ChemCatChem

Cover image for Vol. 3 Issue 11

November 18, 2011

Volume 3, Issue 11

Pages 1665–1831

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Highlights
    7. Reviews
    8. Communications
    9. Full Papers
    10. Preview
    1. Cover Picture: Noble Metal-Modified Porous Titania Networks and their Application as Photocatalysts (ChemCatChem 11/2011) (page 1665)

      Dr. Xingdong Wang, Dr. Geoffrey I. N. Waterhouse, Dr. David R. G. Mitchell, Dr. Kathryn Prince and Prof. Rachel A. Caruso

      Article first published online: 15 NOV 2011 | DOI: 10.1002/cctc.201190045

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      Photocatalysts The cover picture shows the photocatalytic degradation of an organic pollutant in aqueous solution by the use of a noble metal modified porous TiO2 network. In their Full paper on p. 1763 ff., Caruso et al. describe the preparation, characterization and photocatalytic studies of these materials, using the agarose gel template to produce the porosity and a deposition precipitation method to deposit noble metal nanoparticles onto the porous titania materials. These materials are highly efficient photocatalysts for the photocatalytic decomposition of methylene blue under UV light, with the addition of Pd nanoparticles demonstrating highest efficiency followed by Au, Ag, and then Pt. The correlation between the material properties and photocatalytic activity gives a solid foundation for the design of advanced photocatalysts in the future.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Highlights
    7. Reviews
    8. Communications
    9. Full Papers
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    1. Inside Cover: The Synthesis of Chiral Phosphorus Ligands for use in Homogeneous Metal Catalysis (ChemCatChem 11/2011) (page 1666)

      Dr. Susan Lühr, Dr. Jens Holz and Prof. Dr. Armin Börner

      Article first published online: 15 NOV 2011 | DOI: 10.1002/cctc.201190046

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      Chiral Phosphorus Ligands Although currently a large amount of phosphorus ligands are commercially available, efforts towards the synthesis of new phosphorus ligands continue. In their Review on p. 1708 ff., S. Lühr, J. Holz, and A. Börner summarize the multitude of protocols for chiral phosphorus ligand synthesis used in homogeneous metal catalysis. The syntheses of new P-chirogenic ligands, as well as ligands with supramolecular structures are likewise reviewed.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Highlights
    7. Reviews
    8. Communications
    9. Full Papers
    10. Preview
  4. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Highlights
    7. Reviews
    8. Communications
    9. Full Papers
    10. Preview
  5. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Highlights
    7. Reviews
    8. Communications
    9. Full Papers
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    1. Silver-Catalyzed Carbene Functionalization of Methane in Supercritical Carbon Dioxide (pages 1681–1682)

      Prof. Dr. Michael P. Doyle

      Article first published online: 8 SEP 2011 | DOI: 10.1002/cctc.201100228

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      Supercritical, methane? It is insertion! Carbon–hydrogen insertion occurs between the least reactive hydrocarbon, methane, and the carbene intermediate formed from ethyl diazoacetate.

    2. Nitrile Reductases: A Forthcoming Wave in Biocatalysis? (pages 1683–1685)

      Dr. Pablo Domínguez de María

      Article first published online: 17 AUG 2011 | DOI: 10.1002/cctc.201100220

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      A new toy? The discovery of oxidoreductases enabling the four-electron reduction of nitriles to primary amines may open new, unprecedented, and exciting leads in (asymmetric) biocatalysis.

  6. Reviews

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Highlights
    7. Reviews
    8. Communications
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    1. Ionic Liquids as Tools for the Acid-Catalyzed Hydrolysis/Dehydration of Saccharides to Furanic Aldehydes (pages 1686–1706)

      Dr. Sérgio Lima, Margarida M. Antunes, Dr. Martyn Pillinger and Dr. Anabela A. Valente

      Article first published online: 26 JUL 2011 | DOI: 10.1002/cctc.201100105

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      Cast in a dual role: High expectations have been put on the use of ionic liquids (ILs) as tools for the acid-catalyzed conversion of carbohydrate biomass into furanic aldehydes, under mild reaction conditions: ILs have been coupled with different types of acid catalysts or when the actual IL is functionalized with acid groups, allowing it to play a dual solvent-acid role. An assessment of the present state-of-the art on this topic is made in this review.

    2. The Synthesis of Chiral Phosphorus Ligands for use in Homogeneous Metal Catalysis (pages 1708–1730)

      Dr. Susan Lühr, Dr. Jens Holz and Prof. Dr. Armin Börner

      Article first published online: 16 SEP 2011 | DOI: 10.1002/cctc.201100164

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      An atmos-phosphoric symphony: Chiral phosphorus ligands are the most versatile ancillary ligands used in asymmetric homogeneous metal catalysis. The review summarizes recent developments in the synthesis of these compounds. In several cases application in asymmetric reactions is considered.

  7. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Highlights
    7. Reviews
    8. Communications
    9. Full Papers
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    1. Expanding the Horizons of Hierarchical Zeolites: Beyond Laboratory Curiosity towards Industrial Realization (pages 1731–1734)

      Prof. Javier Pérez-Ramírez, Dr. Sharon Mitchell, Danny Verboekend, Maria Milina, Nina-Luisa Michels, Dr. Frank Krumeich, Dr. Nadia Marti and Dr. Mandy Erdmann

      Article first published online: 12 SEP 2011 | DOI: 10.1002/cctc.201100264

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      Scale up for the win! Hierarchically structured zeolites are prepared on a large scale by desilication followed by forming into mm-sized bodies. Extrapolation of the superior catalytic properties is proven by the remarkable similarity between pilot and laboratory scale results. The binder and the shaping process does not alter the enhanced porous properties of the mesoporous zeolite. These results unlock the door towards the study of further key steps in the design of mesoporous zeolite catalysts for large scale applications.

    2. Unprecedented Oxygenate Selectivity in Aqueous-Phase Fischer–Tropsch Synthesis by Ruthenium Nanoparticles (pages 1735–1738)

      Xian-Yang Quek, Dr. Yejun Guan , Prof. Dr. Rutger A. van Santen and Prof. Dr. Emiel J. M. Hensen

      Article first published online: 23 SEP 2011 | DOI: 10.1002/cctc.201100219

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      Not just for anglers: An unprecedented oxygenate selectivity of 70 % in the Fischer–Tropsch synthesis is achieved by using a Ru nanoparticle catalyst in the aqueous phase. A kinetic analysis of the anomalous temperature dependence of the chain growth probability shows that hydrocarbons and oxygenates are formed on different sites. Oxygenates (hydrocarbons) form on sites with high (low) barrier for CO dissociation.

    3. Promoting the Formation of Active Sites with Ionic Liquids: A Case Study of MoS2 as Hydrogen-Evolution-Reaction Electrocatalyst (pages 1739–1742)

      Vincent Wing-hei Lau, Prof. Dr. Anthony F. Masters, Prof. Dr. Alan M. Bond and Prof. Dr. Thomas Maschmeyer

      Article first published online: 23 SEP 2011 | DOI: 10.1002/cctc.201100212

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      Pushing HER over the edge! By using ionic liquids as the synthesis media, MoS2 samples with a greater population of the catalytically active edge sites, compared to the control samples, can be prepared. Consequently, these catalysts exhibited superior electrocatalytic activity for the hydrogen evolution reaction (HER).

    4. Rhenium-Catalyzed Benzannulation of o-Alkynylbenzaldehyde with Alkynes to Multiple 2,3-Disubstituted Naphthalenes (pages 1743–1746)

      Dr. Rui Umeda, Kenta Kaiba, Shigeru Morishita and Prof. Dr. Yutaka Nishiyama

      Article first published online: 8 SEP 2011 | DOI: 10.1002/cctc.201100203

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      Bring on the super-subs: Rhenium-catalyzed benzannulation of o-alkynylbenzaldehydes and alkynes in the presence of trichloroacetic acid, afforded the corresponding 2,3-disubstituted naphthalenes. Furthermore, this benzannulation protocol can be applied to the synthesis of multiple and sterically hindered polycyclic aromatic hydrocarbons having 2,3-disubstituted naphthalene units.

    5. Well-Defined Cyclopentadienyl NHC Iron Complex as the Catalyst for Efficient Hydrosilylation of Amides to Amines and Nitriles (pages 1747–1750)

      David Bézier, Dr. Gopaladasu T. Venkanna, Dr. Jean-Baptiste Sortais and Prof. Dr. Christophe Darcel

      Article first published online: 30 AUG 2011 | DOI: 10.1002/cctc.201100202

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      Iron comes first, second, and third: By using the well-defined Cp-IMes iron cationic complex ([Fe], see scheme) as the catalyst, an efficient and versatile hydrosilylation reduction reaction of secondary and tertiary amides is performed in solvent-free conditions at 100 °C under visible light irradiation for 16 h to give the corresponding amines in good yields. When the reaction is performed with primary amides, the corresponding nitrile derivatives are obtained.

    6. The Effects of Cofeeding Chlorinated Hydrocarbons in the Direct Epoxidation of Propylene by Molecular Oxygen (pages 1751–1754)

      Dr. Anusorn Seubsai and Prof. Dr. Selim Senkan

      Article first published online: 2 SEP 2011 | DOI: 10.1002/cctc.201100178

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      Chlorine does it again: Similar to the ethylene epoxidation, the introduction of chlorinated hydrocarbon (CHC) additives to the C3H6/O2 feed enables the steady production of propylene oxide (PO), albeit at a slight decrease in propylene conversion.

    7. Direct Synthesis of N-Substituted Anilines from Nitroaromatics and Alcohols under H2 by Alumina-Supported Silver Cluster Catalysts (pages 1755–1758)

      Dr. Kenichi Shimizu, Dr. Katsuya Shimura, Masanari Nishimura and Prof. Atsushi Satsuma

      Article first published online: 26 AUG 2011 | DOI: 10.1002/cctc.201100171

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      Anilines go silver: An alumina-supported silver cluster using KF as a cocatalyst is presented as the first example of the heterogeneously catalyzed one-step synthesis of N-substituted anilines from nitroaromatics and benzyl alcohols under H2 (0.2 MPa).

    8. An ITQ-2/TUD-1 Micro-/Mesoporous Composite: In Situ Delamination as a Tool for the Preparation of Innovative Materials (pages 1759–1762)

      Dr. Cindy C. Aquino , Prof. Heloise O. Pastore, Prof. Anthony F. Masters and Prof. Thomas Maschmeyer

      Article first published online: 27 SEP 2011 | DOI: 10.1002/cctc.201100077

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      Layered success: A new one-pot method to prepare a highly active and yet selective and stable acidic micro-/mesoporous zeolite catalyst composite is reported. The process involves generating highly dispersed zeolitic sheets (ITQ-2) inside the synthesis gel of a mesoporous host structure (siliceous TUD-1) by in situ delamination of MCM-22 zeolite.

  8. Full Papers

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Highlights
    7. Reviews
    8. Communications
    9. Full Papers
    10. Preview
    1. Noble Metal-Modified Porous Titania Networks and their Application as Photocatalysts (pages 1763–1771)

      Dr. Xingdong Wang, Dr. Geoffrey I. N. Waterhouse, Dr. David R. G. Mitchell, Dr. Kathryn Prince and Prof. Rachel A. Caruso

      Article first published online: 14 OCT 2011 | DOI: 10.1002/cctc.201100213

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      Noble increase: Noble metals were deposited onto porous TiO2 supports prepared using an agarose gel templating technique coupled with sol–gel chemistry. The photocatalytic activity of the materials improved if the metal was in a zero oxidation state and was homogenously distributed in the titania network and for samples with a higher adsorption of organic pollutant.

    2. Synthesis of CeO2-Based Quantum Dots through a Polyol-Hydrolysis Method for Fuel-Borne Catalysts (pages 1772–1778)

      Ying Xin, Xi Yang, Pin Jiang, Prof. Zhaoliang Zhang, Prof. Zhongpeng Wang and Prof. Yihe Zhang

      Article first published online: 29 AUG 2011 | DOI: 10.1002/cctc.201100179

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      Dots for diesel: Transparent colloidal solutions of (Fe doped) CeO2 quantum dots (QDs) were prepared by heating a triethylene glycol solution of Ce(NO3)3⋅6 H2O (and Fe(NO3)3⋅9 H2O) at 180 °C. The QDs show improved activity for soot combustion compared with their nanometer counterparts. The high surface area and especially small particle size of QDs result in a large number of contact points between the catalyst and the soot.

    3. Lithium as a Modifier for Morphology and Defect Structure of Porous Magnesium Oxide Materials Prepared by Gel Combustion Synthesis (pages 1779–1788)

      Dr. Ulyana Zavyalova, Gisela Weinberg, Wiebke Frandsen, Dr. Frank Girgsdies, Prof. Dr. Thomas Risse, Prof. Dr. Klaus Peter Dinse, Prof. Dr. Robert Schloegl and Dr. Raimund Horn

      Article first published online: 7 SEP 2011 | DOI: 10.1002/cctc.201100146

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      Once intimately united—though, at the end divided: Gel combustion synthesis is used in an attempt to synthesize Li doped MgO, a classical catalyst for methane oxidative coupling. At low Li loadings, hierarchically structured materials are obtained resistant to temperatures up to 800 °C. At higher Li loadings, these structures collapse into phase separated Li2CO3 and MgO. Li+ incorporated in MgO could not be detected. Addition of Li modifies the morphology and defect structure of MgO, which is studied systematically using a multimethod approach.

    4. Selective Oxidation of D-Galactose over Gold Catalysts (pages 1789–1798)

      Bright T. Kusema, Dr. Betiana C. Campo, Olga A. Simakova, Anne-Riika Leino, Dr. Krisztián Kordás, Dr. Päivi Mäki-Arvela, Prof. Tapio Salmi and Prof. Dmitry Yu Murzin

      Article first published online: 20 SEP 2011 | DOI: 10.1002/cctc.201100183

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      Gold takes over from palladium and platinum: The selective oxidation of D-galactose to galactonic acid over gold catalysts is studied isothermally in a semi-batch shaker reactor under pH-controlled conditions. The catalytic properties of the gold nanoparticles are affected by the cluster size. Au/Al2O3 with a mean particle size of 2.6 nm exhibits the highest activity. Alkaline conditions are characterized by high catalyst activity and high selectivity to aldonic acid.

    5. Heavy Metal with a Heavy Impact: Olefin Dimerization Reactions in Triphenylbismuth Buffered Chloroaluminate Ionic Liquids (pages 1799–1804)

      Dr. Matthias Dötterl and Prof. Dr. Helmut G. Alt

      Article first published online: 2 SEP 2011 | DOI: 10.1002/cctc.201100182

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      Rockin′ out with bismuth: The addition of BiPh3 to Lewis acidic chloroaluminate melts in combination with nickel catalysts yields a highly efficient biphasic olefin dimerization catalyst. Owing to a reduced melting point upon BiPh3 addition and the absence of alkylaluminum groups, many different organic halide salts can be employed. In the case of organic hydrochloride salts, the corresponding amine as well as BiPh3 can be recycled by a simple acid base extraction of the spent ionic liquid catalyst systems.

    6. Activity, Stability, and Degradation Mechanisms of Dealloyed PtCu3 and PtCo3 Nanoparticle Fuel Cell Catalysts (pages 1805–1813)

      Frédéric Hasché, Mehtap Oezaslan and Prof. Dr. Peter Strasser

      Article first published online: 2 SEP 2011 | DOI: 10.1002/cctc.201100169

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      Stamina & durability: In this work, we studied the long-term stability of dealloyed PtCo3/HSAC (high-surface-area carbon) and PtCu3/HSAC nanoparticle catalysts under typical fuel cell conditions and correlated with the Pt electrochemically active surface area, particle size distribution, composition, and activity for oxygen reduction. Altogether, both Pt alloy catalysts exhibit a significantly improved cycling durability and activity compared with pure Pt.

    7. Controlled Synthesis and Characterization of Highly Dispersed Molybdenum Oxide Supported on Silica SBA-15 (pages 1814–1821)

      Dr. Jörg P. Thielemann, Gisela Weinberg and Prof. Christian Hess

      Article first published online: 29 AUG 2011 | DOI: 10.1002/cctc.201100154

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      Heavy on dispersion: A controlled synthesis approach yields SBA-15-supported molybdenum oxide catalysts with homogeneous molybdenum oxide distributions and loadings up to 3.5 atoms nm−2. Based on spectroscopic studies, a synthesis mechanism is proposed. New quasi in situ X-ray photoelectron spectroscopy results allow for a detailed charcterization of the molybdenum-oxide dispersion and a direct correlation of the molybdenum-oxide structure and dispersion.

    8. Continuous Gas-Phase Hydroformylation of a Highly Diluted Technical C4 Feed using Supported Ionic Liquid Phase Catalysts (pages 1822–1827)

      Dr. Marco Haumann, Michael Jakuttis, Dr. Robert Franke, Andreas Schönweiz and Prof. Peter Wasserscheid

      Article first published online: 5 OCT 2011 | DOI: 10.1002/cctc.201100117

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      A silppery business: The concept of supported ionic liquid phase (SILP) hydroformylation catalysis has been extended to reactions with a highly diluted, technical C4 feed containing 1.5 % 1-butene, 28.5 % 2-butenes, and 70 % inert n-butane. The Rh-biphephos 1 catalyst system is immobilized in the SILP system to allow for consecutive isomerization-hydroformylation activity. The resultant SILP catalyst material converts up to 81 % of the reactive butenes. Post-reaction NMR studies reveal no significant loss of the phosphite ligand during the reaction to oxidation of the ligand.

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    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Highlights
    7. Reviews
    8. Communications
    9. Full Papers
    10. Preview
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