  7. The characterization and activity of F-doped vanadia/titania for the selective catalytic reduction of NO with NH3 at low temperatures.

    Science.gov (United States)

    Li, Yuntao; Zhong, Qin

    2009-12-30

    A F-doped vanadia/titania catalyst has been developed by partly substituting the lattice oxygen of the catalyst with fluorine, using NH(4)F as a precursor. The aim of this novel design was to promote the activity of a catalyst with low vanadia loading in the low-temperature selective catalytic reduction of NO with NH(3). Analysis by N(2) physisorption, XPS, ICP, XRD, ESR and PL spectra showed that fluorine doping facilitated the formation of V(4+) and Ti(3+) ions mainly by charge compensation, promoted the distribution of vanadium on the catalyst surface, and increased the amount of surface superoxide ions. The catalytic activity of NO removal was promoted by F-doping. And the catalyst with [F]/[Ti]=1.35 x 10(-2) showed the highest NO removal efficiency in SCR reaction at low temperatures.

  8. Green synthesis of layered 1T-MoS2/reduced graphene oxide nanocomposite with excellent catalytic performances for 4-nitrophenol reduction

    Science.gov (United States)

    Meng, Nannan; Cheng, Jian; Zhou, Yifeng; Nie, Wangyan; Chen, Pengpeng

    2017-02-01

    A green and facile process was developed to prepare layered octahedral phase MoS2/reduced graphene oxide (1T-MoS2/RGO) nanocomposite by a Vitamin C-assisted self-assemble method, in which graphene oxide (GO) and LiMoS2 were used as starting materials. Catalytic performances of 1T-MoS2/RGO were evaluated by hydrogenation of 4-nitrophenol (4-NP). It was demonstrated that the prepared 1T-MoS2/RGO nanocomposite presented excellent catalytic performance and cycling stability for 4-NP reduction, which made it a promising noble-metal-free catalyst. Additionally, broadening work suggested some other RGO-based metal nanocomposite with well-defined porous structure could be also generated via this facile self-assembly method.

  9. 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.

  10. Synthesis of Au nanoparticles decorated graphene oxide nanosheets: Noncovalent functionalization by TWEEN 20 in situ reduction of aqueous chloroaurate ions for hydrazine detection and catalytic reduction of 4-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Wenbo [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, Jilin (China); Ning, Rui [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, Jilin (China); Graduate School of the Chinese Academy of Sciences, Beijing 100039 (China); Qin, Xiaoyun; Zhang, Yingwei; Chang, Guohui; Liu, Sen; Luo, Yonglan [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, Jilin (China); Sun, Xuping, E-mail: sunxp@ciac.jl.cn [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, Jilin (China)

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer TWEEN 20 is used as a stabilizing agent for GO as well as a reducing and immobilizing agent for Au nanoparticles. Black-Right-Pointing-Pointer The hydrazine sensor based on the nanocomposites has a fast amperometric response. Black-Right-Pointing-Pointer The detection limit of the hydrazine sensor is estimated to be 78 nM. Black-Right-Pointing-Pointer The nanocomposites also exhibit good catalytic activity toward 4-nitrophenol reduction. - Abstract: In this paper, we develop a cost-effective and simple route for the synthesis of Au nanoparticles (AuNPs) decorated graphene oxide (GO) nanosheets using polyoxyethylene sorbitol anhydride monolaurate (TWEEN 20) as a stabilizing agent for GO as well as a reducing and immobilizing agent for AuNPs. The AuNPs assemble on the surface of TWEEN-functionalized GO by the in situ reduction of HAuCl{sub 4} aqueous solution. The morphologies of these composites were characterized by atomic force microscopy (AFM) and transmission electron microscopy (TEM). It is found that the resultant AuNPs decorated GO nanosheets (AuNPs/TWEEN/GO) exhibit remarkable catalytic performance for hydrazine oxidation. This hydrazine sensor has a fast amperometric response time of less than 3 s. The linear range is estimated to be from 5 {mu}M to 3 mM (r = 0.999), and the detection limit is estimated to be 78 nM at a signal-to-noise ratio of 3. The AuNPs/TWEEN/GO composites also exhibit good catalytic activity toward 4-nitrophenol (4-NP) reduction and the GO supports also enhance the catalytic activity via a synergistic effect.

  11. Enantioselective Synthesis of N-PMP-1,2-dihydropyridines via Formal [4 + 2] Cycloaddition between Aqueous Glutaraldehyde and Imines.

    Science.gov (United States)

    Ramaraju, Panduga; Mir, Nisar A; Singh, Deepika; Gupta, Vivek K; Kant, Rajni; Kumar, Indresh

    2015-11-20

    A simple and highly practical one-pot formal [4 + 2] cycloaddition approach for the enantioselective synthesis of N-PMP-1,2-dihydropyridines (DHPs) is described. This chemistry involves an amino-catalytic direct Mannich reaction/cyclization followed by IBX-mediated chemo- and regioselective oxidation sequence between readily available aqueous glutaraldehyde and imines under very mild conditions. A series of N-PMP-1,2-DHPs have been prepared in high yields and excellent enantioselectivity. This method also gives access to both enantiomers of 1,2-DHPs in surplus amount by shifting the catalyst configuration.

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

    NARCIS (Netherlands)

    Deka, U.; Lezcano-Gonzalez, I.; Weckhuysen, B.M.; Beale, A.M.

    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 r

  13. 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.

  14. Promotional Effect on Selective Catalytic Reduction of NOx with NH3 over Overloaded W and Ce on V2O5/TiO2 Catalysts

    OpenAIRE

    Seunghee Youn; Inhak Song; Do Heui Kim

    2015-01-01

    W and Ce are known to be a good promoters to improve selective catalytic reduction (SCR) activity for V2O5/TiO2 catalysts. This work aimed at finding the optimum ratio and loading of promoters (W and Ce) on V2O5/TiO2 catalyst in order to improve SCR reactivity in low temperature region and to minimize N2O formation in high temperature region. In addition, we changed the order of impregnation between W and Ce precursors on V2O5/TiO2 catalyst during the preparation and observed its effect on SC...

  15. Structural and kinetic changes to small-pore Cu-zeolites after hydrothermal aging treatments and selective catalytic reduction of NO_x with ammonia

    OpenAIRE

    Albarracin-Caballero, Jonatan D.; Khurana, Ishant; Di Iorio, John R.; Shih, Arthur J.; Schmidt, Joel E.; Dusselier, Michiel; Davis, Mark E.; Yezerets, Aleksey; Miller, Jeffrey T.; Ribeiro, Fabio H.; Gounder, Rajamani

    2016-01-01

    Three small-pore, eight-membered ring (8-MR) zeolites of different cage-based topology (CHA, AEI, RTH), in their proton- and copper-exchanged forms, were first exposed to high temperature hydrothermal aging treatments (1073 K, 16 h, 10% (v/v) H_2O) and then to reaction conditions for low temperature (473 K) standard selective catalytic reduction (SCR) of NO_x with ammonia, in order to study the effect of zeolite topology on the structural and kinetic changes that occur to Cu-zeolites used in ...

  16. Bauxite-supported Transition Metal Oxides: Promising Low-temperature and SO2-tolerant Catalysts for Selective Catalytic Reduction of NOx

    OpenAIRE

    Xiuyun Wang; Wen Wu; Zhilin Chen; Ruihu Wang

    2015-01-01

    In order to develop low-temperature (below 200 °C) and SO2-tolerant catalysts for selective catalytic reduction (SCR) of NOx, a series of cheap M/bauxite (M = Mn, Ni and Cu) catalysts were prepared using bauxite as a support. Their SCR performances are much superior to typical V2O5/TiO2, the addition of M into bauxite results in significant promotion of NOx removal efficiency, especially at low temperature. Among the catalysts, Cu/bauxite exhibits wide temperature window over 50–400 °C, stron...

  17. Selective catalytic reduction of NO by ammonia using mesoporous Fe-containing HZSM-5 and HZSM-12 zeolite catalysts: An option for automotive applications

    DEFF Research Database (Denmark)

    Kustov, Arkadii; Hansen, T. W.; Kustova, Marina;

    2007-01-01

    Mesoporous and conventional Fe-containing ZSM-5 and ZSM-12 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnation method and tested in the selective catalytic reduction (SCR) of NO with NH3. It was found that for both Fe/HZSM-5 and Fe/HZSM-12 catalysts with similar Fe contents......, the activity of the mesoporous samples in NO SCR with NH3 is significantly higher than for conventional samples. Such a difference in the activity is probably related with the better diffusion of reactants and products in the mesopores and better dispersion of the iron particles in the mesoporous zeolite...

  18. WO3/CeO2/TiO2 Catalysts for Selective Catalytic Reduction of NO(x) by NH3: Effect of the Synthesis Method.

    Science.gov (United States)

    Michalow-Mauke, Katarzyna A; Lu, Ye; Ferri, Davide; Graule, Thomas; Kowalski, Kazimierz; Elsener, Martin; Kröcher, Oliver

    2015-01-01

    WO3/CeO2/TiO2, CeO2/TiO2 and WO3/TiO2 catalysts were prepared by wet impregnation. CeO2/TiO2 and WO3/TiO2 showed activity towards the selective catalytic reduction (SCR) of NO(x) by NH3, which was significantly improved by subsequent impregnation of CeO/TiO2 with WO3. Catalytic performance, NH3 oxidation and NH3 temperature programmed desorption of wet-impregnated WO3/CeO2/TiO2 were compared to those of a flame-made counterpart. The flame-made catalyst exhibits a peculiar arrangement of W-Ce-Ti-oxides that makes it very active for NH3-SCR. Catalysts prepared by wet impregnation with the aim to mimic the structure of the flame-made catalyst were not able to fully reproduce its activity. The differences in the catalytic performance between the investigated catalysts were related to their structural properties and the different interaction of the catalyst components.

  19. Performance of nitrogen-containing macroporous carbon supported cobalt catalyst synthesized through in-situ construction of catalytic sites for oxygen reduction reaction

    Science.gov (United States)

    He, Fan; Yang, Jun; Li, Rui; Liu, Bin Hong; Li, Zhou Peng

    2015-01-01

    A novel method of in-situ catalytic site (CoNx) construction in macroporous carbon (MPC) is developed. The nitrogen-containing MPC-supported cobalt (Co/N-MPC) catalysts are synthesized via the pyrolysis of a mixture of glucose-urea resin, nano-CaCO3, and cobalt nitrate. The nano-CaCO3 functions as a template to fabricate MPC that provides high electric conductivity and large specific surface area. The catalytic CoNx sites are simultaneously created during the formation of N-MPC. The use of glucose-urea resin as the carbon and nitrogen sources significantly increases the nitrogen content as high as 8.8 at% in the MPC. The synthesized Co/N-MPC demonstrates superb catalytic activity toward oxygen reduction reaction. The direct borohydride fuel cell using the Co/N-MPC shows a power density as high as 170 mW cm-2 which is much higher than the cell using 10 wt.% Pt/C but slightly lower than the cell using 20 wt.% Pt/C as the cathode catalyst at ambient conditions.

  20. 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.

  1. Influence of calcination temperature on selective catalytic reduction of NOx with NH3 over CeO2-ZrO2-WO3 catalyst

    Institute of Scientific and Technical Information of China (English)

    李军燕; 宋忠贤; 宁平; 张秋林; 刘昕; 李昊; 黄真真

    2015-01-01

    A series of CeO2-ZrO2-WO3 catalysts for the selective catalytic reduction (SCR) of NO with NH3 were prepared by hydro-thermal method. The influence of calcination temperature on the catalytic activity, microstructure, surface acidity and redox behavior of CeO2-ZrO2-WO3 catalyst was investigated using various characterization methods. It was found that the CeO2-ZrO2-WO3 catalyst calcined at 600 ºC showed the best catalytic performance and excellent N2 selectivity, and yielded more than 90% NO conversion in a wide temperature range of 250–500 ºC with a space velocity (GHSV) of 60000 h–1. As the calcination temperature was increased from 400 to 600 ºC, the NO conversion obviously increased, but decreased at higher calcination temperature. The results implied that the higher surface area, the strongest synergistic interaction, the superior redox property and the highly dispersed or amorphous WO3 species contributed to the excellent SCR activity of the CeO2-ZrO2-WO3 catalyst calcined at 600 ºC.

  2. 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.

  3. Influence of Sulfation on the Catalytic Activity of Ni-ZrO2 for NO Reduction with Propane in Excess Oxygen

    Institute of Scientific and Technical Information of China (English)

    Shujuan Zhang; Landong Li; Fuxiang Zhang; Naijia Guan

    2005-01-01

    Selective catalytic reduction (SCR) of nitric oxide with propane in excess oxygen was investigated on Ni-ZrO2 (NZ) and sulfated Ni-ZrO2 (SNZ), prepared by coprecipitation from a mixture of nickel nitrate-zirconium oxychloride followed by modifying with (NH4)2SO4. It was found that sulfated Ni-ZrO2catalyst showed higher activity for the SCR of NO with propane than that of Ni-ZrO2. The structural and surface properties of catalysts were studied by XRD, BET, SEM and FT-IR of pyridine adsorption. The experimental results indicated that the modification of (NH4)2SO4 resulted in the generation of strong Bronsted and Lewis acid sites and promoted the dispersion of the Ni species, which could lead to higher NO conversion and propane efficiency in NO reduction.

  4. 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

  5. Study on methane selective catalytic reduction of NO on Pt/Ce0.67Zr0.33O2 and its application

    Institute of Scientific and Technical Information of China (English)

    Zhimin Liu; Kangcai Wang; Xiaoyu Zhang; Jianli Wang; Hongyan Cao; Maochu Gong; Yaoqiang Chen

    2009-01-01

    Monolithic catalysts of Pt/La-Al2O3 and Pt/Ce0.67Zr0.33O2 were prepared to investigate methane selective catalytic reduction (SCR) of NO.The results indicate that Pt/Ce0.67Zr0.33O2 shows high activity and both NO and CH4 can be converted completely at 450 ℃.Meanwhile,NO and CH4 can be converted completely when there exists excess oxygen.The Pt/Ce0.67Zr0.33O2 catalyst were further investigated by using methane as reducing agent to SCR NO in a novel equipment which combined the CH4 selective catalytic reduction of NO with methane combustion.The result shows that the catalyst is high active and the novel equipment is very effective.The conversion of NO is above 92% under the conditions used in this work.The prepared burner and catalysts have great potential for application.

  6. Crystal structure and characterization of esterase Est25 mutants reveal improved enantioselectivity toward (S)-ketoprofen ethyl ester.

    Science.gov (United States)

    Kim, Jinyeong; Seok, Seung-Hyeon; Hong, Eunsoo; Yoo, Tae Hyeon; Seo, Min-Duk; Ryu, Yeonwoo

    2017-03-01

    Esterases comprise a group of enzymes that catalyze the cleavage and synthesis of ester bonds. They are important in biotechnological applications owing to their enantioselectivity, regioselectivity, broad substrate specificity, and the fact that they do not require cofactors. In a previous study, we isolated the esterase Est25 from a metagenomic library. Est25 showed catalytic activity toward the (R,S)-ketoprofen ethyl ester but had low enantioselectivity toward the (S)-ketoprofen ethyl ester. Because (S)-ketoprofen has stronger anti-inflammatory effects and fewer side effects than (R)-ketoprofen, enantioselectivity of this esterase is important. In this study, we generated Est25 mutants with improved enantioselectivity toward the (S)-ketoprofen ethyl ester; improved enantioselectivity of mutants was established by analysis of their crystal structures. The enantioselectivity of mutants was influenced by substitution of Phe72 and Leu255. Substituting these residues changed the size of the binding pocket and the entrance hole that leads to the active site. The enantioselectivity of Est25 (E = 1.1 ± 0.0) was improved in the mutants F72G (E = 1.9 ± 0.2), L255W (E = 16.1 ± 1.1), and F72G/L255W (E = 60.1 ± 0.5). Finally, characterization of Est25 mutants was performed by determining the optimum reaction conditions, thermostability, effect of additives, and substrate specificity after substituting Phe72 and Leu255.

  7. Proline Based Chiral Ionic Liquids for Enantioselective Michael Reaction

    Directory of Open Access Journals (Sweden)

    Kaoru Nobuoka

    2014-01-01

    Full Text Available Chiral ionic liquids, starting from (S-proline, have been prepared and evaluated the ability of a chiral catalyst. In Michael reaction of trans-β-nitrostyrene and cyclohexanone, all the reactions were carried out under homogeneous conditions without any solvent except for excess cyclohexanone. The chiral ionic liquid catalyst with the positive charge delocalized bulky pyrrolidinium cation shows excellent yields (up to 92%, diastereoselectivities (syn/anti = 96/4, and enantioselectivities (up to 95% ee and could be reused at least three times without any loss of its catalytic activity. Such results demonstrated a promising new approach for green and economic chiral synthesis by using the chiral ionic liquids as a chiral catalyst and a chiral medium.

  8. Pd/Sulfated Alumina: a Novel Catalyst for Selective Catalytic Reduction of NO with Methane%Pd/硫酸化氧化铝——一种新型甲烷选择还原NO催化剂

    Institute of Scientific and Technical Information of China (English)

    李宁; 王爱琴; 郑明远; 王晓东; 张涛

    2003-01-01

    Recently, much attention has been directed to the selective catalytic reduction (SCR) of NO with methane as reductant[1,2]. Pd-based catalysts have been found to be active for the reaction[3~6]. However, the performance of the Pd-based catalysts for this reaction depends strongly on the nature of the supports[3,4].

  9. 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

  10. 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....

  11. pH dependence of proton translocation in the oxidative and reductive phases of the catalytic cycle of cytochrome c oxidase. The role of H2O produced at the oxygen-reduction site.

    Science.gov (United States)

    Capitanio, Giuseppe; Martino, Pietro Luca; Capitanio, Nazzareno; De Nitto, Emanuele; Papa, Sergio

    2006-02-14

    A study is presented on the pH dependence of proton translocation in the oxidative and reductive phases of the catalytic cycle of purified cytochrome c oxidase (COX) from beef heart reconstituted in phospholipid vesicles (COV). Protons were shown to be released from COV both in the oxidative and reductive phases. In the oxidation by O2 of the fully reduced oxidase, the H+/COX ratio for proton release from COV (R --> O transition) decreased from approximately 2.4 at pH 6.5 to approximately 1.8 at pH 8.5. In the direct reduction of the fully oxidized enzyme (O --> R transition), the H+/COX ratio for proton release from COV increased from approximately 0.3 at pH 6.5 to approximately 1.6 at pH 8.5. Anaerobic oxidation by ferricyanide of the fully reduced oxidase, reconstituted in COV or in the soluble case, resulted in H+ release which exhibited, in both cases, an H+/COX ratio of 1.7-1.9 in the pH range 6.5-8.5. This H+ release associated with ferricyanide oxidation of the oxidase, in the absence of oxygen, originates evidently from deprotonation of acidic groups in the enzyme cooperatively linked to the redox state of the metal centers (redox Bohr protons). The additional H+ release (O2 versus ferricyanide oxidation) approaching 1 H+/COX at pH or = 8.5, this additional proton release takes place in the reductive phase of the catalytic cycle of the oxidase. The H+/COX ratio for proton release from COV in the overall catalytic cycle, oxidation by O2 of the fully reduced oxidase directly followed by re-reduction (R --> O --> R transition), exhibited a bell-shaped pH dependence approaching 4 at pH 7.2. A mechanism for the involvement in the proton pump of the oxidase of H+/e- cooperative coupling at the metal centers (redox Bohr effects) and protonmotive steps of reduction of O2 to H2O is presented.

  12. Reduction of sulfur in gasoline using catalytic cracking; Reducao de enxofre na gasolina via craqueamento catalitico (FCC)

    Energy Technology Data Exchange (ETDEWEB)

    Roncolatto, Rodolfo E.; Gilbert, William; Chamberlain, Oscar [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas; Keyworth, Don [Akzo Nobel, Arnhem (Netherlands)

    2000-07-01

    FCC catalysts or additives can help in reducing sulfur in cracked naphta. The type of sulfur compounds in the feed has a considerable impact in the sulfur reduction, thiophenic species are less reactive while mercaptans and sulfides are more reactive. Contaminant metals like nickel and vanadium can help in the reduction of sulfur due to their dehydrogenation ability. (author)

  13. Facile preparation of ordered mesoporous MnCo2O4 for low-temperature selective catalytic reduction of NO with NH3

    Science.gov (United States)

    Qiu, Mingying; Zhan, Sihui; Yu, Hongbing; Zhu, Dandan; Wang, Shengqiang

    2015-01-01

    Ordered mesoporous MnCo2O4 nanomaterials were successfully prepared through the nanocasting route using SBA-15 and KIT-6 as hard templates. These mesoporous nanomaterials were characterized using XRD, BET, TEM, NH3-TPD, H2-TPR, NO-TPD, XPS and DRIFT. The low temperature selective catalytic reduction (SCR) activity of NO with NH3 was investigated, which revealed that 3D-MnCo2O4 using KIT-6 as a template can totally clean all NO over a wide temperature range of 100-250 °C with a gas hourly space velocity (GHSV) of 32 000 h-1, while 2D-MnCo2O4 with SBA-15 as a template had 95% conversion rate at the same condition. 3D-MnCo2O4 showed the best performance to clean NO due to its typical three-dimensional porous structure, large specific surface area, abundant active surface oxygen species and Lewis acid sites. All the results indicate that a novel, cheap catalyst for catalytic removal of NO can be designed by controlling the morphology at the nanoscale.Ordered mesoporous MnCo2O4 nanomaterials were successfully prepared through the nanocasting route using SBA-15 and KIT-6 as hard templates. These mesoporous nanomaterials were characterized using XRD, BET, TEM, NH3-TPD, H2-TPR, NO-TPD, XPS and DRIFT. The low temperature selective catalytic reduction (SCR) activity of NO with NH3 was investigated, which revealed that 3D-MnCo2O4 using KIT-6 as a template can totally clean all NO over a wide temperature range of 100-250 °C with a gas hourly space velocity (GHSV) of 32 000 h-1, while 2D-MnCo2O4 with SBA-15 as a template had 95% conversion rate at the same condition. 3D-MnCo2O4 showed the best performance to clean NO due to its typical three-dimensional porous structure, large specific surface area, abundant active surface oxygen species and Lewis acid sites. All the results indicate that a novel, cheap catalyst for catalytic removal of NO can be designed by controlling the morphology at the nanoscale. Electronic supplementary information (ESI) available: Low-angle XRD

  14. Active and Recyclable Catalytic Synthesis of Indoles by Reductive Cyclization of 2-(2-Nitroaryl)acetonitriles in the Presence of Co-Rh Heterobimetallic Nanoparticles with Atmospheric Hydrogen under Mild Conditions.

    Science.gov (United States)

    Choi, Isaac; Chung, Hyunho; Park, Jang Won; Chung, Young Keun

    2016-11-04

    A cobalt-rhodium heterobimetallic nanoparticle-catalyzed reductive cyclization of 2-(2-nitroaryl)acetonitriles to indoles has been achieved. The tandem reaction proceeds without any additives under the mild conditions (1 atm H2 and 25 °C). This procedure could be scaled up to the gram scale. The catalytic system is significantly stable under these reaction conditions and could be reused more than ten times without loss of catalytic activity.

  15. 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.

  16. 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.

  17. Highly diastereoselective and enantioselective olefin cyclopropanation using engineered myoglobin-based catalysts.

    Science.gov (United States)

    Bordeaux, Melanie; Tyagi, Vikas; Fasan, Rudi

    2015-02-01

    Using rational design, an engineered myoglobin-based catalyst capable of catalyzing the cyclopropanation of aryl-substituted olefins with catalytic proficiency (up to 46,800 turnovers) and excellent diastereo- and enantioselectivity (98-99.9%) was developed. This transformation could be carried out in the presence of up to 20 g L(-1) olefin substrate with no loss in diastereo- and/or enantioselectivity. Mutagenesis and mechanistic studies support a cyclopropanation mechanism mediated by an electrophilic, heme-bound carbene species and a model is provided to rationalize the stereopreference of the protein catalyst. This work shows that myoglobin constitutes a promising and robust scaffold for the development of biocatalysts with carbene-transfer reactivity.

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

    Science.gov (United States)

    An, Baiyi; Fan, Hailin; Wu, Zhuofu; Zheng, Lu; Wang, Lei; Wang, Zhi; Chen, Guang

    2016-04-28

    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.

  19. Enantioselective Intramolecular Hydroarylation of Alkenes via Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Harada, Hitoshi; Thalji, Reema; Bergman, Robert; Ellman, Jonathan

    2008-05-22

    Highly enantioselective catalytic intramolecular ortho-alkylation of aromatic imines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using [RhCl(coe){sub 2}]{sub 2} and chiral phosphoramidite ligands. Cyclization of substrates containing 1,1- and 1,2-disubstituted as well as trisubstituted alkenes were achieved with enantioselectivities >90% ee for each substrate class. Cyclization of substrates with Z-alkene isomers proceeded much more efficiently than substrates with E-alkene isomers. This further enabled the highly stereoselective intramolecular alkylation of certain substrates containing Z/E-alkene mixtures via a Rh-catalyzed alkene isomerization with preferential cyclization of the Z-isomer.

  20. [Nano-MnO(x) catalyst for the selective catalytic reduction of NO by NH3 in low-temperature].

    Science.gov (United States)

    Tang, Xiao-Long; Hao, Ji-Ming; Xu, Wen-Guo; Li, Jun-Hua

    2007-02-01

    Nanometer particles composed of manganese oxides (Nano-MnO(x)), which prepared by rheological phase reaction method, show superior low-temperature SCR activity for NO with NH3 in the presence of excess O2. In experiments, the NO conversion is 98.25% at 80 degrees C, and nearly 100% NO could be converted in 100 - 150 degrees C. Due to the reason of competing adsorption, H2O has a slight impact on the activity and the deactivation of SO2 is reversible. The experiments implied that the superior low-temperature catalytic activity of Nano-MnO(x) was mainly due to its high BET specific areas and poor crystallinity.

  1. Evaluation of a catalytic reduction technique for the measurement of total reactive odd-nitrogen NOy in the atmosphere

    Science.gov (United States)

    Fahey, D. W.; Eubank, C. S.; Hubler, C. S.; Fehsenfeld, F. C.

    1985-01-01

    The suitability of a technique for the measurement of total reactive odd-nitrogen NOy-containing species in the atmosphere has been examined. In the technique, an NOy component species, which may include NO, NO2, NO3, HNO3, peroxyacetyl nitrate, and particulate nitrate, are catalytically reduced by CO to form NO molecules on the surface of a metal converter tube, and the NO product is detected by chemiluminescence produced in reaction with O3. Among the catalysts tested in the temperature range of 25-500 C, Au was the preferred catalyst. The results of laboratory tests investigating the effects of pressure, O3, and H2O on NOy conversion, and the possible sources of interference, have shown that the technique is suitable for atmospheric analyses. The results of a test in ambient air at a remote ground-based field site are included.

  2. Low temperature selective catalytic reduction of NO by C3H6 over CeOx loaded on AC treated by HNO3

    Institute of Scientific and Technical Information of China (English)

    楚英豪; 尹华强; 张腾腾; 朱晓帆; 郭家秀; 刘勇军; 刘超

    2015-01-01

    The activated carbons from coal were treated by HNO3 (named as NAC) and used as carriers to load 7% Ce (named as Ce(0.07)/NAC) by impregnation method. The physical and chemical properties were investigated by thermogravimetric-differential thermal analysis (TG-DTA), Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), scanning electron microscopy (SEM) and NH3-temperature programmed desorption (NH3-TPD) and NO-temperature programmed desorption techniques. The catalytic activities of Ce(0.07)/NAC were evaluated for the low temperature selective catalytic reduction (SCR) of NO with C3H6 using temperature-programmed reaction (TP-reaction) in NO, C3H6, O2 and N2 as a balance. The results showed that the specific surface area of Ce(0.07)/NAC was 850.8 m2/g and less than NAC, but Ce oxides could be dispersed highly on the acti-vated carbons. Ce oxides could change acid sites and NO adsorption as well as oxygen-containing functional groups of activated car-bons, and Ce4+ and Ce3+ coexisted in catalysts. The conversion of NO with C3H6 achieved 70% at 280 °C over Ce(0.07)/NAC, but with the increase of O2 concentration, heat accumulation and nonselective combustion were exacerbated, which could cause surface ashing and roughness, resulting in a sharp decrease of catalytic activities. The optimum O2 concentration used in the reaction system was 3% and achieved the high conversion of NO and the widest temperature window. The conversion of NO was closely related to the NO concentrations and [NO]/[C3H6] ratios, and the stoichiometric number was just close to 2:1, but the presence of H2O could af-fect the denitration efficiency of catalyst.

  3. TiO2-Supported Binary Metal Oxide Catalysts for Low-temperature Selective Catalytic Reduction of NOx with NH3

    Institute of Scientific and Technical Information of China (English)

    WU Bi-jun; LIU Xiao-qin; XIAO Ping; WANG Shu-gang

    2008-01-01

    Binary metal oxide(MnOx-A/TiO2) catalysts were prepared by adding the second metal to manganese oxides supported on titanium dioxide(TiO2),where,A indicates Fe2O3,WO3,MoO3,and Cr2O3.Their catalytic activity,N2 selectivity,and SO2 poisonous tolerance were investigated.The catalytic performance at low temperatures decreased in the following order:Mn-W/TiO2>Mn-Fe/TiO2>Mn-Cr/TiO2>Mn-Mo/TiO2,whereas the N2 selectivity decreased in the order:Mn-Fe/TiO2>Mn-W/TiO2>Mn-Mo/TiO2>Mn-Cr/TiO2.In the presence of 0.01% SO2 and 6% H2O,the NOx conversions in the presence of Mn-W/TiO2,Mn-Fe/TiO2,or Mn-Mo/TiO2 maintain 98.5%,95.8% and 94.2%,respectively,after 8 h at 120 ℃ at GHSV 12600 h-1.As effective promoters,WO3 and Fe2O3 can increase N2 selectivity and the resistance to SO2 of MnOx/TiO2 significantly.The Fourier transform infrared(FTIR) spectra of NH3 over WO3 show the presence of Lewis acid sites.The results suggest that WO3 is the best promoter of MnOx/TiO2,and Mn-W/TiO2 is one of the most active catalysts for the low temperature selective catalytic reduction of NO with NH3.

  4. 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.

  5. New phosphine-diamine and phosphine-amino-alcohol tridentate ligands for ruthenium catalysed enantioselective hydrogenation of ketones and a concise lactone synthesis enabled by asymmetric reduction of cyano-ketones

    Directory of Open Access Journals (Sweden)

    Fuentes José A

    2012-12-01

    Full Text Available Abstract Enantioselective hydrogenation of ketones is a key reaction in organic chemistry. In the past, we have attempted to deal with some unsolved challenges in this arena by introducing chiral tridentate phosphine-diamine/Ru catalysts. New catalysts and new applications are presented here, including the synthesis of phosphine-amino-alcohol P,N,OH ligands derived from (R,S-1-amino-2-indanol, (S,S-1-amino-2-indanol and a new chiral P,N,N ligand derived from (R,R-1,2-diphenylethylenediamine. Ruthenium pre-catalysts of type [RuCl2(L(DMSO] were isolated and then examined in the hydrogenation of ketones. While the new P,N,OH ligand based catalysts are poor, the new P,N,N system gives up to 98% e.e. on substrates that do not react at all with most catalysts. A preliminary attempt at realising a new delta lactone synthesis by organocatalytic Michael addition between acetophenone and acrylonitrile, followed by asymmetric hydrogenation of the nitrile functionalised ketone is challenging in part due to the Michael addition chemistry, but also since Noyori pressure hydrogenation catalysts gave massively reduced reactivity relative to their performance for other acetophenone derivatives. The Ru phosphine-diamine system allowed quantitative conversion and around 50% e.e. The product can be converted into a delta lactone by treatment with KOH with complete retention of enantiomeric excess. This approach potentially offers access to this class of chiral molecules in three steps from the extremely cheap building blocks acrylonitrile and methyl-ketones; we encourage researchers to improve on our efforts in this potentially useful but currently flawed process.

  6. 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.

  7. Catalytic, Conjugate Reduction-Aldol Addition Reaction of β'Oxoal kyl α, β-Unsatu rated Carboxylates%Catalytic, Conjugate Reduction-Aldol Addition Reaction of β'Oxoal kyl α, β-Unsatu rated Carboxylates

    Institute of Scientific and Technical Information of China (English)

    郑爱军; 姜岚; 李争宁

    2012-01-01

    Intramolecular conjugate reduction-aldol addition reactions of β'-oxoalkyl a,fl-unsaturated carboxylates were performed in the presence of copper catalysts generated in situ from copper salts, phosphine ligands and silanes. Moderate to good yields and high diastereoselectivities were obtained in 15 min to 3 h using bis[(2-diphenyl- phosphino)phenyl] ether as the ligand.

  8. 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.

  9. Catalytic hydrolysis of urea with fly ash for generation of ammonia in a batch reactor for flue gas conditioning and NOx reduction

    Energy Technology Data Exchange (ETDEWEB)

    Sahu, J.N.; Gangadharan, P.; Patwardhan, A.V.; Meikap, B.C. [Indian Institute of Technology, Kharagpur (India). Dept. of Chemical Engineering

    2009-01-15

    Ammonia is a highly volatile noxious material with adverse physiological effects, which become intolerable even at very low concentrations and present substantial environmental and operating hazards and risk. Yet ammonia has long been known to be used for feedstock of flue gas conditioning and NOx reduction. Urea as the source of ammonia for the production of ammonia has the obvious advantages that no ammonia shipping, handling, and storage is required. The process of this invention minimizes the risks and hazards associated with the transport, storage, and use of anhydrous and aqueous ammonia. Yet no such rapid urea conversion process is available as per requirement of high conversion in shorter time, so here we study the catalytic hydrolysis of urea for fast conversion in a batch reactor. The catalyst used in this study is fly ash, a waste material originating in great amounts in combustion processes. A number of experiments were carried out in a batch reactor at different catalytic doses, temperatures, times, and at a constant concentration of urea solution 10% by weight, and equilibrium and kinetic studies have been made.

  10. The Cu-CHA deNOx Catalyst in Action: Temperature-Dependent NH3-Assisted Selective Catalytic Reduction Monitored by Operando XAS and XES.

    Science.gov (United States)

    Lomachenko, Kirill A; Borfecchia, Elisa; Negri, Chiara; Berlier, Gloria; Lamberti, Carlo; Beato, Pablo; Falsig, Hanne; Bordiga, Silvia

    2016-09-21

    The small-pore Cu-CHA zeolite is today the object of intensive research efforts to rationalize its outstanding performance in the NH3-assisted selective catalytic reduction (SCR) of harmful nitrogen oxides and to unveil the SCR mechanism. Herein we exploit operando X-ray spectroscopies to monitor the Cu-CHA catalyst in action during NH3-SCR in the 150-400 °C range, targeting Cu oxidation state, mobility, and preferential N or O ligation as a function of reaction temperature. By combining operando XANES, EXAFS, and vtc-XES, we unambiguously identify two distinct regimes for the atomic-scale behavior of Cu active-sites. Low-temperature SCR, up to ∼200 °C, is characterized by balanced populations of Cu(I)/Cu(II) sites and dominated by mobile NH3-solvated Cu-species. From 250 °C upward, in correspondence to the steep increase in catalytic activity, the largely dominant Cu-species are framework-coordinated Cu(II) sites, likely representing the active sites for high-temperature SCR.

  11. Novel ultrasonic-modified MnOx/TiO2 for low-temperature selective catalytic reduction (SCR) of NO with ammonia.

    Science.gov (United States)

    Zhang, Yaping; Zhao, Xiaoyuan; Xu, Haitao; Shen, Kai; Zhou, Changcheng; Jin, Baosheng; Sun, Keqin

    2011-09-01

    A novel ultrasonic-modified MnO(x)/TiO(2) catalyst was prepared and compared with two different kinds of MnO(x)/TiO(2) catalysts in the process of low-temperature selective catalytic reduction of NO with NH(3). The physicochemical properties of the catalysts were studied by using various characterization techniques, such as Brunauer-Emmett-Teller (BET) surface measurement, X-ray diffraction (XRD), high-resolution transmission electron microscope (HRTEM), and in situ Fourier transform infrared spectroscopy (in situ FT-IR). The ultrasonic-modified process introduced ultrasound in the solution impregnation step of traditional impregnation method for MnO(x)/TiO(2) catalyst preparation. In this study, ultrasonic process significantly improved the dispersion behavior and surface acid property of manganese oxide on TiO(2) as well as the catalytic activity, especially at temperature below 120°C. The NO conversion could reach 90% at 100°C. For the novel ultrasonic-modified catalyst, the combination analysis of XRD and HRTEM confirmed that manganese oxide was in a highly dispersed state and Ti and Mn had strong interaction. Furthermore, in situ FT-IR studies revealed that there were significant amounts of Lewis acidity and high Mn atom concentration on the surface of the novel catalysts.

  12. Ce-Mn mixed oxides supported on glass-fiber for low-temperature selective catalytic reduction of NO with NH3

    Institute of Scientific and Technical Information of China (English)

    李乐; 刁永发; 刘鑫

    2014-01-01

    Samples of cerium-manganese oxides supported on modified glass-fiber with different Ce/Mn molar ratios (Ce-Mn/GF) were prepared by an impregnation method and tested for low-temperature (80-180 ºC) selective catalytic reduction (SCR) of NO with ammonia. This brand-new technology could remove NO and particles matter from coal-fired flue gas. The surface properties of the catalysts were examined by means of Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The experimental results showed that the catalyst with a Ce/Mn molar ratio of 0.2 obtained high activity of 87.4% NO conversion at 150 ºC under a high space velocity of 50000 h-1. Deactivation poisoned by SO2 still occurred, but the Ce-Mn/GF(0.2) catalyst performed desirable tolerance to SO2 with decreasing 50% in 40 min and then maintaining at about 30% NO conversion. Characterization results indicated that the excellent low-temperature catalytic activity was related to the high specific surface area, pore structure, and amorphous phase.

  13. Effect of fluorine additive on CeO2(ZrO2)/TiO2 for selective catalytic reduction of NO by NH3.

    Science.gov (United States)

    Jin, Qijie; Shen, Yuesong; Zhu, Shemin

    2017-02-01

    A series of CeO2(ZrO2)/TiO2 catalysts with fluorine additive were prepared by impregnation method and tested for selective catalytic reduction (SCR) of NO by NH3. These samples were characterized by XRD, N2-BET, Raman spectra, SEM, TEM, NH3-TPD, H2-TPR and XPS, respectively. Results showed that the optimal catalyst with the appropriate HF exhibited excellent performance for NH3-SCR and more than 96% NO conversion at 360°C under GHSV of 71,400h(-1). It was found that the grain size of TiO2 increased and the specific surface area reduced with the modulation of HF, which was not good for the adsorption of gas molecule. However, the modulation of HF exposed the high energy (001) facets of TiO2 and increased the surface chemisorbed oxygen concentration, oxygen storage capacity and Ce(3+) concentration of catalyst. In addition, the synergy of (101) and (001) facets was beneficial to the improvement of catalytic activity.

  14. The upside of downsizing: asymmetric trifunctional organocatalysts as small enzyme mimics for cooperative enhancement of both rate and enantioselectivity with regulation.

    Science.gov (United States)

    Liu, Fei

    2013-11-01

    Small molecule organic catalysts (organocatalysts) are widely used in asymmetric catalysis and synthesis. Compared to their enzymatic and transition-metal counterparts, organocatalysts have advantages in catalytic scope and efficiency but are more limited in proficiency. Chiral trifunctional organocatalysts, in which multiple catalytic motifs act cooperatively on a chiral scaffold, are an emerging class of organocatalysts with improved proficiency. Cooperativity design that enables both enantioselectivity and rate enhancement is essential to developing future generations of organocatalysts in biomimetic asymmetric catalysis.

  15. The poisoning effect of Na and K on Mn/TiO2 catalyst for selective catalytic reduction of NO with NH3: A comparative study

    Science.gov (United States)

    Guo, Rui-tang; Wang, Qing-shan; Pan, Wei-guo; Zhen, Wen-long; Chen, Qi-lin; Ding, Hong-lei; Yang, Ning-zhi; Lu, Chen-zi

    2014-10-01

    Mn/TiO2 catalyst is of high activity for low temperature selective catalytic reduction (SCR) of NO with NH3. And the deposition of alkali metal would lead to the deactivation of Mn/TiO2 catalyst. In this paper, the poisoning effect of Na and K on Mn/TiO2 was investigated based on experimental and theoretical study. It was found that K had a stronger poisoning effect than that of Na. The bad performance of K-Mn/TiO2 may be due to its small surface area, high crystallinity, weak surface acidity, low content of Mn4+ and chemisorbed oxygen, and bad redox ability. The interpretation of the experimental results is supported by DFT calculations.

  16. Green synthesis of core-shell gold-palladium@palladium nanocrystals dispersed on graphene with enhanced catalytic activity toward oxygen reduction and methanol oxidation in alkaline media

    Science.gov (United States)

    Zheng, Jie-Ning; Li, Shan-Shan; Ma, Xiaohong; Chen, Fang-Yi; Wang, Ai-Jun; Chen, Jian-Rong; Feng, Jiu-Ju

    2014-09-01

    Well-defined core-shell gold-palladium@palladium nanocrystals (AuPd@Pd) are facilely prepared by a simple and green wet-chemical method at 25 °C. A Good's buffer, 2-[4-(2-hydroxyethyl)-1-piperazinyl] ethanesulfonic acid (HEPES), is used as a reducing agent and a shape-directing agent, while there is no template, seed, organic solvent, or surfactant involved. The AuPd@Pd nanocrystals are uniformly dispersed on graphene nanosheets by ultrasonication, resulting in the formation of graphene supported AuPd@Pd (G-AuPd@Pd). The as-prepared nanocomposites exhibit the improved catalytic activity, good tolerance, and better stability for oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) in alkaline media, compared with the G-Pd and commercial Pd black catalysts. The as-developed method may provide a promising pathway for large-scale fabrication of AuPd-based catalysts.

  17. MnOx-CeO2 catalysts supported by Ti-Bearing Blast Furnace Slag for selective catalytic reduction of NO with NH3 at low temperature.

    Science.gov (United States)

    Xu, Yifan; Liu, Rong; Ye, Fei; Jia, Feng; Ji, Lingchen

    2017-03-13

    A series of MnOx-CeO2 catalysts supported by Ti-bearing blast furnace slag were prepared by wet impregnation and used for low-temperature selective catalytic reduction (SCR) of NO with NH3. The slag-based catalyst exhibited high deNOx activity and wide effective temperature range. Under the condition of NO=500ppm, NH3=500ppm, O2:7-8vol% and total flow rate=1600 ml/min, the Mn-Ce/Slag catalyst exhibited a NO conversion higher than 95% in the range of 180-260 °C. The activity of Mn/Slag catalysts was greatly enhanced with the addition of CeO2. The results indicated that Ti-bearing blast furnace slag had suitable phase composition as good support of SCR catalyst.

  18. Bauxite-supported Transition Metal Oxides: Promising Low-temperature and SO2-tolerant Catalysts for Selective Catalytic Reduction of NOx.

    Science.gov (United States)

    Wang, Xiuyun; Wu, Wen; Chen, Zhilin; Wang, Ruihu

    2015-05-19

    In order to develop low-temperature (below 200 °C) and SO2-tolerant catalysts for selective catalytic reduction (SCR) of NOx, a series of cheap M/bauxite (M = Mn, Ni and Cu) catalysts were prepared using bauxite as a support. Their SCR performances are much superior to typical V2O5/TiO2, the addition of M into bauxite results in significant promotion of NOx removal efficiency, especially at low temperature. Among the catalysts, Cu/bauxite exhibits wide temperature window over 50-400 °C, strong resistance against SO2 and H2O as well as good regeneration ability in SCR of NOx. NOx conversion is more than 80% at 50-200 °C, and N2 selectivity is more than 98%. Cu/bauxite can serve as a promising catalyst in SCR of NOx.

  19. Effect of rutile phase on V2O5 supported over TiO2 mixed phase for the selective catalytic reduction of NO with NH3

    Science.gov (United States)

    Zhang, Shule; Zhong, Qin; Wang, Yining

    2014-09-01

    A series of V2O5/TiO2 catalysts with different ratios of TiO2 rutile phase was prepared. Focusing on the effect of TiO2 rutile phase on V2O5/TiO2 catalyst for the selective catalytic reduction (SCR) of NO with NH3, the NO conversion for the different catalysts was investigated. The experimental results showed that a small amount of TiO2 rutile phase could improve the NO conversion significantly below 270 °C. Analysis by XRD, NH3-TPD, UV-vis, EPR and DFT calculation showed that the rutile phase of TiO2 supporter decreased the band gap, especially, the conduction band level. It improved the formation of reduced V species and superoxide ions that were important to the low-temperature SCR reaction.

  20. Effect of Ni+2-substituted Fe2TiO5 on the H2-reduction and CO2 Catalytic Decomposition Reactions at 500℃

    Institute of Scientific and Technical Information of China (English)

    M.H.Khedr

    2006-01-01

    CO2 is a major component of the greenhouse gases, which causes the global warming. To reduce CO2 gas,high activity nanosized Ni+2 substituted Fe2TiO5 samples were synthesized by conventional ceramic method.The effect of the composition of the synthesized ferrite on the H2-reduction and CO2-catalytic decomposition was investigated. Fe2TiO5 (iron titanate) phase that has a nanocrystallite size of ~80 nm is formed as a result of heating Fe2O3 and TiO2 while the addition of NiO leads to the formation of new phases (~80 nm)NiTiO3 and NiFe2O4, but the mixed solid of NiO and Fe2O3 results in the formation of NiFe2O4 only.Samples with Ni+2=0 shows the lowest reduction extent (20%); as the extent of Ni+2 increases, the extent of reduction increases. The increase in the reduction percent is attributed to the presence of NiTiO3 and NiFe2O4 phases, which are more reducible phases than Fe2TiO5. The CO2 decomposition reactions were monitored by thermogravimetric analysis (TGA) experiments. The oxidation of the H2-reduced Ni+2 substituted Fe2TiO5 at 500℃ was investigated. As Ni+2 increases, the rate of reoxidation increases. Samples with the highest reduction extents gave the highest reoxidation extent, which is attributed to the highly porous nature and deficiency in oxygen due to the presence of metallic Fe, Ni and/or FeNi alloy. X-ray diffraction (XRD) and transmission electron microscopy (TEM) of oxidized samples show also the presence of carbon in the sample containing Ni+2>0, which appears in the form of nanotubes (25 nm).

  1. The poisoning effect of PbO on Mn-Ce/TiO2 catalyst for selective catalytic reduction of NO with NH3 at low temperature

    Science.gov (United States)

    Zhou, Lingling; Li, Caiting; Zhao, Lingkui; Zeng, Guangming; Gao, Lei; Wang, Yan; Yu, Ming'e.

    2016-12-01

    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/TiO2 catalysts were synthesized by impregnation method. The poisoning effects of PbO over Mn-Ce/TiO2 samples for selective catalytic reduction of NO by NH3 were investigated based on catalytic activity test and characterizations. The NO conversion of Mn-Ce/TiO2 was greatly decreased after the addition of PbO. It was obvious that the NO conversion efficiency of Mn-Ce/TiO2 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 (H2-TPR), Ammonia temperature programmed desorption (NH3-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, Mn4+ as well as Ce3+ concentration and chemisorbed oxygen (Ob) after the introduction of PbO, all of these resulted in a poor SCR performance. Furthermore, the alteration of acid sites (especially Brönsted acid sites), low ammonia adsorbance, an obvious reducing of ad-NOx species (only a spot of bidentate nitrates remained) and the vanishing of amide species contributed to the deactivation of Mn-Ce/TiO2 catalyst by PbO doping as well.

  2. 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.

  3. Comparison of titania nanotubes and titanium dioxide as supports of low-temperature selective catalytic reduction catalysts under sulfur dioxide poisoning.

    Science.gov (United States)

    Lee, TsungYu; Liou, Sihyu; Bai, Hsunling

    2017-03-01

    A series of iron-manganese oxide catalysts supported on TiO2 and titanium nanotubes (TNTs) were studied for low temperature selective catalytic reduction (SCR) of NO with NH3 in the presence of SO2. The results showed that the specific surface area and the amount of Brønsted acid sites were highly correlated. The results also demonstrated that higher Mn(4+)/Mn(3+) ratios and larger specific surface areas might be the main reasons for the excellent performance of MnFe-TNTs catalyst after SO2 poisoning. The SO2 poisoning effect could be minimized by reducing the GHSV, increasing the reaction temperature, or increasing the [NH3]/[NO] molar ratio. The results also indicated that the formation of ammonium sulfate had a stronger effect on the NO conversion efficiency as compared to the formation of metal sulfate. Thus operating the low temperature SCR at above 230 (o)C to avoid the formation of ammonium sulfate would be the priority choice when SO2 poisoning is a concerned issue. Implications: Low-temperature selective catalytic reduction (SCR) has attracted increasing attention due to that it can reduce the energy consumption for the SCR process employed in industries such as steel plants and glass manufacturing plants. However, it also suffers from the sulfur dioxide (SO2) poisoning problem. This study investigates the possibility of using titania nanotubes (TNTs) as the support of Mn/Fe bimetal oxide catalysts for low-temperature SCR to reduce the SO2 poisoning. The results indicated that the MnFe-TNT catalyst can tolerate SO2 for a longer time as compared with the MnFe-TiO2 catalyst.

  4. 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.

  5. 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...

  6. Immobilized redox mediator on metal-oxides nanoparticles and its catalytic effect in a reductive decolorization process.

    Science.gov (United States)

    Alvarez, L H; Perez-Cruz, M A; Rangel-Mendez, J R; Cervantes, F J

    2010-12-15

    Different metal-oxides nanoparticles (MONP) including α-Al(2)O(3), ZnO and Al(OH)(3), were utilized as adsorbents to immobilize anthraquinone-2,6-disulfonate (AQDS). Immobilized AQDS was subsequently tested as a solid-phase redox mediator (RMs) for the reductive decolorization of the azo dye, reactive red 2 (RR2), by anaerobic sludge. The highest adsorption capacity of AQDS was achieved on Al(OH)(3) nanoparticles, which was ∼0.16 mmol g(-1) at pH 4. Immobilized AQDS increased up to 7.5-fold the rate of decolorization of RR2 by anaerobic sludge as compared with sludge incubations lacking AQDS. Sterile controls including immobilized AQDS did not show significant (reduction) were not responsible for the enhanced decolorization achieved. Immobilization of AQDS on MONP was very stable under the applied experimental conditions and spectrophotometric screening did not detect any detachment of AQDS during the reductive decolorization of RR2, confirming that immobilized AQDS served as an effective RMs. The present study constitutes the first demonstration that immobilized quinones on MONP can serve as effective RMs in the reductive decolorization of an azo dye. The immobilizing technique developed could be applied in anaerobic wastewater treatment systems to accelerate the redox biotransformation of recalcitrant pollutants.

  7. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    ZHANG XuMu

    2001-01-01

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

  8. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    ZHANG; XuMu

    2001-01-01

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

  9. Enantioselective Cu-Catalyzed Arylation of Secondary Phosphine Oxides with Diaryliodonium Salts toward the Synthesis of P-Chiral Phosphines

    Science.gov (United States)

    2016-01-01

    Catalytic synthesis of nonracemic P-chiral phosphine derivatives remains a significant challenge. Here we report Cu-catalyzed enantioselective arylation of secondary phosphine oxides with diaryliodonium salts for the synthesis of tertiary phosphine oxides with high enantiomeric excess. The new process is demonstrated on a wide range of substrates and leads to products that are well-established P-chiral catalysts and ligands. PMID:27689432

  10. Saraca indica bark extract mediated green synthesis of polyshaped gold nanoparticles and its application in catalytic reduction

    Science.gov (United States)

    Dash, Shib Shankar; Majumdar, Rakhi; Sikder, Arun Kanti; Bag, Braja Gopal; Patra, Biplab Kumar

    2014-04-01

    The bark extract of the traditional ayurvedic medicinal plant Saraca indica containing redox active polyphenolic compounds has been utilized for the one-step synthesis of gold nanoparticles at room temperature. The polyphenolic compounds acted as the reducing agent as well as the stabilizing agent without any additional capping agent. The synthesis of the gold nanoparticles of 15-23 nm size was complete in several minutes and no photo irradiation or heat treatment was necessary. Surface plasmon resonance, HRTEM, AFM, X-ray diffraction, and FTIR studies have been carried out to characterize the nanoparticles. Gold nanoparticles synthesized were of triangular, tetragonal, pentagonal, hexagonal, and spherical shapes. The synthesized gold nanoparticles have been used as a catalyst for the reduction of 4-nitrophenol to 4-aminophenol at room temperature and the kinetics of the reduction reaction has been studied spectrophotometrically.

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

    Science.gov (United States)

    Muzio, Lawrence J.; Smith, Randall A.

    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.

  12. 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.

  13. Catalytic reduction of nitric oxide with carbon monoxide on copper-cobalt oxides supported on nano-titanium dioxide.

    Science.gov (United States)

    Chen, Xia; Zhang, Junfeng; Huang, Yan; Tong, Zhiquan; Huang, Ming

    2009-01-01

    A series of copper-cobalt oxides supported on nano-titanium dioxide were prepared for the reduction of nitric oxide with carbon monoxide and characterized using techniques such as XRD, BET and TPR. Catalyst CuCoOx/TiO2 with Cu/Co molar ratio of 1/2, Cu-Co total loading of 30% at the calcination temperature of 350 degrees C formed CuCo2O4 spinel and had the highest activity. NO conversion reached 98.9% at 200 degrees C. Mechanism of the reduction was also investigated, N2O was mainly yielded below 100 degrees C, while N2 was produced instead at higher temperature. O2 was supposed to accelerate the reaction between NOx and CO for its oxidation of NO to give more easily reduced NO2, but the oxidation of CO by O2 to CO2 decreased the speed of the reaction greatly. Either SO2 or H2O had no adverse impact on the activity of NO reduction; however, in the presence of both SO2 and H2O, the catalyst deactivated quickly.

  14. 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)

  15. Enantioselectivity in environmental risk assessment of modern chiral pesticides.

    Science.gov (United States)

    Ye, Jing; Zhao, Meirong; Liu, Jing; Liu, Weiping

    2010-07-01

    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.

  16. Nonhydrolytic vanadia-titania xerogels. Synthesis, characterization, and behavior in the selective catalytic reduction of NO by NH{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Mutin, P. Hubert; Popa, Aurelian F.; Vioux, Andre [Chimie Moleculaire et Organisation du Solide-UMR CNRS 5637,Universite Montpellier 2, case 007, Place E. Bataillon, 34095 Montpellier Cedex 5 (France); Delahay, Gerard; Coq, Bernard [Laboratoire de Materiaux Catalytiques et Catalyse en Chimie Organique-UMR CNRS 5618, ENSCM, 8 rue de l' Ecole Normale, 34296 Montpellier Cedex 5 (France)

    2006-12-01

    V{sub 2}O{sub 5}-TiO{sub 2} catalysts with V{sub 2}O{sub 5} contents ranging from 6 to 18wt% were obtained by calcination at 773K of xerogels prepared by a nonhydrolytic sol-gel route from VOCl{sub 3}, TiCl{sub 4}, and {sup i}Pr{sub 2}O. These materials were characterized by X-ray diffraction, micro-FT-Raman spectroscopy, static {sup 51}V NMR, SEM, N{sub 2} physisorption, temperature-programmed desorption of ammonia (NH{sub 3}-TPD), and temperature-programmed reduction by H{sub 2} (H{sub 2}-TPR). In all cases mesoporous solids were obtained with specific surface areas up to 87m{sup 2}g{sup -1}. Raman spectroscopy indicated the presence of the same vanadia species as in conventional vanadia-titania catalysts. Up to a critical V{sub 2}O{sub 5} loading (between 10 and 12wt%), all the vanadium was highly dispersed in the form of monomeric vanadyl and polymeric vanadate species, whereas for higher loadings V{sub 2}O{sub 5} crystallites also formed. Most of the vanadium species (80-90%) were accessible to reduction by H{sub 2}. The catalytic properties of these materials were evaluated in the selective catalytic reduction of NO by NH{sub 3}. The estimated turnover frequency 'TOF' at 473K (mole of NO converted per mole of V per hour) went through a maximum value (16.6h{sup -1}) at a V loading of 8wt%, corresponding to an estimated surface vanadia loading of about 10{mu}molm{sup -2}. The N{sub 2}O selectivity increased upon V loading as expected. A compromise between activity and high N{sub 2} selectivity (98% at 623K) could be found with the material containing 6wt% V{sub 2}O{sub 5}. (author)

  17. 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.

  18. 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.

  19. Low-temperature selective catalytic reduction of NO on CeO2-CuO/Al2O3 catalysts prepared by different methods.

    Science.gov (United States)

    Guo, Rui-Tang; Zhen, Wen-Long; Pan, Wei-Guo; Hong, Jie-Nan; Jin, Qiang; Ding, Cheng-Gang; Guo, Shi-Yi

    2014-08-01

    CeO2-CuO/Al2O3 catalysts were prepared by three different methods and their activities for selective catalytic reduction (SCR) of NO with NH3 were investigated. As can be seen from the experimental results, the catalyst prepared by the single-step sol-gel (SG) method showed the best SCR activity and resistance to SO2 and H2O. In order to investigate the relationship between the preparation method and the performance of SCR catalysts, the catalysts were characterized by using Brunauer-Emmett-Teller, X-ray diffraction, temperature programmed reduction with hydrogen, temperature programmed desorption with ammonia, X-ray photoelectron spectroscopy, Fourier transform infrared and thermo-gravimetric analysis techniques. It was found that the excellent performance of CeO2-CuO/Al2O3 catalyst prepared by the single-step SG method should be resulted from its large surface area, low crystallinity, high oxygen storage capacity, high NH3 adsorption capacity, high concentration of surface chemisorbed oxygen, weak sulphation process and weak water absorption.

  20. In situ supported MnO(x)-CeO(x) on carbon nanotubes for the low-temperature selective catalytic reduction of NO with NH3.

    Science.gov (United States)

    Zhang, Dengsong; Zhang, Lei; Shi, Liyi; Fang, Cheng; Li, Hongrui; Gao, Ruihua; Huang, Lei; Zhang, Jianping

    2013-02-07

    The MnO(x) and CeO(x) were in situ supported on carbon nanotubes (CNTs) by a poly(sodium 4-styrenesulfonate) assisted reflux route for the low-temperature selective catalytic reduction (SCR) of NO with NH(3). X-Ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), H(2) temperature-programmed reduction (H(2)-TPR) and NH(3) temperature-programmed desorption (NH(3)-TPD) have been used to elucidate the structure and surface properties of the obtained catalysts. It was found that the in situ prepared catalyst exhibited the highest activity and the most extensive operating-temperature window, compared to the catalysts prepared by impregnation or mechanically mixed methods. The XRD and TEM results indicated that the manganese oxide and cerium oxide species had a good dispersion on the CNT surface. The XPS results demonstrated that the higher atomic concentration of Mn existed on the surface of CNTs and the more chemisorbed oxygen species exist. The H(2)-TPR results suggested that there was a strong interaction between the manganese oxide and cerium oxide on the surface of CNTs. The NH(3)-TPD results demonstrated that the catalysts presented a larger acid amount and stronger acid strength. In addition, the obtained catalysts exhibited much higher SO(2)-tolerance and improved the water-resistance as compared to that prepared by impregnation or mechanically mixed methods.

  1. Synthesis of magnetically recyclable MnFe2O4@SiO2@Ag nanocatalyst: Its high catalytic performances for azo dyes and nitro compounds reduction

    Science.gov (United States)

    Kurtan, U.; Amir, Md.; Yıldız, A.; Baykal, A.

    2016-07-01

    In this study, magnetically recycable MnFe2O4@SiO2@Ag nanocatalyst (MnFe2O4@SiO2@Ag MRCs) has been synthesized through co-precipition and chemical reduction method. XRD analysis confirmed the synthesis of single phase nanoproduct with crystallite size of 10 nm. VSM measurements showed the superparamagnetic property of the product. Catalytic studies showed that MnFe2O4@SiO2@Ag MRC could catalyze the reduction of the various azo compounds like methyl orange (MO), methylene blue (MB), eosin Y (EY), and rhodamine B (RhB) and also aromatic nitro compounds such as 4-nitrophenol (4-NP), 4-nitroaniline (4-NA) and 2-nitroaniline (2-NA). Moreover, the magnetic nanocatalyst showed an excellent reusability properties that remained unchanged after several cycles. Therefore, MnFe2O4@SiO2@Ag is the potential candidate for the application of organic pollutants for wastewater treatment.

  2. Structural insights into omega-class glutathione transferases: a snapshot of enzyme reduction and identification of a non-catalytic ligandin site.

    Directory of Open Access Journals (Sweden)

    Joseph Brock

    Full Text Available Glutathione transferases (GSTs are dimeric enzymes containing one active-site per monomer. The omega-class GSTs (hGSTO1-1 and hGSTO2-2 in humans are homodimeric and carry out a range of reactions including the glutathione-dependant reduction of a range of compounds and the reduction of S-(phenacylglutathiones to acetophenones. Both types of reaction result in the formation of a mixed-disulfide of the enzyme with glutathione through the catalytic cysteine (C32. Recycling of the enzyme utilizes a second glutathione molecule and results in oxidized glutathione (GSSG release. The crystal structure of an active-site mutant (C32A of the hGSTO1-1 isozyme in complex with GSSG provides a snapshot of the enzyme in the process of regeneration. GSSG occupies both the G (GSH-binding and H (hydrophobic-binding sites and causes re-arrangement of some H-site residues. In the same structure we demonstrate the existence of a novel "ligandin" binding site deep within in the dimer interface of this enzyme, containing S-(4-nitrophenacylglutathione, an isozyme-specific substrate for hGSTO1-1. The ligandin site, conserved in Omega class GSTs from a range of species, is hydrophobic in nature and may represent the binding location for tocopherol esters that are uncompetitive hGSTO1-1 inhibitors.

  3. Structural insights into omega-class glutathione transferases: a snapshot of enzyme reduction and identification of a non-catalytic ligandin site.

    Science.gov (United States)

    Brock, Joseph; Board, Philip G; Oakley, Aaron J

    2013-01-01

    Glutathione transferases (GSTs) are dimeric enzymes containing one active-site per monomer. The omega-class GSTs (hGSTO1-1 and hGSTO2-2 in humans) are homodimeric and carry out a range of reactions including the glutathione-dependant reduction of a range of compounds and the reduction of S-(phenacyl)glutathiones to acetophenones. Both types of reaction result in the formation of a mixed-disulfide of the enzyme with glutathione through the catalytic cysteine (C32). Recycling of the enzyme utilizes a second glutathione molecule and results in oxidized glutathione (GSSG) release. The crystal structure of an active-site mutant (C32A) of the hGSTO1-1 isozyme in complex with GSSG provides a snapshot of the enzyme in the process of regeneration. GSSG occupies both the G (GSH-binding) and H (hydrophobic-binding) sites and causes re-arrangement of some H-site residues. In the same structure we demonstrate the existence of a novel "ligandin" binding site deep within in the dimer interface of this enzyme, containing S-(4-nitrophenacyl)glutathione, an isozyme-specific substrate for hGSTO1-1. The ligandin site, conserved in Omega class GSTs from a range of species, is hydrophobic in nature and may represent the binding location for tocopherol esters that are uncompetitive hGSTO1-1 inhibitors.

  4. In situ IR studies of Co and Ce doped Mn/TiO2 catalyst for low-temperature selective catalytic reduction of NO with NH3

    Science.gov (United States)

    Qiu, Lu; Pang, Dandan; Zhang, Changliang; Meng, Jiaojiao; Zhu, Rongshu; Ouyang, Feng

    2015-12-01

    The Mn-Co-Ce/TiO2 catalyst was prepared by wet co-impregnation method for selective catalytic reduction of NO by NH3 in the presence of oxygen. The adsorption and co-adsorption of NH3, NO and O2 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 NH3 through NH3 migration. Ce addition improved amide ions formation to reach best NO reduction selectivity. A mechanistic pathway over Mn-Co-Ce/TiO2 was proposed. At low-temperature SCR reaction, coordinated NH3 reacted with NO2-, and amide reacted with NO (ad) or NO (g) to form N2. NO2 was related to the formation of nitrite on Co-contained catalysts and the generation of sbnd NH2- on Ce-contained catalysts. At high temperature, the other branch reaction also occurred between the coordinated NH3 and nitrate species, resulting in N2O yield increase.

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

    Science.gov (United States)

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

    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.

  6. Reduction of CO2 to low carbon alcohols on CuO FCs/Fe2O3 NTs catalyst with photoelectric dual catalytic interfaces.

    Science.gov (United States)

    Li, Peiqiang; Wang, Huying; Xu, Jinfeng; Jing, Hua; Zhang, Jun; Han, Haixiang; Lu, Fusui

    2013-12-01

    In this paper, the CuO FCs/Fe2O3 NTs catalyst was obtained after Fe2O3 nanotubes (Fe2O3 NTs) were decorated with CuO flower clusters (CuO FCs) by the pulse electrochemical deposition method. The in situ vertically aligned Fe2O3 NTs were prepared on the ferrous substrate by a potentiostatic anodization method. The SEM result showed the volcano-like Fe2O3 NTs were arranged in order and the CuO FCs constituted of flaky CuO distributed on the Fe2O3 NTs surface uniformly. After CuO FCs were loaded on Fe2O3 NTs, the absorption of visible light was enhanced noticeably, and its band gap narrowed to 1.78 eV from 2.03 eV. The conduction band and valence band locating at -0.73 eV and 1.05 eV, respectively were further obtained. In the PEC reduction of CO2 process, methanol and ethanol were two major products identified by chromatography. Their contents reached 1.00 mmol L(-1) cm(-2) and 107.38 μmol L(-1) cm(-2) after 6 h, respectively. This high-efficiency catalyst with photoelectric dual catalytic interfaces has a great guidance and reference significance for CO2 reduction to liquid carbon fuels.

  7. Enantioselective, iridium-catalyzed monoallylation of ammonia.

    Science.gov (United States)

    Pouy, Mark J; Stanley, Levi M; Hartwig, John F

    2009-08-19

    Highly enantioselective, iridium-catalyzed monoallylations of ammonia are reported. These reactions occur with electron-neutral, -rich, and -poor cinnamyl carbonates, alkyl and trityloxy-substituted allylic carbonates, and dienyl carbonates in moderate to good yields and excellent enantioselectivities. This process is enabled by the use of an iridium catalyst that does not require a Lewis acid for activation and that is stable toward a large excess of ammonia. This selective formation of primary allylic amines allows for one-pot syntheses of heterodiallylamines and allylic amides that are not otherwise accessible via iridium-catalyzed allylic amination without the use of blocking groups and protective group manipulations.

  8. 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.

  9. The strong catalytic effect of Pb(II) on the oxygen reduction reaction on 5 nm gold nanoparticles.

    Science.gov (United States)

    Wang, Ying; Laborda, Eduardo; Plowman, Blake J; Tschulik, Kristina; Ward, Kristopher R; Palgrave, Robert G; Damm, Christine; Compton, Richard G

    2014-02-21

    Citrate-capped gold nanoparticles (AuNPs) of 5 nm in diameter are synthesized via wet chemistry and deposited on a glassy carbon electrode through electrophoresis. The kinetics of the oxygen reduction reaction (ORR) on the modified electrode is determined quantitatively in oxygen-saturated 0.5 M sulphuric acid solution by modelling the cathode as an array of interactive nanoelectrodes. Quantitative analysis of the cyclic voltammetry shows that no apparent ORR electrocatalysis takes place, the kinetics on AuNPs being effectively the same as on bulk gold. Contrasting with the above, a strong ORR catalysis is found when Pb(2+) is added to the oxygen saturated solution or when the modified electrode is cycled in lead alkaline solution such that lead dioxide is repeatedly electrodeposited and stripped off on the nanoparticles. In both cases, the underpotential deposition of lead on the gold nanoparticles is found to be related to the catalysis.

  10. Catalytic Reduction of SO2 on CeO2-La2O3 Rare Earth Mixed Compounds

    Institute of Scientific and Technical Information of China (English)

    胡辉; 李劲; 程国宏; 李胜利

    2004-01-01

    Adding rare earth oxide CeO2 with variable valences to La2O3 formed a mixture of rare earth oxides. By means of dipping CeO2, La2O3 and their mixture, whose carriers were all γ-Al2O3, were used as the catalyst for the reduction of SO2 by CO. The activation process of this catalyst and the impact of temperature and reactant concentration on the activation process were investigated. Using X-ray diffraction, the structure characteristics of catalyst before and after reaction were analyzed to reveal the change of phase structure. The result shows that the rare earth oxide mixtures composing of CeO2 and La2O3, as the catalyst for the reduction of SO2 by CO, diminish activation temperature 50~100 ℃ less and have higher activity than a single oxide CeO2 or La2O3. The reason possibl is that La2O3 goes into in the lattice of CeO2 to form solid phase complex CeO2-La2O3 and increases the capability of CeO2-La2O3/γ-Al2O3 catalyst to store oxygen, which supplies the redox of CeO2 reaction with a better condition. At the same time, elemental sulfur formed in the redox reaction impels La2O3 to be transformed to activation phase La2O2S in a lower temperature, which can be explained with the synergism between redox reaction and COS intermediate mechanism reaction.

  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. Synthesis of novel chiral tetraaza ligands and their application in enantioselective transfer hydrogenation of ketones

    Institute of Scientific and Technical Information of China (English)

    Shen Luan Yu; Yan Yun Li; Zhen Rong Dong; Jing Xing Gao

    2012-01-01

    Novel chiral tetraaza ligands (R)-N,N'-bis[2-(piperidin-l-yl)benzylidene]propane-1,2-diamine 6 and (S)-N-[2-(piperidin-1-yl)benzylidene]-3-{ [2-(piperidin-1-yl)benzylidene]amino}-alanine sodium salt 7 have been synthesized and fully characterized by NMR,IR,MS and CD spectra.The catalytic property of the ligands was investigated in Ir-catalyzed enantioselective transfer hydrogenation of ketones.The corresponding optical active alcohols were obtained with high yields and moderate ees under mild reaction conditions.

  13. Multiphase enantioselective Kharasch-Sosnovsky allylic oxidation based on neoteric solvents and copper complexes of ditopic ligands.

    Science.gov (United States)

    Aldea, Luis; García, José I; Mayoral, José A

    2012-07-21

    Recoverable multiphase enantioselective catalytic systems for the Kharasch-Sosnovsky oxidation of cycloalkenes with tert-butyl peroxybenzoate are described, based on the use of [BMIM][PF(6)] and a new solvent derived from glycerol as the catalyst reservoir phases, and chiral copper complexes with different ligands from the bis(oxazoline) family. The best results are obtained with the glycerol-derived solvent and a recently described azabisoxazoline-based ditopic ligand, allowing up to four uses of the catalytic phase with good results.

  14. 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.

  15. 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.

  16. 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

  17. Novel Ce-W-Sb mixed oxide catalyst for selective catalytic reduction of NOx with NH3

    Science.gov (United States)

    Liu, Jun; Li, Guo-qiang; Zhang, Yong-fa; Liu, Xiao-qing; Wang, Ying; Li, Yuan

    2017-04-01

    A novel Ce3W2SbOx catalyst prepared by the co-precipitation method have been investigated for the selective catalysis reduction (SCR) of NOx with NH3. It was found that the Ce-W-Sb oxide catalyst exhibited an excellent conversion ratio of NOx and a high tolerance to H2O and SO2 in a wide operation temperature window. The catalysts were characterized by N2-adsorption, XRD, Raman, H2-TPR, NH3-TPD, XPS and DRIFTS. The results suggest that the strong interaction between Sb, W and Ce species not only enhances the redox property of the catalyst but also increases the surface acidity, thus promoting the adsorption and activation of NH3 species, which is favorable for high NH3-SCR performance. Based on in situ DRIFTS results, it was concluded that the Langmuir-Hinshelwood (L-H) mechanism existed at the temperature of below 300 °C, while at above 300 °C the Eley-Rideal (E-R) mechanism dominate the NH3-SCR reaction over the Ce3W2SbOx catalyst. Overall, these findings indicate that Ce3W2SbOx is promising for industrial applications.

  18. Enantioselective solvent-free Robinson annulation reactions

    Indian Academy of Sciences (India)

    D Rajagopal; R Narayanan; S Swaminathan

    2001-06-01

    The enantioselective cyclization of the prochiral cyclic substrates 1 to 7 and 26, can be carried out in the neat using -proline as catalyst. The substrates 18 to 22 and 27 could not be cyclized with S-proline but could be cyclized with a mixture of -phenylalanine and -camphorsulphonic acid. The enantioselective cyclization of prochiral acyclic triones 45 and 47 and also the racemic tricarbonyl compounds 54 to 57 could also be carried out in the \\text{neat} using -proline as catalyst. The optically active enediones obtained in the above cyclizations could also be obtained directly from 1,3-diones or 2-hydroxymethylene cycloalkanones in a one-pot reaction with methyl vinyl ketone (MVK) and S-proline in the absence of solvents. 13C NMR studies of the one-pot synthesis of S-11 and S-14 reveal that the annulations involve initial formation of an acid-base complex followed by a Michael reaction and then an enantioselective cyclization. Such enantioselective cyclizations probably occur on the surface of -proline crystals.

  19. DNA Duplex Engineering for Enantioselective Fluorescent Sensor.

    Science.gov (United States)

    Hu, Yuehua; Lin, Fan; Wu, Tao; Zhou, Yufeng; Li, Qiusha; Shao, Yong; Xu, Zhiai

    2017-02-21

    The rapid identification of biomacromolecule structure that has a specific association with chiral enantiomers especially from natural sources will be helpful in developing enantioselective sensor and in speeding up drug exploitation. Herein, owing to its existence also in living cells, apurinic/apyrimidinic site (AP site) was first engineered into ds-DNA duplex to explore its competence in enantiomer selectivity. An AP site-specific fluorophore was utilized as an enantioselective discrimination probe to develop a straightforward chiral sensor using natural tetrahydropalmatine (L- and D-THP) as enantiomer representatives. We found that only L-THP can efficiently replace the prebound fluorophore to cause a significant fluorescence increase due to its specific binding with the AP site (two orders magnitude higher in affinity than binding with D-THP). The AP site binding specificity of L-THP over D-THP was assessed via intrinsic fluorescence, isothermal titration calorimetry, and DNA stability. The enantioselective performance can be easily tuned by the sequences near the AP site and the number of AP sites. A single AP site provides a perfect binding pocket to differentiate the chiral atom-induced structure discrepancy. We expect that our work will inspire interest in engineering local structures into a ds-DNA duplex for developing novel enantioselective sensors.

  20. Directed evolution of an enantioselective lipase

    NARCIS (Netherlands)

    Liebeton, Klaus; Zonta, Albin; Schimossek, Klaus; Nardini, Marco; Lang, Dietmar; Dijkstra, Bauke W.; Reetz, Manfred T.; Jaeger, Karl-Erich

    2000-01-01

    Background: The biocatalytic production of enantiopure compounds is of steadily increasing importance to the chemical and biotechnological industry. In most cases, however, it is impossible to identify an enzyme that possesses the desired enantioselectivity. Therefore, there is a strong need to crea

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

    Science.gov (United States)

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

    2015-06-15

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

  2. Low-temperature selective catalytic reduction of NO with NH3 over nanoflaky MnOx on carbon nanotubes in situ prepared via a chemical bath deposition route

    Science.gov (United States)

    Fang, Cheng; Zhang, Dengsong; Cai, Sixiang; Zhang, Lei; Huang, Lei; Li, Hongrui; Maitarad, Phornphimon; Shi, Liyi; Gao, Ruihua; Zhang, Jianping

    2013-09-01

    Nanoflaky MnOx on carbon nanotubes (nf-MnOx@CNTs) was in situ synthesized by a facile chemical bath deposition route for low-temperature selective catalytic reduction (SCR) of NO with NH3. This catalyst was mainly characterized by the techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N2 adsorption-desorption analysis, X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature-programmed desorption (NH3-TPD). The SEM, TEM, XRD results and N2 adsorption-desorption analysis indicated that the CNTs were surrounded by nanoflaky MnOx and the obtained catalyst exhibited a large surface area as well. Compared with the MnOx/CNT and MnOx/TiO2 catalysts prepared by an impregnation method, the nf-MnOx@CNTs presented better NH3-SCR activity at low temperature and a more extensive operating temperature window. The XPS results showed that a higher atomic concentration of Mn4+ and more chemisorbed oxygen species existed on the surface of CNTs for nf-MnOx@CNTs. The H2-TPR and NH3-TPD results demonstrated that the nf-MnOx@CNTs possessed stronger reducing ability, more acid sites and stronger acid strength than the other two catalysts. Based on the above mentioned favourable properties, the nf-MnOx@CNT catalyst has an excellent performance in the low-temperature SCR of NO to N2 with NH3. In addition, the nf-MnOx@CNT catalyst also presented favourable stability and H2O resistance.Nanoflaky MnOx on carbon nanotubes (nf-MnOx@CNTs) was in situ synthesized by a facile chemical bath deposition route for low-temperature selective catalytic reduction (SCR) of NO with NH3. This catalyst was mainly characterized by the techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N2 adsorption-desorption analysis, X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature

  3. In situ supported MnOx-CeOx on carbon nanotubes for the low-temperature selective catalytic reduction of NO with NH3

    Science.gov (United States)

    Zhang, Dengsong; Zhang, Lei; Shi, Liyi; Fang, Cheng; Li, Hongrui; Gao, Ruihua; Huang, Lei; Zhang, Jianping

    2013-01-01

    The MnOx and CeOx were in situ supported on carbon nanotubes (CNTs) by a poly(sodium 4-styrenesulfonate) assisted reflux route for the low-temperature selective catalytic reduction (SCR) of NO with NH3. X-Ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature-programmed desorption (NH3-TPD) have been used to elucidate the structure and surface properties of the obtained catalysts. It was found that the in situ prepared catalyst exhibited the highest activity and the most extensive operating-temperature window, compared to the catalysts prepared by impregnation or mechanically mixed methods. The XRD and TEM results indicated that the manganese oxide and cerium oxide species had a good dispersion on the CNT surface. The XPS results demonstrated that the higher atomic concentration of Mn existed on the surface of CNTs and the more chemisorbed oxygen species exist. The H2-TPR results suggested that there was a strong interaction between the manganese oxide and cerium oxide on the surface of CNTs. The NH3-TPD results demonstrated that the catalysts presented a larger acid amount and stronger acid strength. In addition, the obtained catalysts exhibited much higher SO2-tolerance and improved the water-resistance as compared to that prepared by impregnation or mechanically mixed methods.The MnOx and CeOx were in situ supported on carbon nanotubes (CNTs) by a poly(sodium 4-styrenesulfonate) assisted reflux route for the low-temperature selective catalytic reduction (SCR) of NO with NH3. X-Ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature-programmed desorption (NH3-TPD) have been used to elucidate the structure and surface properties of the obtained catalysts. It was found that the in situ

  4. 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.

  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. 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 NH3-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), N2 sorption-desorption, nuclear magnetic resonance (NMR), Inductively Coupled Plasma-Atomic Emission spectrometer (ICP-AES), X-ray absorption spectroscopy (XPS), Temperature-programmed desorption of ammonia (NH3-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.

  7. Identification of the arsenic resistance on MoO3 doped CeO2/TiO2 catalyst for selective catalytic reduction of NOx with ammonia.

    Science.gov (United States)

    Li, Xiang; Li, Xiansheng; Li, Junhua; Hao, Jiming

    2016-11-15

    Arsenic resistance on MoO3 doped CeO2/TiO2 catalysts for selective catalytic reduction of NOx with NH3 (NH3-SCR) is investigated. It is found that the activity loss of CeO2-MoO3/TiO2 caused by As oxide is obvious less than that of CeO2/TiO2 catalysts. The fresh and poisoned catalysts are compared and analyzed using XRD, Raman, XPS, H2-TPR and in situ DRIFTS. The results manifest that the introduction of arsenic oxide to CeO2/TiO2 catalyst not only weakens BET surface area, surface acid sites and adsorbed NOx species, but also destroy the redox circle of Ce(4+) to Ce(3+) because of interaction between Ce and As. When MoO3 is added into CeO2/TiO2 system, the main SCR reaction path are found to be changed from the reaction between coordinated NH3 and ad-NOx species to that between an amide and gaseous NO. Additionally, for CeO2-MoO3/TiO2 catalyst, As toxic effect on active sites CeO2 can be released because of stronger As-Mo interaction. Moreover, not only are the reactable Brønsted and Lewis acid sites partly restored, but the cycle of Ce(4+) to Ce(3+) can also be free to some extent.

  8. 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.

  9. NH3-SCR performance of fresh and hydrothermally aged Fe-ZSM-5 in standard and fast selective catalytic reduction reactions.

    Science.gov (United States)

    Shi, Xiaoyan; Liu, Fudong; Xie, Lijuan; Shan, Wenpo; He, Hong

    2013-04-02

    Hydrothermal stability is one of the challenges for the practical application of Fe-ZSM-5 catalysts in the selective catalytic reduction (SCR) of NO with NH3 (NH(3)-SCR) for diesel engines. The presence of NO(3) in the exhaust gases can enhance the deNOx activity because of the fast SCR reaction. In this work, a Fe-ZSM-5 catalyst was prepared by a solid-state ion-exchange method and was hydrothermally deactivated at 800 °C in the presence of 10% H(2)O. The activity of fresh and hydrothermal aged Fe-ZSM-5 catalysts was investigated in standard SCR (NO(2)/NOx = 0) and in fast SCR with NO(2)/NOx = 0.3 and 0.5. In standard SCR, hydrothermal aging of Fe-ZSM-5 resulted in a significant decrease of low-temperature activity and a slight increase in high-temperature activity. In fast SCR, NOx conversion over aged Fe-ZSM-5 was significantly increased but was still lower than that over fresh catalyst. Additionally, production of N(2)O in fast SCR was much more apparent over aged Fe-ZSM-5 than over fresh catalyst. We propose that, in fast SCR, the rate of key reactions related to NO is slower over aged Fe-ZSM-5 than over fresh catalyst, thus increasing the probabilities of side reactions involving the formation of N(2)O.

  10. The Experimental and Simulation Study of Selective Catalytic Reduction System in a Single Cylinder Diesel Engine Using NH3 as a Reducing Agent

    Directory of Open Access Journals (Sweden)

    Manoj Kumar Athrashalil Phaily

    2014-01-01

    Full Text Available Selective catalytic reduction (SCR technology has been widely used in automotive applications in order to meet the stringent limits on emission standards. The maximum NOx conversion efficiency of an SCR depends on temperature and mass flow rate of an exhaust gas. In order to assess the suitability of Cordierite/Pt catalyst for low temperature application, an experimental work is carried out using single cylinder diesel engine for different load conditions by varying ammonia induction rate from 0.2 kg/hr to 0.8 kg/hr. The simulation is carried out using AVL FIRE for the validation of experimental results. From the study, it has been found that for 0.6 kg/hr ammonia induction rate the maximum conversion is achieved, whereas, for 0.8 kg/hr, conversion is reduced due to desorption of ammonia. Also it has been found that, at 75% of load, for all mass flow rates of ammonia the conversion was drastically reduced due to higher exhaust gas temperature and higher emission of unburnt hydrocarbons. More than 55% of NOx conversion was achieved using Cordierite/Pt catalyst at a temperature of 320°C.

  11. The poisoning effect of potassium ions doped on MnOx/TiO2 catalysts for low-temperature selective catalytic reduction

    Science.gov (United States)

    Zhang, Liangjing; Cui, Suping; Guo, Hongxia; Ma, Xiaoyu; Luo, Xiaogen

    2015-11-01

    The poisoning of alkali metal on MnOx/TiO2 catalysts used for selective catalytic reduction (SCR) of NOx by NH3 was investigated. KNO3, KCl and K2SO4 were doped on MnOx/TiO2 catalysts by sol-gel method, respectively. The SCR activity of each catalyst was measured for the removal of NOx with NH3 in the temperature range 90-330 °C. The experimental results showed that catalyst with KNO3 have a stronger deactivation effect than other catalysts. The properties of the catalysts were characterized by XRD, BET, SEM, XPS, H2-TPR, NH3-TPD and in situ DRIFTS analyses. The characterized results indicated that KNO3, KCl and K2SO4 caused the similar decrease of specific surface area and pore volume, but the quantity of acid sites for KNO3-MnOx/TiO2 catalyst reduced sharply. The main reason for catalyst deactivation is attributed to two aspects: one was physical influences for the decrease of surface area and pore volume, another was chemical influences that the K+ ions decomposed by KNO3 neutralized Brønsted acid sites of catalyst and reduced their reducibility. The chemical influence played a leading role on the deactivation of catalysts.

  12. 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...... not cause increased N2O formation or unselective oxidation of NH3. NH3-TPD showed that promotion by HPA instead of WO3 causes the catalysts to possess a higher number of acid sites, both in fresh and alkali poisoned form, which might explain their higher potassium tolerance. Ex-situ EPR spectroscopy......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...

  13. Core-shell Au@Pd nanoparticles with enhanced catalytic activity for oxygen reduction reaction via core-shell Au@Ag/Pd constructions.

    Science.gov (United States)

    Chen, Dong; Li, Chengyin; Liu, Hui; Ye, Feng; Yang, Jun

    2015-07-06

    Core-shell nanoparticles often exhibit improved catalytic properties due to the lattice strain created in these core-shell particles. Herein, we demonstrate the synthesis of core-shell Au@Pd nanoparticles from their core-shell Au@Ag/Pd parents. This strategy begins with the preparation of core-shell Au@Ag nanoparticles in an organic solvent. Then, the pure Ag shells are converted into the shells made of Ag/Pd alloy by galvanic replacement reaction between the Ag shells and Pd(2+) precursors. Subsequently, the Ag component is removed from the alloy shell using saturated NaCl solution to form core-shell Au@Pd nanoparticles with an Au core and a Pd shell. In comparison with the core-shell Au@Pd nanoparticles upon directly depositing Pd shell on the Au seeds and commercial Pd/C catalysts, the core-shell Au@Pd nanoparticles via their core-shell Au@Ag/Pd templates display superior activity and durability in catalyzing oxygen reduction reaction, mainly due to the larger lattice tensile effect in Pd shell induced by the Au core and Ag removal.

  14. Mechanistic Investigation into the Effect of Sulfuration on the FeW Catalysts for the Selective Catalytic Reduction of NOx with NH3.

    Science.gov (United States)

    Wang, Hui; Qu, Zhenping; Dong, Shicheng; Tang, Chen

    2017-03-01

    Iron tungsten (FeW) catalyst is a potential candidate for the selective catalytic reduction (SCR) of NOx with ammonia because of its excellent performance in a wide operating window. Sulfur poisoning effects in SCR catalysts have long been recognized as a challenge in development of efficient catalysts for applications. In this paper, the impact of sulfuration on catalyst structure, NH3-SCR reaction performance and mechanism was systematically investigated through spectroscopic and temperature-programmed approaches. The sulfuration inhibited the SCR activity at low temperatures (catalyst, the organic-like with covalent S═O bonds sulfate species were mainly formed over the FeW catalysts. Combining TPD with in situ DRIFTS results, it was found that the Lewis and the Brønsted acidity were enhanced by the interaction between metal species and sulfate species due to the strong electron withdrawing effect of the S═O double bonds. The in situ DRIFTS study showed that the formation of NO2 was hindered, leading to the "fast-SCR" pathway was partly cut off by the sulfuration process and thereby the loss of SCR activity at low temperatures. However, the Langmuir-Hinshelwood reaction pathway between adsorbed NH3/NH4(+) species and nitrate species was facilitated and dominated at high temperatures, making the as-synthesized FeW catalysts resistant to SO2 poisoning.

  15. DRIFT studies on promotion mechanism of H3PW12O40 in selective catalytic reduction of NO with NH3.

    Science.gov (United States)

    Weng, Xiaole; Dai, Xiaoxia; Zeng, Qingshan; Liu, Yue; Wu, Zhongbiao

    2016-01-01

    Heteropoly acids (HPAs) have been effectively utilized in selective catalytic reduction (SCR) of NO to improve the NH3 absorption capacity and alkaline/alkali metal resistance for SCR catalysts. However, despite the promise on super-acidities, their other properties that would work on SCR process are still lack of exploration. In this study, a 12-tungstaphosphoric acid (H3PW12O40, HPW) was selected to modify a well-reported CeO2 catalyst. The resulted CeO2/HPW catalyst was subsequently utilized for SCR of NO with excess NH3, which revealed a significantly promoted performance in SCR reaction. DRIFT analyses showed that the unique NO2 absorption capacity of HPW could prevent the NO2 being further oxidized into nitrate species and the abundant Brønsted acid sites could effectively retain the NH3, avoiding them being over-oxidized at evaluated temperatures. The presence of NO2 was demonstrated able to induce a so called "fast SCR" reaction over the CeO2/HPW catalyst, which effectively facilitated the SCR reaction. Furthermore, we have also constructed a CeO2@HPW catalyst, which showed an enhanced SO2 poisoning resistance in SCR reaction.

  16. Demonstration of selective catalytic reduction (SCR) technology for the control of nitrogen oxide (NO sub x ) emissions from high-sulfur coal-fired boilers

    Energy Technology Data Exchange (ETDEWEB)

    1991-08-01

    The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from US, Japanese and European catalyst suppliers on a high-sulfur US coal-fired boiler. SCR is a post-combustion nitrogen oxide (NOx) 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 NOx to convert it to nitrogen and water vapor, Although SCR is widely practiced in Japan and Europe, there are numerous technical uncertainties associated with applying SCR to US coals. These uncertainties include: (1) potential catalyst deactivation due to poisoning by trace metal species present in US coals that are not present in other fuel 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}. (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 will be explored by constructing a series of small-scale SCR reactors and simultaneously exposing different SCR catalysts to flue gas derived from the combustion of high sulfur US coal.

  17. Demonstration of selective catalytic reduction (SCR) technology for the control of nitrogen oxide (NO[sub x]) emissions from high-sulfur coal-fired boilers

    Energy Technology Data Exchange (ETDEWEB)

    1992-08-01

    The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from US, Japanese and European catalyst suppliers on a high-sulfur US 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 convert it to nitrogen and water vapor. Although SCR is widely practiced in Japan and Europe, there are numerous technical uncertainties associated with applying SCR to US coals. These uncertainties include: (1) potential catalyst deactivation due to poisoning by trace metal species present in US 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]. (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 will be explored by constructing 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.

  18. Study on the mechanism of NH3-selective catalytic reduction over CuCexZr1-x/TiO2

    Science.gov (United States)

    Chen, Xujuan; Sun, Xiaoliang; Gong, Cairong; Lv, Gang; Song, Chonglin

    2016-06-01

    Copper-cerium-zirconium catalysts loaded on TiO2 prepared by a wet impregnation method were investigated for NH3-selective catalytic reduction (SCR) of NOx. The reaction mechanism was proposed on the basis of results from in situ diffuse reflectance infrared transform spectroscopy (DRIFT). When NH3 is introduced, ammonia bonded to Lewis acid sites is more stable over CuCe0.25Zr0.75/TiO2 at high temperature, while Brønsted acid sites are more important than Lewis acid sites at low temperature. For the NH3+NO+O2 co-adsorption, NH3 species occupy most of activity sites on CuCe0.25Zr0.75/TiO2 catalyst, and mainly exist in the forms of NH4 + (at low temperature) and NH3 coordinated (at high temperature), playing a crucial role in the NH3-SCR process. Two different reaction routes, the L-H mechanism at low temperature ( 200°C), are presented for the SCR reaction over CuCe0.25Zr0.75/TiO2 catalyst.

  19. Selective catalytic reduction of NO with NH3 over CeO2-ZrO2-WO3 catalysts prepared by different methods

    Science.gov (United States)

    Ning, Ping; Song, Zhongxian; Li, Hao; Zhang, Qiulin; Liu, Xin; Zhang, Jinhui; Tang, Xiaosu; Huang, Zhenzhen

    2015-03-01

    The selective catalytic reduction (SCR) of NO by NH3 has been investigated over the CeO2-ZrO2-WO3 (CZW) catalysts prepared by hydrothermal synthesis, incipient impregnation, co-precipitation and sol-gel methods. The results indicate that the CZW catalyst prepared by hydrothermal method shows the best SCR activity, and more than 90% NO conversion is obtained at 195-450 °C with a gas hourly space velocity of 50,000 h-1. The samples are characterized by XRD, N2 adsorption-desorption, SEM, EDS, XPS, H2-TPR, NH3-TPD and Pyridine-IR techniques. The results imply that the superior SCR activity of CZW catalyst is contributed to the excellent redox property, strong acidity and highest content of chemisorbed oxygen species. Furthermore, the larger surface area and greater total pore volume improve the redox ability and enhance NO conversion at low temperature, while the co-existence of Lewis and Brønsted acid sites enhance the SCR activity at high temperature.

  20. 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.

  1. Synthesis of small silver nanoparticles under light radiation by fungus Penicillium oxalicum and its application for the catalytic reduction of methylene blue

    Energy Technology Data Exchange (ETDEWEB)

    Du, Liangwei, E-mail: dulily9@163.com [State Key Laboratory for Conservation and Utilization of Subtropical Agro-bioresources, Guangxi University, 100 Daxue Road, Nanning 530004, Guangxi (China); College of Chemistry and Chemical Engineering, Guangxi University, 100 Daxue Road, Nanning 530004, Guangxi (China); Xu, Qiuhong; Huang, Meiying [State Key Laboratory for Conservation and Utilization of Subtropical Agro-bioresources, Guangxi University, 100 Daxue Road, Nanning 530004, Guangxi (China); College of Chemistry and Chemical Engineering, Guangxi University, 100 Daxue Road, Nanning 530004, Guangxi (China); Xian, Liang [State Key Laboratory for Conservation and Utilization of Subtropical Agro-bioresources, Guangxi University, 100 Daxue Road, Nanning 530004, Guangxi (China); College of Life Science and Technology, Guangxi University, 100 Daxue Road, Nanning 530004, Guangxi (China); Feng, Jia-Xun, E-mail: jiaxunfeng@sohu.com [State Key Laboratory for Conservation and Utilization of Subtropical Agro-bioresources, Guangxi University, 100 Daxue Road, Nanning 530004, Guangxi (China); College of Life Science and Technology, Guangxi University, 100 Daxue Road, Nanning 530004, Guangxi (China)

    2015-06-15

    At present, green and efficient synthetic strategies have been gaining great interest for the synthesis of metal nanoparticles. In this study, the synthesis of extracellular silver nanoparticles (AgNPs) under light radiation was described using the cell filtrate of Penicillium oxalicum 1–208. The pH effect of the cell filtrate on nanosynthesis was investigated by visual observation, ultraviolet–visible absorption spectroscopy, dynamic light scattering and zeta potential. The results showed that the pH of the cell filtrate affected the time of nanosynthesis, and the size, size distribution and stability of the synthesized nanoparticles. The AgNPs synthesized at pH 8.0 and 12.0 were further characterized by X-ray diffraction, selected area electron diffraction, energy-dispersive X-ray spectroscopy and transmission electron microscopy. The synthesized AgNPs were spherical in shape, crystalline in nature and preferentially oriented in (111) plane. Small AgNPs with an average particle size of about 4 nm were successfully synthesized at pH 12.0 and well dispersed in solution without obvious aggregation. Furthermore, the AgNPs synthesized at pH 8.0 were used as catalyst and exhibited excellent catalytic activity for the reduction of methylene blue in the presence of NaBH{sub 4} at ambient temperature. - Highlights: • Extracellular silver nanoparticles were synthesized using Penicillium oxalicum assisted by simulated sunlight. • The pH of the cell filtrate affected the synthesis of silver nanoparticles. • The silver nanoparticles were more stable in weakly alkaline and alkaline solutions. • Small silver nanoparticles with good dispersibility and stability were rapidly synthesized at pH 12.0. • The reduction of methylene blue was instantly completed with silver nanoparticles synthesized at pH 8.0 used as catalyst.

  2. Promotional Effect on Selective Catalytic Reduction of NOx with NH3 over Overloaded W and Ce on V2O5/TiO2 Catalysts

    Directory of Open Access Journals (Sweden)

    Seunghee Youn

    2015-01-01

    Full Text Available W and Ce are known to be a good promoters to improve selective catalytic reduction (SCR activity for V2O5/TiO2 catalysts. This work aimed at finding the optimum ratio and loading of promoters (W and Ce on V2O5/TiO2 catalyst in order to improve SCR reactivity in low temperature region and to minimize N2O formation in high temperature region. In addition, we changed the order of impregnation between W and Ce precursors on V2O5/TiO2 catalyst during the preparation and observed its effect on SCR activity and N2 selectivity. We utilized various analytical techniques, such as N2 adsorption-desorption, X-ray diffraction (XRD, and temperature-programmed reduction with hydrogen (H2 TPR to investigate the physicochemical properties of catalysts. It was found that W- and Ce-overloaded V2O5/TiO2 catalyst such as W/Ce/V/TiO2 (15 : 15 : 1 wt% showed the most remarkable DeNOx properties over the wide temperature region. Additionally, this catalyst significantly suppressed N2O formation during SCR reaction, especially in high temperature region (350–400°C. Based on the characterization results, it was found that such superior activity originated from the improved reducibility and morphology of W and Ce species on V2O5/TiO2 catalyst when they are incorporated together at high loading.

  3. 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.

  4. Low-temperature selective catalytic reduction of NO with NH₃ over nanoflaky MnOx on carbon nanotubes in situ prepared via a chemical bath deposition route.

    Science.gov (United States)

    Fang, Cheng; Zhang, Dengsong; Cai, Sixiang; Zhang, Lei; Huang, Lei; Li, Hongrui; Maitarad, Phornphimon; Shi, Liyi; Gao, Ruihua; Zhang, Jianping

    2013-10-07

    Nanoflaky MnO(x) on carbon nanotubes (nf-MnO(x)@CNTs) was in situ synthesized by a facile chemical bath deposition route for low-temperature selective catalytic reduction (SCR) of NO with NH₃. This catalyst was mainly characterized by the techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N₂ adsorption-desorption analysis, X-ray photoelectron spectroscopy (XPS), H₂ temperature-programmed reduction (H₂-TPR) and NH₃ temperature-programmed desorption (NH₃-TPD). The SEM, TEM, XRD results and N₂ adsorption-desorption analysis indicated that the CNTs were surrounded by nanoflaky MnO(x) and the obtained catalyst exhibited a large surface area as well. Compared with the MnO(x)/CNT and MnO(x)/TiO₂ catalysts prepared by an impregnation method, the nf-MnO(x)@CNTs presented better NH₃-SCR activity at low temperature and a more extensive operating temperature window. The XPS results showed that a higher atomic concentration of Mn(4+) and more chemisorbed oxygen species existed on the surface of CNTs for nf-MnO(x)@CNTs. The H₂-TPR and NH₃-TPD results demonstrated that the nf-MnO(x)@CNTs possessed stronger reducing ability, more acid sites and stronger acid strength than the other two catalysts. Based on the above mentioned favourable properties, the nf-MnO(x)@CNT catalyst has an excellent performance in the low-temperature SCR of NO to N₂ with NH₃. In addition, the nf-MnO(x)@CNT catalyst also presented favourable stability and H₂O resistance.

  5. Catalytic Reduction of Cu(Ⅱ) by Polypyrrole%聚吡咯对Cu(Ⅱ)的催化还原作用

    Institute of Scientific and Technical Information of China (English)

    田颖; 吴艳波; 王晶日; 杨凤林

    2009-01-01

    以对甲苯磺酸钠为掺杂剂在不锈钢(SS)电极表面恒电位合成聚吡咯(PPy)修饰膜,采用恒电位和动电位对Cu(Ⅱ)的还原效果进行了研究,并与不锈钢电极进行了对比.结果表明,由于聚吡咯的催化作用,聚吡咯修饰电极对Cu(Ⅱ)还原效率高于不锈钢电极;聚吡咯膜对析氢有明显的抑制作用,因此电流效率远远高于不锈钢电极,这是采用聚吡咯进行电化学还原的明显优势.通过在不同浓度Cu(Ⅱ)酸性溶液中的循环伏安行为讨论了聚吡咯对Cu(Ⅱ)的还原作用机理.%Polypyrrole (PPy) films were synthesized by a potentiostatic method from apara-toluenesulfonic sodium solution on stainless steel (SS). The effect on Cu(Ⅱ) reduction of the PPy-modified film was investigated through potentiostatic and potentiodynamic conditions and compared with that of SS. A higher removal efficiency was achieved on PPy because of its catalytic effect. The current efficiency obtained with the PPy film is much higher than that of SS because PPy inhibits the effect of hydrogen evolution and this is the greatest advantage for using PPy to remove heavy metals. Cyclic voltammetry of PPy-modified electrodes in acidified Cu(Ⅱ) solutions was conducted and the mechanism of PPy for Cu(Ⅱ) reduction was discussed.

  6. 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.

  7. Low Absorption Vitreous Carbon Reactors for Operando XAS: A Case Study on Cu/Zeolites for Selective Catalytic Reduction of NOx by NH3

    Energy Technology Data Exchange (ETDEWEB)

    Kispersky, Vincent F.; Kropf, Jeremy; Ribeiro, Fabio H; Miller, Jeffrey T

    2012-01-01

    We describe the use of vitreous carbon as an improved reactor material for an operando X-ray absorption spectroscopy (XAS) plug-flow reactor. These tubes significantly broaden the operating range for operando experiments. Using selective catalytic reduction (SCR) of NOx by NH₃ on Cu/Zeolites (SSZ-13, SAPO-34 and ZSM-5) as an example reaction, we illustrate the high-quality XAS data achievable with these reactors. The operando experiments showed that in Standard SCR conditions of 300 ppm NO, 300 ppm NH₃, 5% O₂, 5% H₂O, 5% CO₂ and balance He at 200 °C, the Cu was a mixture of Cu(I) and Cu(II) oxidation states. XANES and EXAFS fitting found the percent of Cu(I) to be 15%, 45% and 65% for SSZ-13, SAPO-34 and ZSM-5, respectively. For Standard SCR, the catalytic rates per mole of Cu for Cu/SSZ-13 and Cu/SAPO-34 were about one third of the rate per mole of Cu on Cu/ZSM-5. Based on the apparent lack of correlation of rate with the presence of Cu(I), we propose that the reaction occurs via a redox cycle of Cu(I) and Cu(II). Cu(I) was not found in in situSCR experiments on Cu/Zeolites under the same conditions, demonstrating a possible pitfall of in situ measurements. A Cu/SiO₂ catalyst, reduced in H₂ at 300 °C, was also used to demonstrate the reactor's operando capabilities using a bending magnet beamline. Analysis of the EXAFS data showed the Cu/SiO₂ catalyst to be in a partially reduced Cu metal–Cu(I) state. In addition to improvements in data quality, the reactors are superior in temperature, stability, strength and ease of use compared to previously proposed borosilicate glass, polyimide tubing, beryllium and capillary reactors. The solid carbon tubes are non-porous, machinable, can be operated at high pressure (tested at 25 bar), are inert, have high material purity and high X-ray transmittance.

  8. Low absorption vitreous carbon reactors for operando XAS: a case study on Cu/Zeolites for selective catalytic reduction of NO(x) by NH3.

    Science.gov (United States)

    Kispersky, Vincent F; Kropf, A Jeremy; Ribeiro, Fabio H; Miller, Jeffrey T

    2012-02-21

    We describe the use of vitreous carbon as an improved reactor material for an operando X-ray absorption spectroscopy (XAS) plug-flow reactor. These tubes significantly broaden the operating range for operando experiments. Using selective catalytic reduction (SCR) of NO(x) by NH(3) on Cu/Zeolites (SSZ-13, SAPO-34 and ZSM-5) as an example reaction, we illustrate the high-quality XAS data achievable with these reactors. The operando experiments showed that in Standard SCR conditions of 300 ppm NO, 300 ppm NH(3), 5% O(2), 5% H(2)O, 5% CO(2) and balance He at 200 °C, the Cu was a mixture of Cu(I) and Cu(II) oxidation states. XANES and EXAFS fitting found the percent of Cu(I) to be 15%, 45% and 65% for SSZ-13, SAPO-34 and ZSM-5, respectively. For Standard SCR, the catalytic rates per mole of Cu for Cu/SSZ-13 and Cu/SAPO-34 were about one third of the rate per mole of Cu on Cu/ZSM-5. Based on the apparent lack of correlation of rate with the presence of Cu(I), we propose that the reaction occurs via a redox cycle of Cu(I) and Cu(II). Cu(I) was not found in in situ SCR experiments on Cu/Zeolites under the same conditions, demonstrating a possible pitfall of in situ measurements. A Cu/SiO(2) catalyst, reduced in H(2) at 300 °C, was also used to demonstrate the reactor's operando capabilities using a bending magnet beamline. Analysis of the EXAFS data showed the Cu/SiO(2) catalyst to be in a partially reduced Cu metal-Cu(I) state. In addition to improvements in data quality, the reactors are superior in temperature, stability, strength and ease of use compared to previously proposed borosilicate glass, polyimide tubing, beryllium and capillary reactors. The solid carbon tubes are non-porous, machinable, can be operated at high pressure (tested at 25 bar), are inert, have high material purity and high X-ray transmittance.

  9. 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

  10. Green chemistry: C-C coupling and asymmetric reduction by innovative catalysis

    Institute of Scientific and Technical Information of China (English)

    Xiaofeng Wu; Jun Mo; Xiaohong Li; Zeyn Hyder; Jianliang Xiao

    2008-01-01

    A catalytic method has been developed, which allows aryl halides to couple with various electron-rich olefins to give 1, 1'-substituted olefins. The palladium-catalysed coupling in ionic liquid solvent proceeds with high efficiency and remarkable regioselectivity without the need for any costly or toxic halide scavengers. Parallel to this, an environmentally-appealing method for the asymmetric reduction of ketones has been established, with which a variety of chiral alcohols can be accessed with high enantioselectivity in water with no need for any organic solvents. The same chemistry has been explored for the reduction of aldehydes, which is shown to be fast and highly chemoselective. These methods add new tools to the armoury of synthetic chemists.

  11. Influence of reduction energy match among CuO species in CuO-CeO2 catalysts on the catalytic performance for CO preferential oxidation in excess hydrogen

    Institute of Scientific and Technical Information of China (English)

    Zhigang Liu; Yunlong Xie; Wensheng Li; Renxian Zhou; Xiaoming Zheng

    2011-01-01

    In the present study,we have investigated the reducibility of CuO species on CuO-CeO2 catalysts and the influence of CuO species on the catalytic performance for CO preferential oxidation(CO PROX)in excess hydrogen.It is revealed that the smaller the difference of reduction temperature(denoted as △T)for two adjacent CuO species is,the higher the catalytic activity of CuO-CeO2 for the PROX in excess hydrogen may be obtained.It means that if the reduction energy of CuO-CU2+pairs matched better,the reduction-oxidation recycle of CuO-Cu2+pairs would go on more easily,then the transferring energy of CuO-Cu2+pairs would be lesser.Therefore,the CuO-CeO2 catalysts will be largely improved in their catalytic performance if the different CuO species on the catalysts have matched the reduction energy,which would allows them to cooperate effectively.

  12. 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.

  13. Ir-Catalyzed Enantioselective Hydrogenation of 2H-1,4-Benzoxazines with a Chiral 1,2,3,4- Tetrahydro-l-naphthylamine Derived Phosphine-aminophosphine Ligand

    Institute of Scientific and Technical Information of China (English)

    胡娟; 王道永; 郑卓; 胡向平

    2012-01-01

    Unsymmetrical hybrid chiral phosphine-aminophosphine ligand derived from 1,2,3,4-tetrahydro-l-naphthyl- amine has been found to be highly efficient in the Ir-catalyzed asymmetric hydrogenation of various 3-aryl-2H-1,4-benzoxazines, providing good enantioselectivities (up to 95% ee) and high catalytic activity (S/C up to 5000).

  14. A simple way to prepare Au@polypyrrole/Fe3O4 hollow capsules with high stability and their application in catalytic reduction of methylene blue dye

    Science.gov (United States)

    Yao, Tongjie; Cui, Tieyu; Wang, Hao; Xu, Linxu; Cui, Fang; Wu, Jie

    2014-06-01

    Metal nanoparticles are promising catalysts for dye degradation in treating wastewater despite the challenges of recycling and stability. In this study, we have introduced a simple way to prepare Au@polypyrrole (PPy)/Fe3O4 catalysts with Au nanoparticles embedded in a PPy/Fe3O4 capsule shell. The PPy/Fe3O4 capsule shell used as a support was constructed in one-step, which not only dramatically simplified the preparation process, but also easily controlled the magnetic properties of the catalysts through adjusting the dosage of FeCl2.4H2O. The component Au nanoparticles could catalyze the reduction of methylene blue dye with NaBH4 as a reducing agent and the reaction rate constant was calculated through the pseudo-first-order reaction equation. The Fe3O4 nanoparticles permitted quick recycling of the catalysts with a magnet due to their room-temperature superparamagnetic properties; therefore, the catalysts exhibited good reusability. In addition to catalytic activity and reusability, stability is also an important property for catalysts. Because both Au and Fe3O4 nanoparticles were wrapped in the PPy shell, compared with precursor polystyrene/Au composites and bare Fe3O4 nanoparticles, the stability of Au@PPy/Fe3O4 hollow capsules was greatly enhanced. Since the current method is simple and flexible to create recyclable catalysts with high stability, it would promote the practicability of metal nanoparticle catalysts in industrial polluted water treatment.Metal nanoparticles are promising catalysts for dye degradation in treating wastewater despite the challenges of recycling and stability. In this study, we have introduced a simple way to prepare Au@polypyrrole (PPy)/Fe3O4 catalysts with Au nanoparticles embedded in a PPy/Fe3O4 capsule shell. The PPy/Fe3O4 capsule shell used as a support was constructed in one-step, which not only dramatically simplified the preparation process, but also easily controlled the magnetic properties of the catalysts through adjusting

  15. 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

    Science.gov (United States)

    Rambabu, Darsi; Pradeep, Chullikkattil P.; Dhir, Abhimanew

    2016-12-01

    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.

  16. Synthesis of Fe3O4@SiO2-Ag magnetic nanocomposite based on small-sized and highly dispersed silver nanoparticles for catalytic reduction of 4-nitrophenol.

    Science.gov (United States)

    Chi, Yue; Yuan, Qing; Li, Yanjuan; Tu, Jinchun; Zhao, Liang; Li, Nan; Li, Xiaotian

    2012-10-01

    In this work, we report a facile method to generate core-shell structured Fe(3)O(4)@SiO(2)-Ag magnetic nanocomposite by an in situ wet chemistry route with the aid of polyvinylpyrrolidone as both reductant and stabilizer. This method can effectively prevent Ag nanoparticles from aggregating on the silica surface, thus resulting highly dispersed and small-sized Ag nanoparticles. The as-prepared nanocomposite is composed of a central magnetite core with a strong response to external fields, an interlayer of SiO(2), and numerous highly dispersed Ag nanoparticles with a narrow size distribution. Furthermore, the Fe(3)O(4)@SiO(2)-Ag nanocomposite showed high performance in the catalytic reduction of 4-nitrophenol and could be easily recycled by applying an external magnetic field while maintaining the catalytic activity without significant decrease even after running 15 times.

  17. 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.

  18. A simple way to prepare Au@polypyrrole/Fe3O4 hollow capsules with high stability and their application in catalytic reduction of methylene blue dye.

    Science.gov (United States)

    Yao, Tongjie; Cui, Tieyu; Wang, Hao; Xu, Linxu; Cui, Fang; Wu, Jie

    2014-07-07

    Metal nanoparticles are promising catalysts for dye degradation in treating wastewater despite the challenges of recycling and stability. In this study, we have introduced a simple way to prepare Au@polypyrrole (PPy)/Fe3O4 catalysts with Au nanoparticles embedded in a PPy/Fe3O4 capsule shell. The PPy/Fe3O4 capsule shell used as a support was constructed in one-step, which not only dramatically simplified the preparation process, but also easily controlled the magnetic properties of the catalysts through adjusting the dosage of FeCl2·4H2O. The component Au nanoparticles could catalyze the reduction of methylene blue dye with NaBH4 as a reducing agent and the reaction rate constant was calculated through the pseudo-first-order reaction equation. The Fe3O4 nanoparticles permitted quick recycling of the catalysts with a magnet due to their room-temperature superparamagnetic properties; therefore, the catalysts exhibited good reusability. In addition to catalytic activity and reusability, stability is also an important property for catalysts. Because both Au and Fe3O4 nanoparticles were wrapped in the PPy shell, compared with precursor polystyrene/Au composites and bare Fe3O4 nanoparticles, the stability of Au@PPy/Fe3O4 hollow capsules was greatly enhanced. Since the current method is simple and flexible to create recyclable catalysts with high stability, it would promote the practicability of metal nanoparticle catalysts in industrial polluted water treatment.

  19. 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.

  20. A Comparative Study of N2O Formation during the Selective Catalytic Reduction of NOx with NH3 on Zeolite Supported Cu Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Hai-Ying; Wei, Zhehao; Kollar, Marton; Gao, Feng; Wang, Yilin; Szanyi, Janos; Peden, Charles HF

    2015-09-01

    A comparative study was carried out on a small-pore CHA.Cu and a large-pore BEA.Cu zeolite catalyst to understand the lower N2O formation on small-pore zeolite supported Cu catalysts in the selective catalytic reduction (SCR) of NOx with NH3. On both catalysts, the N2O yield increases with an increase in the NO2/NOx ratios of the feed gas, suggesting N2O formation via the decomposition of NH4NO3. Temperature-programmed desorption experiments reveal that NH4NO3 is more stable on CHA.Cu than on BEA.Cu. In situ FTIR spectra following stepwise (NO2 + O2) and (15NO + NH3 + O2) adsorption and reaction, and product distribution analysis using isotope-labelled reactants, unambiguously prove that surface nitrate groups are essential for the formation of NH4NO3. Furthermore, CHA.Cu is shown to be considerably less active than BEA.Cu in catalyzing NO oxidation and the subsequent formation of surface nitrate groups. Both factors, i.e., (1) the higher thermal stability of NH4NO3 on CHA.Cu, and (2) the lower activity for this catalyst to catalyze NO oxidation and the subsequent formation of surface nitrates, likely contribute to the higher SCR selectivity with less N2O formation on this catalyst as compared to BEA.Cu. The latter is determined as the primary reason since surface nitrates are the source that leads to the formation of NH4NO3 on the catalysts.

  1. 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.

  2. Active sites, deactivation and stabilization of Fe-ZSM-5 for the selective catalytic reduction (SCR) of NO with NH(3).

    Science.gov (United States)

    Kröcher, Oliver; Brandenberger, Sandro

    2012-01-01

    Fe-ZSM-5 has been systematically investigated as catalyst for the selective catalytic reduction (SCR) of NO with NH(3), concentrating on the active sites, the deactivation mechanism during hydrothermal aging and the chemical possibilities to stabilize this type of SCR catalyst. Regarding the active SCR sites, it could be shown that monomeric species start to become active at the lowest temperatures (E(a,app) ≈ 36.3 ± 0.2 kJ/mol), followed by dimeric species at intermediate temperatures (E(a,app) ≈ 77 ± 16 kJ/mol) and oligomeric species at high temperatures. Experiments with Fe-ZSM-5 samples, in which the Brønsted acidity was specifically removed, proved that Brønsted acidity is not required for high SCR activity and that NH(3) can also be adsorbed on other acidic sites on the zeolite surface. The hydrothermal deactivation of Fe-ZSM-5 could be explained by the migration of active iron ions from the exchange sites. Parallel to the iron migration dealumination of the zeolite framework occurs, which has to be regarded as an independent process. The migration of iron can be reduced by the targeted reaction of the aluminum hydroxide groups in the lattice with trimethylaluminium followed by calcination. With respect to the application of iron zeolites in the SCR process in diesel vehicles, the most efficient stabilization method would be to switch from the ZSM-5 to the BEA structure type. The addition of NO(2) to the feed gas is another effective measure to increase the activity of even strongly deactivated iron zeolites tremendously.

  3. SnxTi1-xO2 Solid Solution Catalysts for Nitrogen Oxide Selective Catalytic Reduction by Propene in Presence of Oxygen

    Institute of Scientific and Technical Information of China (English)

    尉继英; 马军; 朱月香; 蔡小海; 谢有畅

    2001-01-01

    A series of SnO2-TiO2 binary oxide catalysts prepared by cocurrent precipitation method was found to be a novel and good system for the selective catalytic reduction of NO by propene in the presence of oxygen with high activity and good selectivity to N2. The NO conversion to N2 over SnO2-TiO2 oxide catalysts varied with SnO2 content and attainted a maximum at 65% over the catalyst with SnO2 content at 40wt% for a feed with 1186 ppm NO, 948 ppm propene and 2.23% O2 in He and a space velocity of 15000 h-1 at 350℃. The SnO2-TiO2catalysts could sustain moderate activity in the presence of 10% steam. Because of the identical valence and the similar radius of Sn4+ and Ti4+ , SnO2-TiO2 binary oxides can form solid solution in three different phases as proved by XRD,electron diffraction and TPR. Sn4+ is the main active species in the SnO2-TiO2 catalysts, and it is enriched on the solid solution surface as tested by XPS analysis. H2-TPR, NH3-TPD and BET tests show that SnO2-TiO2 solid solution can dilute SnO2 and suppress the activity of propene complete oxidation over SnO2. This may be beneficial to the reactivity enhancement of NO conversion.

  4. Copper-impregnated Al-Ce-pillared clay for selective catalytic reduction of NO by C{sub 3}H{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Qichun; Hao, Jiming; Li, Junhua [Department of Environmental Science and Engineering, Tsinghua University, Beijing 100084 (China); Ma, Zifeng [Department of Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Lin, Weiming [Department of Chemical Engineering, Guangzhou University, Guangzhou 510405 (China)

    2007-08-30

    The selective catalytic reduction (SCR) of NO by hydrocarbon is an efficient way to remove NO emission from lean-burn gasoline and diesel exhaust. In this paper, a thermally and hydrothermally stable Al-Ce-pillared clay (Al-Ce-PILC) was synthesized and then modified by SO{sub 4}{sup 2-}, whose surface area and average pore diameter calcined at 773 K were 161 m{sup 2}/g and 12.15 nm, respectively. Copper-impregnated Al-Ce-pillared clay catalyst (Cu/SO{sub 4}{sup 2-}/Al-Ce-PILC) was applied for the SCR of NO by C{sub 3}H{sub 6} in the presence of oxygen. The catalyst 2 wt% Cu/SO{sub 4}{sup 2-}/Al-Ce-PILC showed good performance over a broad range of temperature, its maximum conversion of NO was 56% at 623 K and remained as high as 22% at 973 K. Furthermore, the presence of 10% water slightly decreased its activity, and this effect was reversible following the removal of water from the feed. Py-IR results showed SO{sub 4}{sup 2-} modification greatly enhanced the number and strength of Broensted acidity on the surface of Cu/SO{sub 4}{sup 2-}/Al-Ce-PILC, which played a vital role in the improvement of NO conversion. TPR and XPS results indicated that both Cu{sup +} and isolated Cu{sup 2+} species existed on the optimal catalyst, mainly Cu{sup +}, as Cu content increased to 5 wt%, another species CuO aggregates which facilitated the combustion of C{sub 3}H{sub 6} were formed. (author)

  5. Enantioselectivity in the phytotoxicity of herbicide imazethapyr.

    Science.gov (United States)

    Zhou, Qingyan; Xu, Chao; Zhang, Yongsong; Liu, Weiping

    2009-02-25

    Chiral compounds usually behave enantioselectively in phyto-biochemical processes. With the increasing application of chiral herbicides, their enantioselective phytotoxicity to plants merits further study, and little information is available in this area. The purpose of this study was to examine the enantioselective phytotoxicity of the herbicide imazethapyr (IM) on the roots of maize (Zea mays L.) seedlings. Enantiomers of IM were separated by HPLC, and their absolute configurations were confirmed as S-(+)-IM and R-(-)-IM by the octant rule. Plant growth measurements and morphological, microscopic, and ultrastructural observations were conducted after treatment with individual IM enantiomers and the racemate. Observations of root morphology showed that the root diameter significantly increased, whereas the root volume, surface area, and number of root tips decreased significantly. IM enantiomers selectively damaged root hair growth and significantly reduced the sloughing of border cells from the tips. IM also had adverse effects on cell organelles, such as statocytes, mitochondria, dictyosomes, and endoplasmic reticulum in maize roots. Moreover, cell membranes and cell walls were thicker than usual after IM treatment. All of the results showed the same trend that the R-(-)-IM affected the root growth of maize seedlings more severely than the S-(+)-IM. The inhibition abilities of (+/-)-IM was between S-(+)- and R-(-)-IM. The behavior of the active enantiomer, instead of just the racemate, may have more relevance to the herbicidal effects and ecological safety of IM. Therefore, enantiomeric differences should be considered when evaluating the bioavailability of the herbicide IM.

  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. Asymmetric Intramolecular Alkylation of Chiral Aromatic Imines via Catalytic C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Watzke, Anja; Wilson, Rebecca; O' Malley, Steven; Bergman, Robert; Ellman, Jonathan

    2007-04-16

    The asymmetric intramolecular alkylation of chiral aromatic aldimines, in which differentially substituted alkenes are tethered meta to the imine, was investigated. High enantioselectivities were obtained for imines prepared from aminoindane derivatives, which function as directing groups for the rhodium-catalyzed C-H bond activation. Initial demonstration of catalytic asymmetric intramolecular alkylation also was achieved by employing a sterically hindered achiral imine substrate and catalytic amounts of a chiral amine.

  8. Chiral separation by enantioselective liquid-liquid extraction

    NARCIS (Netherlands)

    Schuur, B.; Verkuijl, B. J. V.; Minnaard, A. J.; De Vries, J. G.; Heeres, H. J.; Feringa, B. L.

    2011-01-01

    The literature on enantioselective liquid-liquid extraction (ELLE) spans more than half a century of research. Nonetheless, a comprehensive overview has not appeared during the past few decades. Enantioselective liquid-liquid extraction is a technology of interest for a wide range of chemists and ch

  9. Enantioselective N-heterocyclic carbene-catalyzed synthesis of trifluoromethyldihydropyridinones.

    Science.gov (United States)

    Wang, Dong-Ling; Liang, Zhi-Qin; Chen, Kun-Quan; Sun, De-Qun; Ye, Song

    2015-06-05

    The enantioselective N-heterocyclic carbene-catalyzed [4 + 2] cyclocondensation of α-chloroaldehydes and trifluoromethyl N-Boc azadienes was developed, giving the corresponding 3,4-disubstituted-6-trifluoromethyldihydropyridin-2(1H)-ones in good yields with exclusive cis-selectivities and excellent enantioselectivities.

  10. 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

  11. The first catalytic asymmetric addition of diethylzinc to aldehyde promoted by chiral thiourea

    Institute of Scientific and Technical Information of China (English)

    Zhi Guo Qiao; Tian Hua Shen; Zhen Fang Fu; Jun Qi Li; Hong Wang; Qing Bao Song

    2011-01-01

    A series of C2-symmetric and asymmetric chiral thiourea derivatives were synthesized from commercial L-phenylalanine. All of the new compounds have been fully characterized by IR, 1H NMR, 13C NMR, MS spectra and elemental analyses. The chiral thioureas were used as chiral ligands in the catalytic enantioselective ethylation of aldehydes with diethylzinc, the corresponding sec-alcohols were gained with excellent enantioselectivities (up to 87.1 % ee) and high yields (up to 76.7%) after the conditions were optimized.

  12. Using a dual plasma process to produce cobalt--polypyrrole catalysts for the oxygen reduction reaction in fuel cells -- part I: characterisation of the catalytic activity and surface structure

    CERN Document Server

    Walter, Christian; Vyalikh, Denis; Brüser, Volker; Quade, Antje; Weltmann, Klaus-Dieter; 10.1149/2.078208jes

    2012-01-01

    A new dual plasma coating process to produce platinum-free catalysts for the oxygen reduction reaction in a fuel cell is introduced. The catalysts thus produced were analysed with various methods. Electrochemical characterisation was carried out by cyclic voltammetry, rotating ring- and rotating ring-disk electrode. The surface porosity of the different catalysts thus obtained was characterised with the nitrogen gas adsorption technique and scanning electron microscopy was used to determine the growth mechanisms of the films. It is shown that catalytically active compounds can be produced with this dual plasma process. Furthermore, the catalytic activity can be varied significantly by changing the plasma process parameters. The amount of H$_2$O$_2$ produced was calculated and shows that a 2 electron mechanism is predominant. The plasma coating mechanism does not significantly change the surface BET area and pore size distribution of the carbon support used. Furthermore, scanning electron microscopy pictures o...

  13. Achillea millefolium L. extract mediated green synthesis of waste peach kernel shell supported silver nanoparticles: Application of the nanoparticles for catalytic reduction of a variety of dyes in water.

    Science.gov (United States)

    Khodadadi, Bahar; Bordbar, Maryam; Nasrollahzadeh, Mahmoud

    2017-05-01

    In this paper, silver nanoparticles (Ag NPs) are synthesized using Achillea millefolium L. extract as reducing and stabilizing agents and peach kernel shell as an environmentally benign support. FT-IR spectroscopy, UV-Vis spectroscopy, X-ray Diffraction (XRD), Field emission scanning electron microscopy (FESEM), Energy Dispersive X-ray Spectroscopy (EDS), Thermo gravimetric-differential thermal analysis (TG-DTA) and Transmission Electron Microscopy (TEM) were used to characterize peach kernel shell, Ag NPs, and Ag NPs/peach kernel shell. The catalytic activity of the Ag NPs/peach kernel shell was investigated for the reduction of 4-nitrophenol (4-NP), Methyl Orange (MO), and Methylene Blue (MB) at room temperature. Ag NPs/peach kernel shell was found to be a highly active catalyst. In addition, Ag NPs/peach kernel shell can be recovered and reused several times with no significant loss of its catalytic activity.

  14. Testing and design of selective catalytic reduction DENOX catalysts on the basis of titanium dioxide for flue gas cleaning plants. Pruefung und Auslegung von SCR-DENOX-Katalysatoren auf Basis TiO sub 2 fuer Rauchgasreinigungsanlagen

    Energy Technology Data Exchange (ETDEWEB)

    Neufert, R.; Zuerbig, J. (Siemens AG Unternehmensbereich KWU, Redwitz (Germany, F.R.). Keramik- und Porzellanwerk)

    1990-12-01

    Selective catalytic reduction catalysts based on titanium dioxide enjoy a commanding position in the market. Reasons for this are high catalytic activity with simultaneous high specificity, low SO{sub 2}/SO{sub 3} oxidation rates, chemical resistance against acid, flue gas constituents and mechanical stabiliy. The principle of DENOX catalyst design is precise knowledge and analyses of the limiting conditions under which use in the power station shall result. A suitable type of catalyst has to be selected in accordance with the conditions of application. Manufacture has to be supported by a complex system of quality assurance measures and tests, so that the catalyst characteristics specified in the design can be guaranteed. (orig.).

  15. Iridium-catalyzed enantioselective hydrogenation of imines in supercritical carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Kainz, S.; Brinkmann, A.; Leitner, W.; Pfaltz, A.

    1999-07-14

    Supercritical carbon dioxide (scCO{sub 2}) was shown to be a reaction medium with unique properties for highly efficient iridium-catalyzed enantioselective hydrogenation of prochiral imines. Cationic iridium(I) complexes with chiral phosphinodihydrooxazoles, modified with perfluoroalkyl groups in the ligand or in the anion, were synthesized and tested in the hydrogenation of N-(1-phenylethylidene)aniline. Both the side chains and the lipophilic anions increased the solubility, but the choice of the anion also had a dramatic effect on the enantioselectivity with tetrakis-3,5-bis(trifluoromethyl)phenylborate (BARF) leading to the highest asymmetric induction. (R)-N-phenyl-1-phenylethylamine was formed quantitatively within 1 h in scCO{sub 2}[d(CO{sub 2}) = 0.75 g mL{sup {minus}1}] at 40 C and a H{sub 2} pressure of 30 bar with enantiomeric excesses of up to 81% using 0.078 mol % catalyst. The use of scCO{sub 2} instead of conventional solvents such as CH{sub 2}Cl{sub 2} allowed the catalyst loading to be lowered significantly owing to a change in the rate profile of the reaction. the homogeneous nature of the catalytically active species under the reaction conditions was demonstrated and was found to depend strongly on the composition of the reaction mixture and especially on the presence of the substrate. Utilizing the selective extractive properties of scCO{sub 2}, the product could be readily separated from the catalyst, which could be recycled several times without significant loss of activity and enantioselectivity. High-pressure FT-IR and NMR investigations revealed that the reactivity of the products to form the corresponding carbamic acids plays an important role for the application of this new methodology.

  16. Enantioselective cellular uptake of chiral semiconductor nanocrystals

    Science.gov (United States)

    Martynenko, I. V.; Kuznetsova, V. A.; Litvinov, I. K.; Orlova, A. O.; Maslov, V. G.; Fedorov, A. V.; Dubavik, A.; Purcell-Milton, F.; Gun'ko, Yu K.; Baranov, A. V.

    2016-02-01

    The influence of the chirality of semiconductor nanocrystals, CdSe/ZnS quantum dots (QDs) capped with L- and D-cysteine, on the efficiency of their uptake by living Ehrlich Ascite carcinoma cells is studied by spectral- and time-resolved fluorescence microspectroscopy. We report an evident enantioselective process where cellular uptake of the L-Cys QDs is almost twice as effective as that of the D-Cys QDs. This finding paves the way for the creation of novel approaches to control the biological properties and behavior of nanomaterials in living cells.

  17. Conjugate addition–enantioselective protonation reactions

    Directory of Open Access Journals (Sweden)

    James P. Phelan

    2016-06-01

    Full Text Available The addition of nucleophiles to electron-deficient alkenes represents one of the more general and commonly used strategies for the convergent assembly of more complex structures from simple precursors. In this review the addition of diverse protic and organometallic nucleophiles to electron-deficient alkenes followed by enantioselective protonation is summarized. Reactions are first categorized by the type of electron-deficient alkene and then are further classified according to whether catalysis is achieved with chiral Lewis acids, organocatalysts, or transition metals.

  18. Conjugate addition–enantioselective protonation reactions

    Science.gov (United States)

    Phelan, James P

    2016-01-01

    Summary The addition of nucleophiles to electron-deficient alkenes represents one of the more general and commonly used strategies for the convergent assembly of more complex structures from simple precursors. In this review the addition of diverse protic and organometallic nucleophiles to electron-deficient alkenes followed by enantioselective protonation is summarized. Reactions are first categorized by the type of electron-deficient alkene and then are further classified according to whether catalysis is achieved with chiral Lewis acids, organocatalysts, or transition metals. PMID:27559372

  19. 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.

  20. Catalytic asymmetric synthesis of enantioenriched heterocycles bearing a C-CF3 stereogenic center.

    Science.gov (United States)

    Huang, Yi-Yong; Yang, Xing; Chen, Zhuo; Verpoort, Francis; Shibata, Norio

    2015-06-08

    Given the important agricultural and medicinal application of optically pure heterocycles bearing a trifluoromethyl group at the stereogenic carbon center in the heterocyclic framework, the exploration of efficient and practical synthetic strategies to such types of molecules remains highly desirable. Catalytic enantioselective synthesis has one clear advantage that it is more cost-effective than other synthetic methods, but remains limited by challenges in achieving excellent yield and stereoselectivities with a low catalyst loading. Thus far, numerous models of organo- and organometal-catalyzed asymmetric reactions have been exploited to achieve this elusive goal over the past decade. This review article describes recent progress on this research topic, and focuses on an understanding of the catalytic asymmetric protocols exemplified in the catalytic enantioselective synthesis of a wide range of complex enantioenriched trifluoromethylated heterocycles.

  1. SELECTIVE CATALYTIC REDUCTION (SCR OF NO BY AMMONIA OVER V2O5/TiO2 CATALYST IN A CATALYTIC FILTER MEDIUM AND HONEYCOMB REACTOR: A KINETIC MODELING STUDY

    Directory of Open Access Journals (Sweden)

    M. Nahavandi

    2015-12-01

    Full Text Available Abstract The present study addresses a numerical modeling and simulation based on the available knowledge of SCR kinetics for prediction of NO conversion over a V2O3/TiO3 catalyst through a catalytic filter medium and honeycomb reactor. After introducing the NH3-SCR system with specific operational criteria, a reactor model was developed to evaluate the effect of various operating parameters such as flue gas temperature, velocity, NH3/NO molar ratio, etc., on the SCR process. Computational investigations were performed based on the proposed model and optimum operational conditions were identified. Simulation results indicate that SCR performance is substantially under the effects of reactant concentration and operating temperature, so that the concentration of unreacted ammonia emitted from reactor discharge (ammonia slip increases significantly at NH3/NO ratios of more than 1.14 and operating temperatures less than 360 ºC and 300 ºC, respectively, in the catalytic filter medium and honeycomb reactor. The results also show that there are three sections in NO conversion variation versus changing temperature and the required conversion with a maximum of almost 87% and low level of ammonia slip can be achieved at the NH3/NO ratio of 1 and temperature range of 240–360 ºC in both reactors.

  2. Soluble Expression of (+)-γ-Lactamase in Bacillus subtilis for the Enantioselective Preparation of Abacavir Precursor.

    Science.gov (United States)

    Xue, Tian-Yun; Xu, Guo-Chao; Han, Rui-Zhi; Ni, Ye

    2015-07-01

    Chiral Vince lactam (γ-lactam) is an important precursor of many carbocyclic nucleoside analogues and pharmaceuticals. Here, a (+)-γ-lactamase encoding gene delm from Delftia sp. CGMCC 5755 was identified through genome hunting. To achieve its soluble and functional expression, Escherichia coli and Bacillus subtilis expression systems were introduced. Compared with E. coli system, recombinant (+)-γ-lactamase showed improved protein solubility and catalytic activity in B. subtilis 168. Reaction conditions for enantioselective resolution of γ-lactam were optimized to be at 30 °C, pH 9.0, and 300 rpm when employing the recombinant B. subtilis 168/pMA5-delm whole cells. Kinetic analysis showed that the apparent V max and K m were 0.595 mmol/(min · gDCW) and 378 mmol/L, respectively. No obvious substrate inhibition was observed. In a 500-mL reaction system, enantioselective resolution of 100 g/L γ-lactam was achieved with 10 g/L dry cells, resulting in 55.2 % conversion and 99 % ee of (-)-γ-lactam. All above suggested that recombinant B. subtilis 168/pMA5-delm could potentially be applied in the preparation of optically pure (-)-γ-lactam.

  3. 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.

  4. 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.)

  5. 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. Quarterly report No. 3, January--March 1991

    Energy Technology Data Exchange (ETDEWEB)

    1991-07-01

    The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from US, Japanese and European catalyst suppliers on a high-sulfur US coal-fired boiler. SCR is a post-combustion nitrogen oxide (NOx) 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 NOx to convert it to nitrogen and water vapor.

  6. 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

    Energy Technology Data Exchange (ETDEWEB)

    1991-07-01

    The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from US, Japanese and European catalyst suppliers on a high-sulfur US coal-fired boiler. SCR is a post-combustion nitrogen oxide (NOx) 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 NOx to convert it to nitrogen and water vapor.

  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 1995

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-05-01

    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 convert it to nitrogen and water vapor.

  8. 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

    Energy Technology Data Exchange (ETDEWEB)

    1991-02-01

    The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from US, Japanese and European catalyst suppliers on a high-sulfur US 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 convert it to nitrogen and water vapor.

  9. 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. Quarterly report No. 2, October--December 1990

    Energy Technology Data Exchange (ETDEWEB)

    1991-02-01

    The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from US, Japanese and European catalyst suppliers on a high-sulfur US 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 convert it to nitrogen and water vapor.

  10. Synthesis of novel chiral tridentate Schiff-base ligands and their applications in catalytic asymmetric Henry reaction.

    Science.gov (United States)

    Qiang, Gen-Rong; Shen, Tian-Hua; Zhou, Xiao-Cong; An, Xiao-Xia; Song, Qing-Bao

    2014-12-01

    A series of chiral tridentate Schiff-bases were prepared and used as ligands in the catalytic asymmetric Henry reaction. Under the optimal conditions, a variety of arylaldehydes were smoothly converted into corresponding adducts with high yields (up to 98%) and excellent enantioselectivities (up to 97% ee).

  11. La{sub 1−x}Ce{sub x}Mn{sub 1−y}Co{sub y}O{sub 3} perovskite oxides: Preparation, physico-chemical properties and catalytic activity for the reduction of diesel soot

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Shaohua; Song, Chonglin, E-mail: songchonglin@tju.edu.cn; Bin, Feng; Lv, Gang; Song, Jinou; Gong, Cairong

    2014-11-14

    La{sub 1−x}Ce{sub x}Mn{sub 1−y}Co{sub y}O{sub 3} catalysts were prepared by the “glucose method”. The structures and physico-chemical properties for these catalysts were characterized using X-ray diffraction (XRD), nitrogen adsorption, scanning electron microscopy (SEM), Fourier transform infrared spectra (FT-IR), H{sub 2}-temperature-programmed reduction (H{sub 2}-TPR) and O{sub 2}-tempreature-programmed desorption (O{sub 2}-TPD). Results showed that cerium substitution at the A-site in LaMnO{sub 3} produced a CeO{sub 2} phase. The cobalt can be introduced into the B-site in La{sub 0.8}Ce{sub 0.2}MnO{sub 3} at any substitution ratio because of the similar ionic radii between cobalt and manganese. The catalytic activity for soot combustion in air was evaluated using a TG/DTA analyzer. Cerium substitution at A-site enhances the catalytic activity, while cobalt substitution at B-site inhibits the catalytic activity. The activation energy for soot combustion was calculated using the Horowitz method. The activation energy for non-catalytic soot combustion was 164.1 kJ mol{sup −1}. The addition of catalysts decreased the activation energy by about 26–63 kJ mol{sup −1}. Among the applied catalysts, Ce20Mn exhibited the lowest activation energy (101.1 kJ mol{sup −1}). - Highlights: • Cerium substitution at A-site in Mn100 enhances the catalytic activity. • Cerium substitution leads to the formation of the CeO{sub 2} phase. • Cobalt substitution at B-site in Ce20Mn generally decreases the catalytic activity. • Cerium substitution increases the α-O{sub 2} amount and low-temperature reducibility. • Cobalt substitution decreases the α-O{sub 2} amount and low-temperature reducibility.

  12. Multivalent polyglycerol supported imidazolidin-4-one organocatalysts for enantioselective Friedel–Crafts alkylations

    Directory of Open Access Journals (Sweden)

    Tommaso Pecchioli

    2015-05-01

    Full Text Available The first immobilization of a MacMillan’s first generation organocatalyst onto dendritic support is described. A modified tyrosine-based imidazolidin-4-one was grafted to a soluble high-loading hyperbranched polyglycerol via a copper-catalyzed alkyne–azide cycloaddition (CuAAC reaction and readily purified by dialysis. The efficiency of differently functionalized multivalent organocatalysts 4a–c was tested in the asymmetric Friedel–Crafts alkylation of N-methylpyrrole with α,β-unsaturated aldehydes. A variety of substituted enals was investigated to explore the activity of the catalytic system which was also compared with monovalent analogues. The catalyst 4b showed excellent turnover rates and no loss of activity due to immobilization, albeit moderate enantioselectivities were observed. Moreover, easy recovery by selective precipitation allowed the reuse of the catalyst for three cycles.

  13. Enantiomer separation by ultrafiltration of enantioselective micelles in multistage systems

    NARCIS (Netherlands)

    Overdevest, P.E.M.

    2000-01-01

    The Food and Bioprocess Engineering Group of Wageningen University, The Netherlands, is developing a new enantiomer separation system that is based on ultrafiltration (UF) of enantioselective micelles containing chiral selector molecules. Enantiomer molecules are optical isomers (mirror images), and

  14. Enantioselective alcohol synthesis using ketoreductases, lipases or an aldolase

    NARCIS (Netherlands)

    Sorgedrager, M.J.

    2006-01-01

    The demand for optically pure secondary alcohols, which has grown rapidly in recent years, has spurred the development of adequate enantioselective synthetic procedures. Although there are various chemical methods available, biocatalysts are increasingly applied due to their natural characteristic t

  15. Combined effects Na and SO2 in flue gas on Mn-Ce/TiO2 catalyst for low temperature selective catalytic reduction of NO by NH3 simulated by Na2SO4 doping

    Science.gov (United States)

    Zhou, Aiyi; Yu, Danqing; Yang, Liu; Sheng, Zhongyi

    2016-08-01

    A series of Mn-Ce/TiO2 catalysts were synthesized through an impregnation method and used for low temperature selective catalytic reduction (SCR) of NOx with ammonia (NH3). Na2SO4 was added into the catalyst to simulate the combined effects of alkali metal and SO2 in the flue gas. Experimental results showed that Na2SO4 had strong and fluctuant influence on the activity of Mn-Ce/TiO2, because the effect of Na2SO4 included pore occlusion and sulfation effect simultaneously. When Na2SO4 loading content increased from 0 to 1 wt.%, the SCR activities of Na2SO4-doped catalysts decreased greatly. With further increasing amount of Na2SO4, however, the catalytic activity increased gradually. XRD results showed that Na2SO4 doping could induce the crystallization of MnOx phases, which were also confirmed by TEM and SEM results. BET results showed that the surface areas decreased and a new bimodal mesoporous structure formed gradually with the increasing amount of Na2SO4. XPS results indicated that part of Ce4+ and Mn3+ were transferred to Ce3+ and Mn4+ due to the sulfation after Na2SO4 deposition on the surface of the catalysts. When the doped amounts of Na2SO4 increased, NH3-TPD results showed that the Lewis acid sites decreased and the Brønsted acid sites of Mn-Ce/TiO2 increased quickly, which could be considered as another reason for the observed changes in the catalytic activity. The decreased Mn and Ce atomic concentration, the changes of their oxidative states, and the variation in acidic properties on the surface of Na2SO4-doped catalysts could be the reasons for the fluctuant changes of the catalytic activity.

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

    Science.gov (United States)

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

    2012-01-01

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

  17. Enantioselective Organocatalytic Cascade Approach to Different Classes of Benzofused Acetals.

    Science.gov (United States)

    Paz, Bruno Matos; Klier, Lydia; Naesborg, Line; Lauridsen, Vibeke Henriette; Jensen, Frank; Jørgensen, Karl Anker

    2016-11-14

    A novel enantioselective organocatalytic strategy is presented for the synthesis of tetrahydrofurobenzofuran and methanobenzodioxepine natural product core structures. The strategy is based on a pair of divergent reaction pathways in which hydroxyarenes react with γ-keto-α,β-unsaturated aldehydes, catalyzed by a chiral secondary amine. One reaction pathway, which leads to chiral 5,5-fused acetals with two stereocenters-the tetrahydrofurobenzofuran scaffolds-proceeds in moderate yields and up to 96 % ee. The other reaction pathway provides 5,6-bridged methanobenzodioxepine scaffolds with three stereocenters in moderate to good yields and up to 95 % ee. The reaction is remarkable as it can proceed with catalyst loadings as low as 0.25 mol %, providing one of the highest known turnover numbers in iminium ion catalysis. Furthermore, the hemiacetal tetrahydrofurobenzofuran can undergo functionalizations including reduction, oxidation, and allylation. Finally, the effects involved in the substrate control for the divergent pathways, based on both experimental and computational studies, have been investigated. A model involving steric, electronic and stereoelectronic interactions is discussed to rationalize the observed selectivities.

  18. Enantioselective Organocatalytic α-Fluorination of Cyclic Ketones

    OpenAIRE

    Kwiatkowski, Piotr; Beeson, Teresa D.; Conrad, Jay C.; MacMillan, David W. C.

    2011-01-01

    The first highly enantioselective α-fluorination of ketones using organocatalysis has been accomplished. The long-standing problem of enantioselective ketone α-fluorination via enamine activation has been overcome via high-throughput evaluation of a new library of amine catalysts. The optimal system, a primary amine functionalized Cinchona alkaloid, allows the direct and asymmetric α-fluorination of a variety of carbo- and heterocyclic substrates. Furthermore, this protocol also provides dias...

  19. Enantioselective Degradation of Triadimefon in Green-house Soil

    Directory of Open Access Journals (Sweden)

    Liu Hong Cheng

    2015-09-01

    Full Text Available To study enantioselctive degradation of triadimefon, the enantioselective degradation of triadimefon in greenhouse soil and normal soil were investigated in detail. The enantiomers of triadimefon were separated by Chiralpak AD column and determined by Liquid Chromatography Via Tandem Mass Spectrometry (LC-MS/MS. The degradation exhibited some enantioselective, resulting in a concentration order of R-(- tridimefon>S-(+ triadimefon and the degradation of triadimefon in greenhouse soils with high content of organic matter was faster than normal soil.

  20. Emerging functional chiral microporous materials: synthetic strategies and enantioselective separations

    Directory of Open Access Journals (Sweden)

    Ming Xue

    2016-11-01

    Full Text Available In recent years, chiral microporous materials with open pores have attracted much attention because of their potential applications in enantioselective separation and catalysis. This review summarizes the recent advances on chiral microporous materials, such as metal-organic frameworks (MOFs, hydrogen-bonded organic frameworks (HOFs and covalent organic frameworks (COFs. We will introduce the synthetic strategies in detail and highlight the current status of chiral microporous materials on solid enantioselective adsorption, chiral chromatography resolution and membrane separation.

  1. Unsteady catalytic processes and sorption-catalytic technologies

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-07-31

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

  2. 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

    ) 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......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......, 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....

  3. Studies of Electrochemical Catalytic Reduction Reactions of Tetraphenylporphinatocobalt/1,2-Dibromoethane and 1,2-Dichloroethane Systems in Nonaqueous Media

    Institute of Scientific and Technical Information of China (English)

    林祥钦; 刘殿骏; 汪尔康

    1994-01-01

    Electrochemical catalytic reactions of tetraphenylporphmatocobalt were studied in DMF and EtCl2 solutions in the presence of 1,2 dibroraoethane and 1,2-dichloroethane utilizing cyclic voltamme-try, thin-layer electrochemistry, in situ UV-visible spectroelectrochemistry and computer digital simulation methods. Homogeneous rate constants for reactions of electrogenerated Co(Ⅰ)TPP species with 1,2-dibro-moethane and 1,2-dichloroethane were determined as 1. 2×103 and 5 mol-1 · dm3 × s-1, respectively. Neither alkylation nor degradation of CoTPP was observed.

  4. Catalytic activity and mechanistic approach of NO reduction by CO over M0.05Co2.95O4 (M = Rh, Pd & Ru) spinel system

    Science.gov (United States)

    Salker, A. V.; Desai, M. S. Fal

    2016-12-01

    Pd, Rh and Ru doped cobalt oxide spinels have been prepared by citric acid assisted sol-gel method to yield nano-catalysts. Compositions have been characterized by XRD, FTIR, TG/DTA, BET, SEM, TEM, TPD and XPS techniques. Simultaneous catalytic detoxification of nitric oxide and carbon monoxide is investigated over the doped and pristine catalysts. Metal doping is found to enhance the activity of the catalysts due to their better adsorption capacity. Moisture and oxygen tolerance is investigated for Rh and Pd substituted catalysts. A probable reaction mechanism on the catalyst surface has been proposed.

  5. Fabrication of MgAl2Si2O8 : M0.01 (M = Ni2+, Cu2+, Pd2+, Pt2+ and Ru3+): catalytic effects for the reduction of 2- or 4-nitroanilines in water

    Indian Academy of Sciences (India)

    Serkan Dayan; Sevgi Öztürk; Nilgün Kayaci; Nilgun Kalaycioglu Ozpozan; Esra Öztürk

    2015-10-01

    Five new MgAl2Si2O8 : M0.01 (M = Ni2+, Cu2+, Pd2+, Pt2+ and Ru3+) materials were developed for the reduction of nitroarenes as catalysts by conventional solid state reaction at 1300°C. The prepared materials were characterized by thermal analysis, Fourier transform infrared spectroscopy, X-ray powder diffraction analysis, scanning electron microscopy, energy-dispersive X-ray analysis and nitrogen adsorption–desorption analysis. The catalytic activities of the prepared catalysts were tested in the reduction of 2- or 4-nitroanilines in aqueous media at ambient temperature in the presence of NaBH4 by UV–vis spectrophotometer. Furthermore, the MgAl2Si2O8 : M0.01 catalysts can be recovered by filtration and reused for five cycles for the reduction of 2-nitroaniline. These results show that the MgAl2Si2O8 : M0.01 catalysts can be used in practical applications in the reduction of nitroanilines.

  6. Design of multi-shell Fe2O3@MnOx@CNTs for the selective catalytic reduction of NO with NH3: improvement of catalytic activity and SO2 tolerance

    Science.gov (United States)

    Cai, Sixiang; Hu, Hang; Li, Hongrui; Shi, Liyi; Zhang, Dengsong

    2016-02-01

    -NOx performance. Moreover, the Fe2O3 shell could effectively suppress the formation of the surface sulfate species, leading to the desirable SO2 resistance to the multi-shell catalyst. Hence, the synthesis protocol could provide guidance for the preparation and elevation of manganese based catalysts. Electronic supplementary information (ESI) available: Experimental details and catalytic performance of the Fe-Mn@CNTs IM, TEM images of Fe@Mn CNTs, stability and H2O resistance studies of the catalysts. See DOI: 10.1039/c5nr08701e

  7. Comparative hepatic and extrahepatic enantioselective sulfoxidation of albendazole and fenbendazole in sheep and cattle.

    Science.gov (United States)

    Virkel, G; Lifschitz, A; Sallovitz, J; Pis, A; Lanusse, C

    2004-05-01

    The enantioselective sulfoxidation of the prochiral anthelmintic compounds albendazole (ABZ) and fenbendazole (FBZ) was investigated in liver, lung and small intestinal microsomes obtained from healthy sheep and cattle. The microsomal fractions were incubated with a 40 microM concentration of either ABZ or FBZ. Inhibition of the flavin-containing monooxygenase (FMO) system was carried out by preincubation with 100 microM methimazole (MTZ) either with or without heat pretreatment (2 min at 50 degrees C). ABZ and FBZ were metabolized to the (+) and (-) enantiomers of their sulfoxide metabolites, named albendazole sulfoxide (ABZSO) and oxfendazole (OFZ), respectively. ABZ sulfoxidation rates were higher (p < 0.001) than those observed for FBZ. The FMO-mediated liver sulfoxidation of ABZ was enantioselective (100%) toward the (+) ABZSO production in both species. Liver sulfoxidation of FBZ by FMO was also enantioselective toward (+) OFZ (sheep = 65%; cattle = 79%). Cytochrome P450 was found to be mainly involved in the production of (-) ABZSO in the liver. MTZ did not affect the sulfoxidation of ABZ by lung microsomes, which may indicate that FMO is not involved in the production of ABZSO in this tissue. A significant (p < 0.05) inhibition of (-) ABZSO production by liver microsomes was observed after ABZ incubation in the presence of erythromycin (cattle = 21%) and ketoconazole (sheep = 36%). Both CYP3A substrates induced a reduction in the production of (-) ABZSO (sheep = 67-78%, cattle = 50-78%) by lung microsomes. Overall, the results reported here contribute to the identification of the metabolic pathways involved in the biotransformation of benzimidazole anthelmintics extensively used for parasite control in ruminants.

  8. Effect of active component addition and support modification on catalytic activity of Ag/Al2O3 for the selective catalytic reduction of NOx by hydrocarbon - A review.

    Science.gov (United States)

    More, Pavan M

    2017-03-01

    The effect of active component addition and support modification of Ag/Al2O3 has been reviewed to examine their contribution to HC-SCR of NOx. This review has depicted the possible mechanisms of reduction of NO by hydrocarbon using metal/metal oxide doped Ag/Al2O3. The addition of second metal results in the maximum formation of well dispersed Agn(δ+) clusters. Specifically, addition of Au improves the low-temperature activity of the catalyst. However, the role of second metal also depends on the pretreatment to the catalyst and nature of the reductants. The support modification of Ag/Al2O3 by the addition of different metal oxides has also been reviewed. Modification by MgO showed improvement in activity besides sulfur tolerance. In situ DRIFT study demonstrates that the modification by MgO leads to the inhibition of sulfate formation of Ag and Al2O3. Enhancement in activity after second metal addition and support modification attributed to the synergistic effect and improved surface properties of Ag/Al2O3 catalyst.

  9. Catalytic performance of functionalized polyurethane foam on the reductive decolorization of Reactive Red K-2G in up-flow anaerobic reactor under saline conditions.

    Science.gov (United States)

    Zhou, Yang; Lu, Hong; Wang, Jing; Li, Jianan; Zhou, Jiti; Jin, Ruofei

    2015-01-01

    Soluble anthraquinone compounds including anthraquinone-2-sulfonate (AQS) and anthraquinone-2,6-disulfonate can accelerate anaerobic decolorization of azo dyes. To realize the application of these compounds, the catalytic performance and stability of AQS-modified polyurethane foam (AQS-PUF) for Reactive Red K-2G decolorization were investigated in an up-flow anaerobic bioreactor under saline conditions. The results showed that the optimal influent pH value and hydraulic retention time were 7 and 10 h, respectively, in a continuous-flow bioreactor amended with AQS-PUF (R1). Under the above conditions, R1 (93.8 % color removal) displayed better decolorization performance than the bioreactor amended with PUF (R2, 64 % color removal) in 10 days, when influent K-2G concentration was 50 mg/L. Moreover, compared with R2, R1 could more effectively cope with 50-400 mg/L K-2G and exhibited better stability with over 85 % color removal efficiency within 75 days. Further bacterial community analysis using polymerase chain reaction-denaturing gradient gel electrophoresis showed that AQS-reducing bacteria played an important role in accelerating K-2G decolorization in R1. Extracellular polymeric substances analysis found that biofilm formed on AQS-PUF had very limited negative effects on K-2G decolorization. The catalytic performance of used AQS-PUF only decreased less than 9 % in batch experiments. These findings indicate that AQS-PUF has potential application for the treatment of azo dye-containing wastewater.

  10. Hollow-shell-structured nanospheres: a recoverable heterogeneous catalyst for rhodium-catalyzed tandem reduction/lactonization of ethyl 2-acylarylcarboxylates to chiral phthalides.

    Science.gov (United States)

    Liu, Rui; Jin, Ronghua; An, Juzeng; Zhao, Qiankun; Cheng, Tanyu; Liu, Guohua

    2014-05-01

    Chiral organorhodium-functionalized hollow-shell-structured nanospheres were prepared by immobilization of a chiral N-sulfonylated diamine-based organorhodium complex within an ethylene-bridged organosilicate shell. Structural analysis and characterization reveal its well-defined single-site rhodium active center, and transmission electron microscopy images reveal a uniform dispersion of hollow-shell-structured nanospheres. As a heterogenous catalyst, it exhibits excellent catalytic activity and enantioselectivity in synthesis of chiral phthalides by a tandem reduction/lactonization of ethyl 2-acylarylcarboxylates in aqueous medium. The high catalytic performance is attributed to the synergistic effect of the high hydrophobicity and the confined chiral organorhodium catalytic nature. The organorhodium-functionalized nanospheres could be conveniently recovered and reused at least 10 times without loss of catalytic activity. This feature makes it an attractive catalyst in environmentally friendly organic reactions. The results of this study offer a new approach to immobilize chiral organometal functionalities within the hollow-shell-structured nanospheres to prepare materials with high activity in heterogeneous asymmetric catalysis.

  11. Influence of the addition of transition metals (Cr, Zr, Mo) on the properties of MnOx-FeOx catalysts for low-temperature selective catalytic reduction of NOx by Ammonia.

    Science.gov (United States)

    Zhou, Changcheng; Zhang, Yaping; Wang, Xiaolei; Xu, Haitao; Sun, Keqin; Shen, Kai

    2013-02-15

    The co-precipitation and citric acid methods were employed to prepare MnO(x)-FeO(x) catalysts for the low-temperature selective catalytic reduction (SCR) of NO(x) by ammonia. It was found that the Mn-Fe (CP) sample obtained from the co-precipitation method, which exhibited low crystalline of manganese oxides on the surface, high specific surface area and abundant acid sites at the surface, had better catalytic activity. The effects of doping different transition metals (Mo, Zr, Cr) in the Mn-Fe (CP) catalysts were further investigated. The study suggested that the addition of Cr can obviously reduce the take-off temperature of Mn-Fe catalyst to 90°C, while the impregnation of Zr and Mo raised that remarkably. The texture and micro-structure analysis revealed that for the Cr-doped Mn-Fe catalysts, the active components had better dispersion with less agglomeration and sintering and the largest BET surface specific area. In situ FTIR study indicated that the addition of Cr can increase significantly the surface acidity, especially, the Lewis acid sites, and promote the formation of the intermediate -NH(3)(+). H(2)-TPR results confirmed the better low-temperature redox properties of Mn-Fe-Cr.

  12. In situ DRIFTs investigation of the reaction mechanism over MnOx-MOy/Ce0.75Zr0.25O2 (M = Fe, Co, Ni, Cu) for the selective catalytic reduction of NOx with NH3

    Science.gov (United States)

    Hu, Hang; Zha, Kaiwen; Li, Hongrui; Shi, Liyi; Zhang, Dengsong

    2016-11-01

    A series of MnOx-MOy/Ce0.75Zr0.25O2 (M = Fe, Co, Ni, Cu) catalysts were synthesized by an impregnation method and used for selective catalytic reduction (SCR) of NOx with NH3. The catalytic performances of various MnOx-MOy/Ce0.75Zr0.25O2 catalysts were studied. It was found that MnOx-FeOy/Ce0.75Zr0.25O2 catalyst showed excellent low-temperature activity and a broad temperature window. The catalysts were characterized by N2 adsorption/desorption, X-ray diffraction, X-ray photoelectron spectroscopy and in situ diffuse reflectance infrared transform spectroscopy (DRIFTS). Characterization of the catalyst confirmed the addition of iron oxide can enhance the NO oxidation ability of the catalyst which results in the outstanding low-temperature SCR activity. Meanwhile, iron oxides were well dispersed on catalyst surface which could avoid the agglomeration of active species, contributing to the strong interaction between active species and the support. More importantly, in situ DRIFTS results confirmed that bidentate nitrates are general active species on these catalysts, whereas the reactivity of gaseous NO2 and bridged nitrates got improved because of the addition of Fe.

  13. Examination of surface phenomena of V₂O₅ loaded on new nanostructured TiO₂ prepared by chemical vapor condensation for enhanced NH₃-based selective catalytic reduction (SCR) at low temperatures.

    Science.gov (United States)

    Cha, Woojoon; Yun, Seong-Taek; Jurng, Jongsoo

    2014-09-01

    In this article, we describe the investigation and surface characterization of a chemical vapor condensation (CVC)-TiO2 support material used in a V2O5/TiO2 catalyst for enhanced selective catalytic reduction (SCR) activity and confirm the mechanism of surface reactions. On the basis of previous studies and comparison with a commercial TiO2 catalyst, we examine four fundamental questions: first, the reason for increased surface V(4+) ion concentrations; second, the origin of the increase in surface acid sites; third, a basis for synergistic influences on improvements in SCR activity; and fourth, a reason for improved catalytic activity at low reaction temperatures. In this study, we have cited the result of SCR with NH3 activity for removing NOx and analyzed data using the reported result and data from previous studies on V2O5/CVC-TiO2 for the SCR catalyst. In order to determine the properties of suitable CVC-TiO2 surfaces for efficient SCR catalysis at low temperatures, CVC-TiO2 specimens were prepared and characterized using techniques such as XRD, BET, HR-TEM, XPS, FT-IR, NH3-TPD, photoluminescence (PL) spectroscopy, H2-TPR, and cyclic voltammetry. The results obtained for the CVC-TiO2 materials were also compared with those of commercial TiO2.

  14. Catalytic asymmetric Povarov reaction of isatin-derived 2-azadienes with 3-vinylindoles.

    Science.gov (United States)

    Zhang, Hong-Hao; Sun, Xiao-Xue; Liang, Jing; Wang, Yue-Ming; Zhao, Chang-Chun; Shi, Feng

    2014-12-21

    The first catalytic asymmetric Povarov reaction of isatin-derived 2-azadienes with 3-vinylindoles was established in the presence of chiral phosphoric acid, which tolerates a wide range of substrates with generally excellent diastereoselectivity and good enantioselectivity (up to >95 : 5 dr, 89 : 11 er). This approach will greatly enrich the chemistry of the catalytic asymmetric Povarov reaction, in particular ketone-involved transformations. Furthermore, this protocol represents the first diastereo- and enantio-selective construction of a spiro[indolin-3,2'-quinoline] framework bearing an indole moiety. This novel type of spiro-compound not only contains two chiral centers, including one quaternary stereogenic center, but also integrates two biologically important structures of spiro[indolin-3,2'-quinoline] and indole, which may find medicinal applications after bioassay.

  15. Chemical Reduction of CO2 to Different Products during Photo Catalytic Reaction on TiO2 under Diverse Conditions: an Overview

    Institute of Scientific and Technical Information of China (English)

    G.R.Dey

    2007-01-01

    The chemical reduction of CO2 remains a challenge with respect to the reversal of the oxidative degradation of any organic materials.The conversion of CO2 into useful substances is essential in developing alternative fuels and various raw materials for different industries.This also aids in preventing the continuous rise in tropospheric temperature due to the green house effect of CO2.In this article an overview of the growth taken place so far in the field of CO2 chemical reduction is presented.The discussion comprises of photochemical methods for the development of different products,viz.CO,CH3OH and CH4,through chemical reduction of CO2.This includes the use of photo catalysts,mainly TiO2,and the role of a hole scavenger(such as 2-propan01) for this purpose.

  16. The selective catalytic reduction of NO with NH{sub 3} over a novel Ce–Sn–Ti mixed oxides catalyst: Promotional effect of SnO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    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); 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); Zeng, Guangming; Zhou, Yang; Zhang, Xunan; Xie, Yin’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)

    2015-07-01

    Graphical abstract: - Highlights: • A novel catalyst was developed for selective catalytic reduction of NO with NH{sub 3}. • The NO removal efficiency of CeTi catalyst was improved by the addition of SnO{sub 2}. • The novel catalyst possessed remarkable resistance to H{sub 2}O and SO{sub 2}. • The promotional effects of SnO{sub 2} were investigated in detail. • Possible reaction mechanism over the novel catalyst was discussed. - Abstract: A series of novel catalysts (CexSny) for the selective catalytic reduction of NO by NH{sub 3} 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 SnO{sub 2}. 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{sup −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 H{sub 2}O and SO{sub 2} poisoning due to the introduction of SnO{sub 2}. The promotional effect of SnO{sub 2} was studied by N{sub 2} adsorption–desorption, X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectroscopy (XPS) and H{sub 2} temperature programmed reduction (H{sub 2}-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 SnO{sub 2} could result in not only greater conversion of Ce{sup 4+} to Ce{sup 3+} but also the increase amount of chemisorbed oxygen, which are beneficial to improve the SCR

  17. 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.

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

    Institute of Scientific and Technical Information of China (English)

    张志强; 徐勇鹏; 时文歆; 张瑞君; 鲍现; 崔福义

    2016-01-01

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

  19. Research progress on catalytic reduction technique for denitration of cement flue gas%水泥窑炉烟气催化还原脱硝技术研究进展

    Institute of Scientific and Technical Information of China (English)

    房晶瑞; 马忠诚; 汪澜

    2013-01-01

    Cement production is one of the highest NOx emission industries, where the post-combustion control technology should be utilized in future because the combustion control technology used is difficult to meet the enhanced demand of environmental protection and emission standard. Selective catalytic reduction technique is the most efficient denitration technology and has been widely used in the field of power plants. However, its utilization in cement industry is relatively few because the commercial SCR technique is not applicable to the condition and component of the exhausted gas from cement kilns. This paper briefly introduced the mechanism of selective catalytic reduction process, reaction mechanism, concluded the application of SCR in cement kilns and discussed the research focus on catalysts for denitration of cement kilns.%水泥工业是NOx的高排放行业,现有的燃烧控制技术难以满足日益提高的环保要求,因此烟气脱硝技术在水泥工业的应用将势在必行.选择性催化还原(SCR)脱硝技术是脱硝率最高的烟气脱硝技术,在燃煤电厂已有较大规模的应用,但是在水泥工业中的研究和应用相对滞后.简要介绍了SCR脱硝技术工作原理及其在水泥窑炉的应用现状,总结了催化材料研究和应用进展,探讨了水泥窑炉NOx减排用SCR脱硝技术和催化材料的研究方向.

  20. Enantioselective bioconversion using Escherichia coli cells expressing Saccharomyces cerevisiae reductase and Bacillus subtilis glucose dehydrogenase.

    Science.gov (United States)

    Park, Hyun Joo; Jung, Jihye; Choi, Hyejeong; Uhm, Ki-Nam; Kim, Hyung Kwoun

    2010-09-01

    Ethyl (R, S)-4-chloro-3-hydroxybutanoate (ECHB) is a useful chiral building block for the synthesis of L-carnitine and hypercholesterolemia drugs. The yeast reductase, YOL151W (GenBank locus tag), exhibits an enantioselective reduction activity, converting ethyl-4-chlorooxobutanoate (ECOB) exclusively into (R)-ECHB. YOL151W was generated in Escherichia coli cells and purified via Ni- NTA and desalting column chromatography. It evidenced an optimum temperature of 45 degrees C and an optimum pH of 6.5-7.5. Bacillus subtilis glucose dehydrogenase (GDH) was also expressed in Escherichia coli, and was used for the recycling of NADPH, required for the reduction reaction. Thereafter, Escherichia coli cells co-expressing YOL151W and GDH were constructed. After permeablization treatment, the Escherichia coli whole cells were utilized for ECHB synthesis. Through the use of this system, the 30 mM ECOB substrate could be converted to (R)-ECHB.