ChemCatChem

Cover image for Vol. 5 Issue 7

July 2013

Volume 5, Issue 7

Pages 1617–2058

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Review
    7. Minireview
    8. Highlights
    9. Communications
    10. Full Papers
    11. Book Review
    1. You have free access to this content
      Cover Picture: Electrocatalytic Reduction of Nitrate on a Pt Electrode Modified by p-Block Metal Adatoms in Acid Solution (ChemCatChem 7/2013) (page 1617)

      Jian Yang, Dr. Federico Calle-Vallejo, Dr. Matteo Duca and Prof. Marc T. M. Koper

      Version of Record online: 25 JUN 2013 | DOI: 10.1002/cctc.201390031

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      Tin soldiers The cover picture shows the interaction of nitrate with a tin-covered platinum surface in an aqueous electrolyte. In their Full Paper on p. 1773 ff., J. Yang et al. study a wide range of promoters for the electrocatalytic reduction of nitrate, a reaction of importance in industry and the environmental remediation of nitrate-laden waste water. Of all the p-block elements, tin outperforms as the most active promoter. First-principles DFT calculations suggest that the hydroxylated surface-adsorbed tin atoms promote nitrate reduction most efficiently by enhancing the bonding of nitrate to the platinum–tin surface.

    2. You have free access to this content
      Inside Cover: Mesoporous Gallosilicate with 3 D Architecture as a Robust Energy-Efficient Heterogeneous Catalyst for Diphenylmethane Production (ChemCatChem 7/2013) (page 1618)

      Dr. Chokkalingam Anand, Stalin Joseph, Geoffrey Lawrence, Dr. Dattatray S. Dhawale, Dr. Md. Abdul Wahab, Prof. Jin-Ho Choy and Prof. Ajayan Vinu

      Version of Record online: 25 JUN 2013 | DOI: 10.1002/cctc.201390032

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      Green catalytic boat The cover picture shows the eco-friendly synthesis of diphenylmethane by using a gallosilicate with a 3 D porous structure. In their Full Paper on p. 1863 ff., C. Anand, A. Vinu et al. demonstrate the role of gallium in the KIT-6 molecular sieves on the Friedel–Crafts alkylation of aromatics. The prepared highly stable and recyclable catalyst shows a high activity even at reaction temperatures as low as 313 K with a high benzylchloride conversion and diphenylmethane selectivity.

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      Inside Back Cover: Imidazolium-Based Organic–Inorganic Hybrid Silica as a Functional Platform Dramatically Boosts Chiral Organometallics Performance in Asymmetric Catalysis (ChemCatChem 7/2013) (page 2059)

      Daquan Xia, Tanyu Cheng, Wei Xiao, Ketang Liu, Zhaoliang Wang, Prof. Dr. Guohua Liu, Hexing Li and Prof. Dr. Wei Wang

      Version of Record online: 25 JUN 2013 | DOI: 10.1002/cctc.201390035

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      A blaze of chirality The cover picture shows a phase-transfer featured imidazolium-based organic-inorganic hybrid silica as an efficient heterogeneous catalyst for promoting the highly enantioselective Michael addition of malonates to nitrostyrenes. In their Full Paper on p. 1784 ff., G. Liu, W. Wang et al. reveal how their hybridized catalyst is exceptionally stable and can be recovered and recycled easily without loss of activity or selectivity.

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      Back Cover: Photodegradation by a Heterogeneous Mixture of Micro-Sized Anatase and Truncated Rhomboid Anatase Hollow Spheres (ChemCatChem 7/2013) (page 2060)

      Min-Han Yang, Dr. Min-Chiao Tsai, Yuan-Wei Chang, Ya-Chen Chang, Prof. Hsin-Tien Chiu and Prof. Chi-Young Lee

      Version of Record online: 25 JUN 2013 | DOI: 10.1002/cctc.201390036

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      Enhanced effective photocatalyst! The cover picture shows the photodegradation of methylene blue by a heterogeneous mixture of highly uniform hollow spheres, assembled from truncated rhomboid anatase TiO2 nanoparticles and conventional micro-sized TiO2. In their Full Paper on p. 1871 ff., C.-Y. Lee et al. reveal the factors that enhanced the photocatalytic performance. The scattering structure enhanced the light harvesting, the heterojunction increased the photo-efficiency, and the active surface, {1 0 1} and {0 0 1}, improved the reaction activity. The rate constant for methylene blue degradation by this catalyst was approximately twice that of commercial P25.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Review
    7. Minireview
    8. Highlights
    9. Communications
    10. Full Papers
    11. Book Review
  3. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Review
    7. Minireview
    8. Highlights
    9. Communications
    10. Full Papers
    11. Book Review
  4. Concept

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Review
    7. Minireview
    8. Highlights
    9. Communications
    10. Full Papers
    11. Book Review
    1. On the Use of Seawater as Reaction Media for Large-Scale Applications in Biorefineries (pages 1643–1648)

      Dr. Pablo Domínguez de María

      Version of Record online: 11 APR 2013 | DOI: 10.1002/cctc.201200877

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      Seawater and biorefineries: From enzymes to microorganisms to chemocatalysts… Many biorefinery-oriented methods can be performed in seawater, which enables the use of nonpotable water resources for biomass (e.g., algae) valorization. Provided that adequate waste(sea)water treatments are implemented, the use of seawater may enable the local delivery of chemicals and biofuels for coastal regions.

  5. Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Review
    7. Minireview
    8. Highlights
    9. Communications
    10. Full Papers
    11. Book Review
    1. Biorelevant Metals in Sustainable Metal Catalysis—A Survey (pages 1650–1679)

      Michael S. Holzwarth and Prof. Dr. Bernd Plietker

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/cctc.201200592

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      Nature's metals: For a wide range of catalytic transformations, the nature of the catalyst has to be considered when evaluating the necessary steps to take academic research to industrial application. Herein we survey state of the art progress in sustainable metal catalysis, that is, catalytic reactions performed with inexpensive biorelevant metals such as B, Mg, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Se, Si, and W.

  6. Minireview

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Review
    7. Minireview
    8. Highlights
    9. Communications
    10. Full Papers
    11. Book Review
    1. Advanced Core–Shell Nanoparticle Catalysts for Efficient Organic Transformations (pages 1681–1691)

      Dr. Takato Mitsudome and Prof. Kiyotomi Kaneda

      Version of Record online: 12 MAR 2013 | DOI: 10.1002/cctc.201200724

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      Straight to the core of the matter: Recent progress in conceptual designs of state-of-the-art core–shell nanostructured catalysts with active species in the core is reviewed. The core–shell catalysts possess multifunctions and show unique catalysis for efficient organic transformations.

  7. Highlights

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Review
    7. Minireview
    8. Highlights
    9. Communications
    10. Full Papers
    11. Book Review
    1. Alloyed Ultrathin Nanowires: A New Choice in Electrocatalysts (pages 1693–1695)

      Hui-Hui Li, Dr. Chun-Hua Cui and Prof. Dr. Shu-Hong Yu

      Version of Record online: 9 MAY 2013 | DOI: 10.1002/cctc.201300155

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      Skinnier than a supermodel: There will be an optimal size for ultrathin alloyed nanowires (NWs) as electrocatalysts. The ultrathin size of the NWs maximizes the surface area and utilization of precious metals, thereby lowering the precious metals loading and reducing the cost while increasing their electroactivity and stability.

    2. Subtle Changes, Dramatic Effects: Homogeneous Catalysis of the Oxygen-Reduction Reaction (pages 1696–1697)

      Dr. Micheál D. Scanlon

      Version of Record online: 31 MAY 2013 | DOI: 10.1002/cctc.201300251

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      A just cause: Fukuzumi and co-workers have employed experimental methods to tease out “cause and effect” relationships between subtle modification of the catalyst design or reaction conditions, and the resultant changes in the homogeneous oxygen-reduction mechanistic pathways.

    3. Nanocrafting Iron–Cobalt for Fischer–Tropsch Catalysis (pages 1698–1700)

      Prof. Dr. Tewodros Asefa

      Version of Record online: 31 MAY 2013 | DOI: 10.1002/cctc.201300243

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      A Fischer-mans friend: The nanostructuring of iron and cobalt oxides with core–shell structures through rational design allows the development of a synthetic approach to a very efficient, cost-effective, scalable, and selective catalyst for Fischer–Tropsch synthesis and for the conversion of syngas into liquid fuel.

  8. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Review
    7. Minireview
    8. Highlights
    9. Communications
    10. Full Papers
    11. Book Review
    1. Interfacial Engineering of Platinum Catalysts for Fuel Cells: Methanol Oxidation is Dramatically Improved by Polymer Coating on a Platinum Catalyst (pages 1701–1704)

      Prof. Tsuyohiko Fujigaya, Minoru Okamoto, Dr. Kazuya Matsumoto, Prof. Kenji Kaneko and Prof. Naotoshi Nakashima

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/cctc.201300157

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      All coated up: Platinum nanoparticles loaded on multiwalled carbon nanotubes (MWNTs) are coated with pyridine-containing polybenzimidazole (PyPBI). Interestingly, although a slight decrease in the accessibility of methanol is observed after coating, the methanol oxidation activity of Pt dramatically improves after coating with PyPBI.

    2. Selective Gas-Phase Oxidation of Alcohols over Nanoporous Silver (pages 1705–1708)

      Zhiwen Li, Junling Xu, Xiaohu Gu, Kang Wang, Wenhui Wang, Prof. Dr. Xiaomei Zhang, Prof. Dr. Zhonghua Zhang and Prof. Dr. Yi Ding

      Version of Record online: 16 APR 2013 | DOI: 10.1002/cctc.201200862

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      Hi ho silver lining: Dealloyed nanoporous silver showed high activity and selectivity for the partial oxidation of MeOH into formaldehyde and of several primary and secondary aliphatic alcohols into their corresponding aldehydes or ketones.

    3. Design of Pt-Based Bimetallic Alloys for the Oxidation of H2O2: A Combined Computational and Experimental Approach (pages 1709–1712)

      Mon-Che Tsai, John Rick and Prof. Bing-Joe Hwang 

      Version of Record online: 21 MAY 2013 | DOI: 10.1002/cctc.201200816

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      Grand designs: A strategy for the design of Pt-based bimetallic alloy catalysts for the oxidation of H2O2, which was achieved through a combination of DFT calculations and experiments, is reported.

    4. Immobilizing Carbon Nanotubes on SiC Foam as a Monolith Catalyst for Oxidative Dehydrogenation Reactions (pages 1713–1717)

      Hua Yuan, Prof. Zhenhua Sun, Prof. Hongyang Liu, Dr. Bingsen Zhang, Chunlin Chen, Haihua Wang, Prof. Zhenming Yang, Prof. Jinsong Zhang, Prof. Fei Wei and Prof. Dang Sheng Su

      Version of Record online: 11 APR 2013 | DOI: 10.1002/cctc.201200758

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      Foam party: A new method is reported for the immobilization of carbon nanotubes (CNTs) onto silicon carbide foam to afford a CNT/SiC monolith catalyst for sustainable chemistry applications. The as-synthesized monolith displayed good stability and high catalytic performance in the oxidative dehydrogenation (ODH) of 1-butene into butadiene.

    5. Novel Catalyst Design by using Cisplatin To Covalently Anchor Catalytically Active Copper Complexes to DNA (pages 1718–1721)

      Lorina Gjonaj and Dr. Gerard Roelfes

      Version of Record online: 2 MAY 2013 | DOI: 10.1002/cctc.201300082

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      Anchored to DNA: Covalent anchoring of catalytically active complexes to DNA is achieved through a tethered cisplatin moiety. The resulting DNA-based catalysts give good enantiomeric excess values in the catalyzed Diels–Alder and Friedel–Crafts alkylation reactions.

    6. You have full text access to this OnlineOpen article
      On the Unique Reactivity of Pd(OAc)2 with Organic Azides: Expedient Synthesis of Nitriles and Imines (pages 1722–1724)

      Laura Martínez-Sarti and Dr. Silvia Díez-González

      Version of Record online: 10 APR 2013 | DOI: 10.1002/cctc.201300064

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      As good as it gets: Pd(OAc)2 is a highly efficient catalyst for the transformation of primary azides into nitriles or imines under neutral, technical-grade conditions, with unprecedented selectivities.

    7. A Monovacant Lacunary Silicotungstate as an Efficient Heterogeneous Catalyst for Dehydration of Primary Amides to Nitriles (pages 1725–1728)

      Shintaro Itagaki, Dr. Keigo Kamata, Dr. Kazuya Yamaguchi and Prof. Dr. Noritaka Mizuno

      Version of Record online: 15 APR 2013 | DOI: 10.1002/cctc.201300063

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      Acting up with nitriles: A monovacant lacunary silicotungstate, TBA4[α-H4SiW11O39] (I) could act as an efficient heterogeneous catalyst for dehydration of primary amides. Various kinds of primary amides, including benzylic, double bond-containing, heteroaromatic, and aliphatic could be converted into the corresponding nitriles in moderate to excellent yields.

    8. A Microfluidic System for the Continuous Recycling of Unmodified Homogeneous Palladium Catalysts through Liquid/Liquid Phase Separation (pages 1729–1733)

      Prof. Dr. Pengfei Li, Dr. Jason S. Moore  and Prof. Dr. Klavs F. Jensen

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/cctc.201300054

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      A parting of the waves: A prototype microflow system for the continuous recycling of homogeneous catalysts through liquid/liquid phase separation was developed and its effectiveness demonstrated in a challenging palladium-catalyzed hydroxylation reaction. The unmodified catalyst is recycled under standard reaction conditions by using a combination of chemical and engineering methods.

    9. One-Pot Production of Enantiopure Alkylamines and Arylalkylamines of Opposite Chirality Catalyzed by ω-Transaminase (pages 1734–1738)

      Eul-Soo Park, Dr.  M. Shaheer Malik, Joo-Young Dong and Prof. Dr. Jong-Shik Shin

      Version of Record online: 22 APR 2013 | DOI: 10.1002/cctc.201300052

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      Looking for favors: The thermodynamically favorable asymmetric amination of alkyl ketones was catalyzed by ω-transaminase with racemic arylalkylamines as an amine donor, thus affording enantiopure alkylamines and arylalkylamines of opposite chirality.

    10. Selective Hydrogenation of Nitroaromatic Compounds with a Nickel-Oxide-Supported Nano-Palladium Catalyst under Ambient Reaction Conditions (pages 1739–1743)

      Huimin Yang, Dr. Xinjiang Cui, Prof. Dr. Youquan Deng and Dr. Feng Shi

      Version of Record online: 18 APR 2013 | DOI: 10.1002/cctc.201300039

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      Very supportive: An active nickel-oxide-supported nano-palladium catalyst, Pd/NiO-M, promotes the selective hydrogenation of nitroaromatic compounds into anilines under ambient conditions. The catalyst was recovered and reused without deactivation.

    11. Asymmetric Biocatalytic Cannizzaro-Type Reaction (pages 1744–1748)

      Christiane Wuensch, Horst Lechner, Dr. Silvia M. Glueck, Prof. Dr. Klaus Zangger, Dr. Mélanie Hall and Prof. Dr. Kurt Faber

      Version of Record online: 12 APR 2013 | DOI: 10.1002/cctc.201300028

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      Blowing out of disproportion: Alcohol dehydrogenases were found to catalyze a bio-Cannizzaro-type reaction. The disproportionation of various aldehydes into their corresponding alcohols and carboxylic acids was achieved in a redox-neutral process. The asymmetric variant proceeded with high stereoselectivities.

    12. Highly Porous Organic Polymer containing Free -CO2H Groups: A Convenient Carbocatalyst for Indole C[BOND]H Activation at Room Temperature (pages 1749–1753)

      Arindam Modak, John Mondal and Prof. Asim Bhaumik

      Version of Record online: 30 APR 2013 | DOI: 10.1002/cctc.201300009

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      Rich in more ways than one: High surface area -CO2H rich organic polymer have been designed, which acts as an excellent carbocatalyst in a series of indole 3-substitution reactions at room temperature.

    13. Zeolite Catalyzed Transformation of Carbohydrates to Alkyl Levulinates (pages 1754–1757)

      Dr. Shumugavel Saravanamurugan and Prof. Anders Riisager

      Version of Record online: 9 APR 2013 | DOI: 10.1002/cctc.201300006

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      Caught in an acid trap! Zeolites with moderate acidity are demonstrated to be versatile and reusable solid-acid catalysts for the transformation of biomass derived carbohydrates to alkyl levulinates in alcohol solvents. In short-chained alcohols it proved possible to obtain significantly higher yields of alkyl levulinates, than what is achievable of levulinic acid in analogous reactions performed in water.

    14. Dimensional Effects in the Carbidization of Supported Iron Nanoparticles (pages 1758–1761)

      Prof. Petr A. Chernavskii, Dr. Vladimir I. Zaikovskii, Dr. Galina V. Pankina and Dr. Andrei Y. Khodakov

      Version of Record online: 15 APR 2013 | DOI: 10.1002/cctc.201200960

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      Iron-clad results: The effect of nanoparticle size on the kinetics of iron carbidization on silica-supported catalysts was studied by using an in situ magnetic method combined with simultaneous analysis of the reaction products. The activation energy of carbide formation in both CO and syngas grew with a decrease in the particle size of iron: Smaller iron carbide particles (d=9 nm) appear to be less stable than their larger counterparts.

    15. Catalytic Dehydrogenative Amide and Ester Formation with Rhenium–Triphos Complexes (pages 1762–1764)

      P. Philipp M. Schleker, Roman Honeker, Prof. Dr. Jürgen Klankermayer and Prof. Dr. Walter Leitner

      Version of Record online: 11 APR 2013 | DOI: 10.1002/cctc.201200942

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      [Re]ad all about it: The first examples of the rhenium-catalyzed dehydrogenative formation of amides and esters with the highly active ReH5(triphos) complex are demonstrated. The addition of a tertiary amine additive improves the selectivity and the stability of the catalyst in the formation of esters from primary alcohols.

    16. Enhancing Biocatalysis: The Case of Unfolded Cytochrome c Immobilized on Kaolinite (pages 1765–1768)

      Dr. Elena Castellini, Dr. Carlo Augusto Bortolotti, Dr. Giulia Di Rocco, Dr. Fabrizio Bernini and Dr. Antonio Ranieri

      Version of Record online: 5 APR 2013 | DOI: 10.1002/cctc.201200876

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      Enhanced catalysis! Urea-unfolded wild-type cytochrome c and its variants immobilized on kaolinite show peroxidase activity that is significantly higher than that of the folded wild-type protein. The accessibility of the substrate to the metal center and the influence of strategic amino acidic residues on the surface of the protein are discussed. This approach sheds light on the factors affecting the catalytic activity of a new versatile biocatalytic interface.

    17. Catalytic Hydrogenation of CO2 to Formic Acid with Silica-Tethered Iridium Catalysts (pages 1769–1771)

      Dr. Zheng Xu, Nicholas D. McNamara, Gregory T. Neumann, Prof. William F. Schneider and Prof. Jason C. Hicks

      Version of Record online: 11 APR 2013 | DOI: 10.1002/cctc.201200839

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      Tetherball: A heterogeneous, mesoporous silica-tethered iridium catalyst (Ir-PN/SBA-15) containing a bidentate iminophosphine ligand is synthesized for the hydrogenation of CO2 to formic acid in aqueous solution. This new recyclable catalyst exhibits high activities to formic acid production under mild conditions [60 °C, 4.0 MPa total pressure (H2/CO2=1:1)].

  9. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Review
    7. Minireview
    8. Highlights
    9. Communications
    10. Full Papers
    11. Book Review
    1. Electrocatalytic Reduction of Nitrate on a Pt Electrode Modified by p-Block Metal Adatoms in Acid Solution (pages 1773–1783)

      Jian Yang, Dr. Federico Calle-Vallejo, Dr. Matteo Duca and Prof. Marc T. M. Koper

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/cctc.201300075

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      Some metals do it better: Polycrystalline platinum electrodes are modified with p-block elements and their abilities for nitrate reduction to volatile nitrogen oxides in perchloric and sulfuric acid solutions investigated. Online electrochemical mass spectrometry is used to detect volatile products on the electrode surface and DFT calculations give insight into the nature of the promoting action.

    2. Imidazolium-Based Organic–Inorganic Hybrid Silica as a Functional Platform Dramatically Boosts Chiral Organometallics Performance in Asymmetric Catalysis (pages 1784–1789)

      Daquan Xia, Tanyu Cheng, Wei Xiao, Ketang Liu, Zhaoliang Wang, Prof. Dr. Guohua Liu, Hexing Li and Prof. Dr. Wei Wang

      Version of Record online: 10 APR 2013 | DOI: 10.1002/cctc.201200954

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      A phase-transfer featured, imidazolium-based, organic–inorganic hybrid silica as a functional platform, is used to develop a bifunctionalized heterogeneous catalyst that displays comparable or higher catalytic activity and enantioselectivity than its homogeneous counterpart in asymmetric transformations. This hybrid silica also boosts asymmetric catalysis and can be recovered conveniently and reused without affecting its catalytic efficiency.

    3. You have full text access to this OnlineOpen article
      Electrocatalytic Reduction of Carbon Dioxide to Carbon Monoxide by a Polymerized Film of an Alkynyl-Substituted Rhenium(I) Complex (pages 1790–1796)

      Engelbert Portenkirchner, Jacek Gasiorowski, Kerstin Oppelt, Stefanie Schlager, Dr. Clemens Schwarzinger, Dr. Helmut Neugebauer, Prof. Günther Knör and Prof. Niyazi Serdar Sariciftci

      Version of Record online: 12 APR 2013 | DOI: 10.1002/cctc.201200904

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      Electrocatalytic reduction: The alkynyl-substituted ReI complex [Re(5,5′-bisphenylethynyl-2,2′-bipyridyl)(CO)3Cl] was immobilized by electropolymerization onto a Pt-plate electrode. The polymerized film exhibited electrocatalytic activity for the reduction of CO2 to CO.

    4. Redesign of a Phenylalanine Aminomutase into a Phenylalanine Ammonia Lyase (pages 1797–1802)

      Dr. Sebastian Bartsch, Gjalt G. Wybenga, Maaike Jansen, Matthew M. Heberling, Dr. Bian Wu, Prof. Bauke W. Dijkstra and Prof. Dick B. Janssen

      Version of Record online: 2 APR 2013 | DOI: 10.1002/cctc.201200871

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      The lid dictates: An aminomutase was converted into an ammonia lyase by a rational single-point mutation that destabilizes the closed conformation of the lid covering the active site. The resulting aromatic β-amino acid converting lyase exhibited significantly increased reaction rates (44-fold) and was applied in a preparative-scale asymmetric amination reaction and in kinetic resolution for the production of β-phenylalanine.

    5. Impact of Organic Ligands on the Structure and Hydrogenation Performance of Colloidally Prepared Bimetallic PtSn Nanoparticles (pages 1803–1810)

      Lena Altmann, Dr. Xiaodong Wang, Jörg Stöver, Miriam Klink, Dr. Volkmar Zielasek, Dr. Karsten Thiel, Prof. Dr. Joanna Kolny-Olesiak, Prof. Dr. Katharina Al-Shamery, Dr. Holger Borchert, Prof. Dr. Jürgen Parisi and Prof. Dr. Marcus Bäumer

      Version of Record online: 17 MAY 2013 | DOI: 10.1002/cctc.201200849

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      Thumbs up or thumbs down: As stabilizers and structure-determining components, organic surfactants are irreplaceable in many colloidal nanoparticle preparation methods. The effect of ligands on the structure and catalytic performance of mono- and bimetallic Pt and PtSn nanoparticles toward the selective hydrogenation of acetylene is investigated.

    6. Rh1/γ-Al2O3 Single-Atom Catalysis of O2 Activation and CO Oxidation: Mechanism, Effects of Hydration, Oxidation State, and Cluster Size (pages 1811–1821)

      Tushar K. Ghosh and Dr. Nisanth N. Nair

      Version of Record online: 12 MAR 2013 | DOI: 10.1002/cctc.201200799

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      Be small and neutral! O2 activation and CO oxidation with Rh1 and Rh6 supported on γ-Al2O3 are investigated here through ab initio molecular dynamics techniques. Simulation finds that reactivity varies as Rh0>RhI>Rh6.

    7. Copper-Catalyzed Synthesis of α-Aryl Ketones by Metal–Organic Framework MOF-199 as an Efficient Heterogeneous Catalyst (pages 1822–1831)

      Dr. Nam T. S. Phan, Tung T. Nguyen, Phuong Ho and Khoa D. Nguyen

      Version of Record online: 6 MAR 2013 | DOI: 10.1002/cctc.201200792

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      MOF-199 exhibits high activity in the C-arylation reaction of aryl iodides and acetylacetone to form α-aryl ketones. The catalyst can be facilely separated and be reused without significant degradation in catalytic activity.

    8. Mechanistic Insight into Catalytic Oxidation of Ammonia on Clean, O- and OH-Assisted Ir(1 1 1) Surfaces (pages 1832–1841)

      Dr. Xiaoqing Lu, Zhigang Deng, Ka-Shing Chau, Longfei Li, Zengqiang Wen, Prof. Dr. Wenyue Guo and Prof. Dr. Chi-Man Lawrence Wu

      Version of Record online: 25 FEB 2013 | DOI: 10.1002/cctc.201200762

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      Surface coverage reveals all: Catalytic oxidation mechanisms of NHx (x=1–3) on an Ir(1 1 1) surface with O and OH oxidizing agents are investigated by using DFT calculations. Reactions proceed via NH3+O[RIGHTWARDS ARROW]NH2+OH, NH2+OH[RIGHTWARDS ARROW]NH+H2O, and NH+OH[RIGHTWARDS ARROW]N+H2O, followed by N[BOND]N and/or N[BOND]O recombination reactions. Promotional effects of O and OH are elucidated by energy barrier analysis; relationships between final product selectivity, O and N coverage, and reaction temperature are analyzed.

    9. Proton Shuttle Mechanism in the Transition State of Lipase-Catalyzed N-Acylation of Amino Alcohols (pages 1842–1853)

      Dr. Per-Olof Syrén, Florian Le Joubioux, Yesmine Ben Henda, Prof. Thierry Maugard, Prof. Karl Hult and Prof. Marianne Graber

      Version of Record online: 18 FEB 2013 | DOI: 10.1002/cctc.201200751

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      Tetrahedra prevailing: An increased reaction rate for lipase-catalyzed N-acylation of amino alcohols and related compounds can be explained by a hydrogen shuttle mechanism that avoids nitrogen inversion in the transition state and favors a tetrahedral intermediate for facile amide bond synthesis.

    10. Hydroformylation of 1-Dodecene with Water-Soluble Rhodium Catalysts with Bidentate Ligands in Multiphase Systems (pages 1854–1862)

      Dipl.-Chem. Tobias Hamerla, Dipl.-Chem. Anke Rost, Dipl.-Ing. Yasemin Kasaka and Prof. Dr. Reinhard Schomäcker

      Version of Record online: 7 MAR 2013 | DOI: 10.1002/cctc.201200744

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      Third phase for the catalyst: A hydrophilic metal–ligand complex formed from the precursor [Rh(acac)(CO)2] and the bidentate ligand SulfoXantPhos (see picture) was found to be a suitable candidate as a catalyst complex for the hydroformylation of 1-dodecene in multiphase systems formulated from water, 1-dodecene, and a nonionic surfactant.

    11. Mesoporous Gallosilicate with 3 D Architecture as a Robust Energy-Efficient Heterogeneous Catalyst for Diphenylmethane Production (pages 1863–1870)

      Dr. Chokkalingam Anand, Stalin Joseph, Geoffrey Lawrence, Dr. Dattatray S. Dhawale, Dr. Md. Abdul Wahab, Prof. Jin-Ho Choy and Prof. Ajayan Vinu

      Version of Record online: 9 APR 2013 | DOI: 10.1002/cctc.201200922

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      3 D architecture: We report the preparation and catalytic activity of 3 D mesoporous gallosilicate with Ia3d symmetry (GaKIT-6) and different gallium content, which show a high activity even at reaction temperature as low as 313 K, as well as a high benzyl chloride (BC) conversion and diphenylmethane (DPM) selectivity. The GaKIT-6 catalysts are found to be not only highly active but also stable and recyclable.

    12. Photodegradation by a Heterogeneous Mixture of Micro-Sized Anatase and Truncated Rhomboid Anatase Hollow Spheres (pages 1871–1876)

      Min-Han Yang, Dr. Min-Chiao Tsai, Yuan-Wei Chang, Ya-Chen Chang, Prof. Hsin-Tien Chiu and Prof. Chi-Young Lee

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/cctc.201200891

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      Full of praise for hollow spheres: Factors that dominate the photocatalytic performance of our materials are light harvesting, photoefficiency, and the reaction activity of TiO2. A scattering structure enhanced the light harvesting (red square), a heterojunction improved the photoefficiency (blue square), and an active surface meliorated the reaction activity (green square).

    13. Direct C[BOND]H Bond Arylation of Indoles with Aryl Boronic Acids Catalyzed by Palladium Nanoparticles Encapsulated in Mesoporous Metal–Organic Framework (pages 1877–1883)

      Dr. Yuanbiao Huang, Tao Ma, Dr. Ping Huang, Dongshuang Wu, Dr. Zujin Lin and Prof. Rong Cao

      Version of Record online: 24 MAY 2013 | DOI: 10.1002/cctc.201200957

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      All in a frame's work: The direct C2 arylation of indoles with aryl boronic acids is achieved through the combination of highly dispersed Pd nanoparticles encapsulated in the mesoporous metal–organic framework MIL-101 with O2 or 2,2,6,6-tetramethylpiperidine N-oxyradical (TEMPO) as an external oxidant in acidic media under mild conditions.

    14. Synthesis of Fragrance Compounds from Biorenewables: Tandem Hydroformylation–Acetalization of Bicyclic Monoterpenes (pages 1884–1890)

      Marina C. de Freitas, Camila G. Vieira, Dr. Eduardo N. dos Santos and Prof. Elena V. Gusevskaya

      Version of Record online: 3 MAY 2013 | DOI: 10.1002/cctc.201200948

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      The sweet smell of success: Bicyclic monoterpenes, cheap biomass-based substrates available from coniferous trees, can be transformed into valuable fragrance compounds through an efficient tandem catalytic process by using a Rh catalyst and environmentally friendly ethanol as a solvent.

    15. Extra-Large-Pore Zeolites with UTL Topology: Control of the Catalytic Activity by Variation in the Nature of the Active Sites (pages 1891–1898)

      Dr. Mariya V. Shamzhy, Dr. Oleksiy V. Shvets, Dr. Maksym V. Opanasenko, Lenka Kurfiřtová, Dr. David Kubička and Prof. Jiří Čejka

      Version of Record online: 21 MAY 2013 | DOI: 10.1002/cctc.201200925

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      Control the strength: The catalytic behavior of isomorphously substituted B-, Al-, Ga-, and Fe-containing extra-large-pore UTL zeolites is investigated in the acylation of p-xylene with benzoyl chloride and Beckmann rearrangement of 1-indanone oxime.

    16. On the Nature of Selective Palladium-Based Nanoparticles on Nitrogen-Doped Carbon Nanotubes for the Direct Synthesis of H2O2 (pages 1899–1905)

      Dr. S. Abate, Dr. M. Freni, Dr. R. Arrigo, Dr. M. E. Schuster, Prof. S. Perathoner and Prof. G. Centi

      Version of Record online: 2 MAY 2013 | DOI: 10.1002/cctc.201200914

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      Caps off to gold: High selectivities (>95 %) are obtained if Pd nanoparticles are covered with an organic capping agent, the removal of which during the reaction leads to a decrease in selectivity. With Au, the intrinsic reaction rate decreases but selectivity is better after the removal of the capping agent. The presence of Au creates small Pd terraces fully covered with chemisorbed O2; H2O2 synthesis occurs at the perimeter of these terraces.

    17. Interplay Between Bromine and Iodine in Oxidative Dehydrogenation (pages 1906–1910)

      Dr. Kunlun Ding, Prof. Horia Metiu and Prof. Galen D. Stucky

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/cctc.201200913

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      A single pass to the goal: A single-pass C3H6+C3H7X yield above 80 % was achieved in propane oxidative dehydrogenation using bromine and iodine together as oxidants. This dual-halogen process is promising for the synthesis of many other unsaturated hydrocarbons, including olefins, diolefins, and aromatics.

    18. Pd Ultra-Small Clusters as Precursors for Silica-Encapsulated Pd Nanoreactors: Highly Sinter-Resistant Catalysts (pages 1911–1916)

      Anupam Samanta and Dr.  R. Nandini Devi

      Version of Record online: 6 MAY 2013 | DOI: 10.1002/cctc.201200908

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      The silica sphere is your oyster: Water-dispersible ultra-small clusters of Pd are synthesized by using a quaternary ammonium thiol as the protecting ligand. Further calcination and removal of organics leads to nanoreactors with individual Pd particles encapsulated within porous silica spheres that exhibit excellent catalytic activity and thermal stability.

    19. Sulfur Promotion in Conjugated Isomerization of Safflower Oil over Bifunctional Structured Rh/SBA-15 Catalysts (pages 1917–1934)

      Dr. Nasima Chorfa, Prof. Safia Hamoudi, Prof. Joseph Arul and Prof. Khaled Belkacemi

      Version of Record online: 13 MAY 2013 | DOI: 10.1002/cctc.201200895

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      And they were all yellow: The sulfur-promoted formation of conjugated linoleic acid isomers during the combined hydrogenation and directed isomerization of safflower oil can be explained mechanistically through the preferable formation of the more nucleophilic rhodium sulfide (Rh[BOND]SH) over that of the hydride (Rh[BOND]H). The Rh[BOND]SH species could induce more easily the addition and elimination steps for the double-bond conjugation of linoleic acid.

    20. Lipase-Catalyzed Stereoselective Cross-Aldol Reaction Promoted by Water (pages 1935–1940)

      Zong-Bo Xie, Dr. Na Wang, Long-Hua Zhou, Fang Wan, Ting He, Prof. Dr. Zhang-Gao Le and Prof. Dr. Xiao-Qi Yu

      Version of Record online: 7 MAR 2013 | DOI: 10.1002/cctc.201200890

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      Lip synthing: A lipase-catalyzed, green, and efficient approach for the cross-aldol reaction promoted by water with high yield and good stereoselectivity is described.

    21. KOH Activation of Thermally Modified Carbon as a Support of Ru Catalysts for Ammonia Synthesis (pages 1941–1947)

      Dr. Bingyu Lin, Dr. Kemei Wei, Dr. Jun Ni and Dr. Jianxin Lin

      Version of Record online: 4 APR 2013 | DOI: 10.1002/cctc.201200889

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      Activated carbon: Thermally modified carbon can be activated by KOH treatment and the quantity of the surface groups and the textural properties can be controlled by changing the treatment conditions, which improved the dispersion of Ru particles. The difference in the amount of surface functional groups and the size of Ru particles affected the catalytic activity of Ru catalysts in the synthesis of ammonia.

    22. Catalyst Development for CO2 Hydrogenation to Fuels (pages 1948–1955)

      Dr. Uwe Rodemerck, Dr. Dr. Martin Holeňa, Dr.-Ing. Edmund Wagner, Dr. Quido Smejkal, Dr. Axel Barkschat and Prof. em. Dr. Manfred Baerns

      Version of Record online: 4 APR 2013 | DOI: 10.1002/cctc.201200879

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      Fuel for thought: New active and selective catalyst compositions for hydrogenation of CO2 to mainly fuel-type higher hydrocarbons were developed by application of an evolutionary strategy. A detailed study of the reaction conditions revealed that modified Fe catalysts supported on TiO2 resulted in high selectivities even at high CO2 conversions.

    23. Palladium-Catalysed Regioselective Direct Arylations of Heteroarenes by Bromobenzamides: Direct Synthesis of Heteroaryl Benzamides (pages 1956–1963)

      Lu Chen, Dr. Christian Bruneau, Prof. Pierre H. Dixneuf and Dr. Henri Doucet

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/cctc.201200867

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      A new sensation in direct arylation: In the presence of KOAc, the Pd-catalyzed direct heteroarylation of 2- or 4-bromobenzamides with heteroarenes proceeds without the formation of C[BOND]N or C[BOND]C bonds by the coupling of two bromobenzamides. With 4-bromobenzamides, both primary and tertiary amides can be employed, whereas only tertiary 2-bromobenzamides were reactive. The nature of the heteroarene had a moderate influence on the reaction. DMAc=N,N-dimethylacetamide.

    24. Superior Performance of Fe(BTC) With Respect to Other Metal-Containing Solids in the N-Hydroxyphthalimide-Promoted Heterogeneous Aerobic Oxidation of Cycloalkanes (pages 1964–1970)

      Dr. Yusuke Mikami, Dr. Amarajothi Dhakshinamoorthy, Dr. Mercedes Alvaro and Prof. Dr. Hermenegildo Garcia

      Version of Record online: 7 MAR 2013 | DOI: 10.1002/cctc.201200854

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      Aerobic oxidation: The N-hydroxyphthalimide (NHPI)-promoted aerobic oxidation of cycloalkanes can be performed by supporting NHPI on high-surface-area solids. Of the materials tested, NHPI incorporated onto commercially available Fe(BTC) (BTC=1,3,5-benzenetricarboxylate) appears to be most efficient due to the balance of high combined selectivity toward -ol/-one products and conversion.

    25. Design and Application of a Hybrid Material Featuring Well-Defined, Tuneable Grafting Sites for Supported Catalysis. (pages 1971–1977)

      Dr. Nicolas Popoff, Dr. Jeff Espinas, Dr. Jérémie Pelletier, Dr. Kai C. Szeto, Dr. Jean Thivolle-Cazat, Dr. Laurent Delevoye, Dr. Régis M. Gauvin and Dr. Mostafa Taoufik

      Version of Record online: 7 MAR 2013 | DOI: 10.1002/cctc.201200850

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      To tether a tungsten: A hybrid material, featuring single-site phenolic functionalities on a silica surface was developed and subsequently used to tether a tungstenocarbyne complex. Drastic improvements in terms of activity and stability in propene metathesis were observed with respect to the silica counterpart. Further tuning of the spacer moiety with fluorine atoms led to additional significant improvements in activity.

    26. Ionic Liquid-Mediated α-Fe2O3 Shape-Controlled Nanocrystal-Supported Noble Metals: Highly Active Materials for CO Oxidation (pages 1978–1988)

      Liwei Hou, Dr. Qinghua Zhang, Dr. François Jérôme, Dr. Daniel Duprez, Dr. Fabien Can, Dr. Xavier Courtois, Dr. Hui Zhang and Dr. Sébastien Royer

      Version of Record online: 11 JUN 2013 | DOI: 10.1002/cctc.201200840

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      Haunted with morphology: α-Fe2O3 with different morphologies is synthesised by using an ionic liquid-mediated hydrothermal method. Although α-Fe2O3 with various morphologies possesses comparable reduction properties, large differences in oxygen mobility are observed. Oxygen mobility is favoured by the increase in surface area and decrease in crystal size, which makes the porous nanorod morphology the more active material for oxygen exchange and enables us to design a highly active oxidation catalyst.

    27. Influence of the Precipitation Method on Acid–Base-Catalyzed Reactions over Mg–Zr Mixed Oxides (pages 1989–1997)

      Joseph T. Kozlowski, Malte Behrens, Robert Schlögl and Robert J. Davis

      Version of Record online: 7 MAR 2013 | DOI: 10.1002/cctc.201200833

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      It never rains but it precipitates: Mixed oxides of Zr and Mg are prepared by two precipitation methods to investigate the promotional effect of ZrO2 on MgO for dehydration, dehydrogenation, aldolization, and transesterification. The oxide catalysts are characterized by adsorption microcalorimetry, electron microscopy, and X-ray diffraction, and results are correlated to catalytic performance.

    28. Oxidation of 1,2-Cyclohexanediol to Adipic Acid with Oxygen: A Study Into Selectivity-Affecting Parameters (pages 1998–2008)

      Elena Rozhko, Dr. Katerina Raabova, Francesco Macchia, Andrea Malmusi, Prof. Paolo Righi, Pasquale Accorinti, Stefano Alini, Pierpaolo Babini, Prof. Giuseppina Cerrato, Dr. Maela Manzoli and Prof. Fabrizio Cavani

      Version of Record online: 27 MAR 2013 | DOI: 10.1002/cctc.201200825

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      The synthesis of adipic acid through aerobic oxidative cleavage of trans-1,2-cyclohexanediol is investigated under basic and acid conditions. In the former case, supported Ru(OH)3 catalysts are active but poorly selective, owing to side reactions starting from the key reaction intermediate 1,2-cyclohexanedione. Under acidic conditions, Keggin polyoxometalates are selective to adipic acid, but this then reacts with the unconverted reactant to yield esters.

    29. Efficient Hydrodeoxygenation of Aliphatic Ketones over an Alkali-Treated Ni/HZSM-5 Catalyst (pages 2009–2014)

      Dr. Xiangjin Kong, Weichi Lai, Dr. Jun Tian, Dr. Yang Li, Dr. Xilong Yan and Prof. Dr. Ligong Chen

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/cctc.201200824

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      Alkaline support: The hydrodeoxygenation of aliphatic ketones is studied in a fixed-bed reactor by using cyclohexanone as a model substrate. Alkali-treated Ni/HZSM-5 exhibits excellent performance for this reaction.

    30. Synthesis of Pt/C Catalysts through Reductive Deposition: Ways of Tuning Catalytic Properties (pages 2015–2024)

      Ksenia M. Kaprielova, Igor I. Ovchinnikov, Olga A. Yakovina and Dr. Alexander S. Lisitsyn

      Version of Record online: 18 MAR 2013 | DOI: 10.1002/cctc.201200769

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      Get all you wished for: This study reveals new capabilities of reductive deposition as a method for the preparation of Pt-on-carbon catalysts. It enables one to avoid confinement of Pt nanoparticles in narrow pores, to adjust the particle size to optimum for the reaction of interest, to obtain various types of Pt distribution over the support, and to influence catalytic properties by simple means.

    31. Effects of La, Ce, and Y Oxides on SnO2 Catalysts for CO and CH4 Oxidation (pages 2025–2036)

      Dr. Xianglan Xu, Dr. Rongbin Zhang, Xianrong Zeng, Xue Han, Yucheng Li, Yang Liu and Prof. Dr. Xiang Wang

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/cctc.201200760

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      Good news for doping: Ce cations can be doped into the lattice of SnO2 to form solid-solution structures, which results in catalysts with improved activity and stability. However, La and Y cations react with SnO2 to form very stable pyrochlores, Sn2La2O7 and Sn2Y2O7, which have a decreased catalytic activity.

    32. Maximizing Activity and Stability by Turning Gold Catalysis Upside Down: Oxide Particles on Nanoporous Gold (pages 2037–2043)

      Andre Wichmann, Arne Wittstock, Kristian Frank, Monika M. Biener, Björn Neumann, Prof. Lutz Mädler, Jürgen Biener, Prof. Andreas Rosenauer and Prof. Marcus Bäumer

      Version of Record online: 27 MAR 2013 | DOI: 10.1002/cctc.201200759

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      Gold goes upside down: A highly active and stable gold catalyst is generated by the deposition of metal oxide particles on a monolithic, high-surface area gold support. The catalyst combines exceptional activity for CO oxidation and NO reduction at low temperatures and unprecedented stability at several hundred degrees Celsius. This novel catalyst design opens up applications such as in exhaust gas control.

    33. Selective Production of Aromatics from Alkylfurans over Solid Acid Catalysts (pages 2044–2050)

      Dong Wang, Christian M. Osmundsen, Dr. Esben Taarning and Prof. Dr. James A. Dumesic

      Version of Record online: 30 JAN 2013 | DOI: 10.1002/cctc.201200757

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      Aroma all around! Benzene, toluene, and p-xylene are produced by the reaction of ethylene with furan, 2-methylfuran, and 2,5-dimethylfuran over WOx–ZrO2 catalysts at 523 K in yields of 18, 34, and 80 %, respectively.

    34. Platinum(II) Catalyzed Enantioselective Cycloisomerizations of 3-Hydroxylated 1,5-Enynes (pages 2051–2057)

      Yang Zhang, Hélène Jullien, Dr. Delphine Brissy, Dr. Pascal Retailleau, Dr. Arnaud Voituriez and Dr. Angela Marinetti

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/cctc.201200743

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      The cycloisomerization of 1,5-enynes with hydroxyl functions at their propargylic positions was investigated by using NHC-based platinacyclic phosphoramidite complexes as the chiral catalysts. The (R)-Monophos complexes display good catalytic activity in mild conditions. They afford the desired bicyclo[3.1.0]hexan-3-ones in up to 81 % ee from enynes with aryl-substituted alkyne functions.

  10. Book Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Review
    7. Minireview
    8. Highlights
    9. Communications
    10. Full Papers
    11. Book Review
    1. Design and Applications of Single-Site Heterogeneous Catalysis. Prof. Sir John Meurig Thomas (page 2058)

      Prof. Richard Catlow

      Version of Record online: 11 JUN 2013 | DOI: 10.1002/cctc.201300368

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      Imperial College Press, London, 2012. 324 pp., hardcover, € 47.99.—ISBN 978-1-84816910-4

      Power to the single sites! The science of active sites is central to heterogeneous catalysis; within this field, welldefined single sites play a principal role. This Book Review discusses the detail and range of coverage provided in this book, from mesoporous open structures to enzymatic catalysis.

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