ChemCatChem

Cover image for Vol. 3 Issue 6

Special Issue: Advanced Microscopy

June 14, 2011

Volume 3, Issue 6

Pages 917–1083

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Review
    8. Minireview
    9. Concept
    10. Communications
    11. Full Papers
    12. Preview
    1. Cover Picture: Morphology and Microstructure of Li/MgO Catalysts for the Oxidative Coupling of Methane (ChemCatChem 6/2011) (page 917)

      Dr. Ulyana Zavyalova, Dr. Michael Geske, Dr. Raimund Horn, Gisela Weinberg, Wiebke Frandsen, Manfred Schuster and Prof. Dr. Robert Schlögl

      Article first published online: 7 JUN 2011 | DOI: 10.1002/cctc.201190023

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      The cover picture shows the hierarchical structure of the famous Li/MgO catalyst prepared for the oxidative dimerization of methane. It transpires that the Li/MgOx islands named as active sites are only transient species. Upon their complete volatilization, a modified structure of the parent MgO is generated, which exhibits high-energy surface terminations, such as steps and defect clusters. The porosity on several scales directs the material flow and may accommodate gas-phase reactions coupled to the surface activation of methane. The Minireview “Morphology and Microstructure of Li/MgO Catalysts for the Oxidative Coupling of Methane” on p. 949 ff., by Schlögl et al., reviews the structure-directory function of Li additives modifying the MgO bulk upon exposure to high temperatures and reactive atmospheres. The role of point defects and the redox activity of such modified MgO remain elusive.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Review
    8. Minireview
    9. Concept
    10. Communications
    11. Full Papers
    12. Preview
    1. Inside Cover: Exploitation of Surface-Sensitive Electrons in Scanning Electron Microscopy Reveals the Formation Mechanism of New Cubic and Truncated Octahedral CeO2 Nanoparticles (ChemCatChem 6/2011) (page 918)

      Shunsuke Asahina, Dr. Seiichi Takami, Takeshi Otsuka, Prof. Tadafumi Adschiri and Prof. Osamu Terasaki

      Article first published online: 7 JUN 2011 | DOI: 10.1002/cctc.201190024

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      The inside cover picture shows a range of scanning electron microscopy (SEM) images of CeO2 nanoparticles. In their Full Paper on p. 1038 ff., S. Takami et al. describe how the development of new analytical tools for nanostructures, directly contributes to the study of catalysts. By using SEM with a newly designed signal enhancer, they studied cubic and truncated octahedral cerium oxide (CeO2) nanoparticles and go on to discuss the formation mechanism of the nanoparticles.

  3. Editorial

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Review
    8. Minireview
    9. Concept
    10. Communications
    11. Full Papers
    12. Preview
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  4. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Review
    8. Minireview
    9. Concept
    10. Communications
    11. Full Papers
    12. Preview
    1. Graphical Abstract: ChemCatChem 6/2011 (pages 922–927)

      Article first published online: 7 JUN 2011 | DOI: 10.1002/cctc.201190025

  5. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Review
    8. Minireview
    9. Concept
    10. Communications
    11. Full Papers
    12. Preview
  6. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Review
    8. Minireview
    9. Concept
    10. Communications
    11. Full Papers
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    1. Advanced Electron Microscopy of Metal–Support Interactions in Supported Metal Catalysts (pages 934–948)

      Prof. Dr. Jingyue (Jimmy) Liu

      Article first published online: 7 JUN 2011 | DOI: 10.1002/cctc.201100090

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      Counting atoms on a nanoparticle: A sub-angstrom resolution high-angle annular dark-field image of a PtSn alloy nanoparticle provides information on the arrangement of the surface atoms and its 3D shape. The support is activated carbon (red color). Applications of advanced electron microscopy techniques to the study of metal–support interactions, which are critical to manufacturing nanoscale architectured heterogeneous catalysts for chemical reactions, are reviewed.

  7. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Review
    8. Minireview
    9. Concept
    10. Communications
    11. Full Papers
    12. Preview
    1. Morphology and Microstructure of Li/MgO Catalysts for the Oxidative Coupling of Methane (pages 949–959)

      Dr. Ulyana Zavyalova, Dr. Michael Geske, Dr. Raimund Horn, Gisela Weinberg, Wiebke Frandsen, Manfred Schuster and Prof. Dr. Robert Schlögl

      Article first published online: 15 OCT 2010 | DOI: 10.1002/cctc.201000098

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      From Me to Me: The Li/MgO catalyst has been subject to intense research for the oxidative coupling of methane (OCM). The exact role of Li in this process is enigmatic. By using a combination of electron microscopic techniques, it is shown that the function of Li is clearly related to the transformation of the MgO into a non-equilibrium form, exposing clusters of defects as plausible active sites for OCM.

  8. Concept

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Review
    8. Minireview
    9. Concept
    10. Communications
    11. Full Papers
    12. Preview
    1. New Strategies for e-Beam Characterization of Catalysts (pages 961–964)

      Prof.  A. Howie

      Article first published online: 1 SEP 2010 | DOI: 10.1002/cctc.201000171

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      How exciting is it to be ever so slightly ALOOF? We can answer this question by coincidence detection of emitted secondary electrons (SE). From the threshold excitation energy for SE emission, we may determine the surface barrier height at a nanoparticle facet that is skimmed by a focused fast electron beam.

  9. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Review
    8. Minireview
    9. Concept
    10. Communications
    11. Full Papers
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    1. Towards a More Accurate Particle Size Distribution of Supported Catalyst by using HAADF-STEM (pages 965–968)

      Dr. Bingsen Zhang, Dr. Wei Zhang and Prof. Dr. Dang Sheng Su

      Article first published online: 27 MAY 2011 | DOI: 10.1002/cctc.201100096

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      STEM can make a large difference: Conventionally the catalysis community has used HRTEM (figure, left) imaging to obtain the particle size distribution (PSD) of supported catalysts. Now we have found that by using the analogous HAADF-STEM (figure, right) a more accurate PSD can be calculated, which is crucial for understanding the catalysis mechanisms.

    2. Towards a Selective Heterogeneous Catalyst for Glucose Dehydration to 5-Hydroxymethylfurfural in Water: CrCl2 Catalysis in a Thin Immobilized Ionic Liquid Layer (pages 969–972)

      Dr. Volkan Degirmenci, Dr. Evgeny A. Pidko, Dr. Pieter C. M. M. Magusin and Prof. Dr. Emiel J. M. Hensen

      Article first published online: 21 APR 2011 | DOI: 10.1002/cctc.201000426

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      Sugar it up: Stabilization of the CrCl2 active phase in a thin layer of an ionic liquid covalently grafted to mesoporous silica results in a highly selective catalyst for the dehydration of glucose to 5-hydroxymethylfurfural (HMF) in an aqueous medium. Glucose dehydration in water by using the CrCl2-Im-SBA-15 catalyst leads to a 50 % HMF selectivity that can be further increased to up to 70 % by modifying the solvent system.

  10. Full Papers

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Review
    8. Minireview
    9. Concept
    10. Communications
    11. Full Papers
    12. Preview
    1. A Ligand Structure–Activity Study of DNA-Based Catalytic Asymmetric Hydration and Diels–Alder Reactions. (pages 973–977)

      Fiora Rosati and Dr. Gerard Roelfes

      Article first published online: 21 APR 2011 | DOI: 10.1002/cctc.201000440

      Thumbnail image of graphical abstract

      Hydration with a twist: A structure–activity relationship study of first generation ligands for the catalytic enantioselective hydration and Diels–Alder reactions is presented. The results clearly show the potential of the second coordination sphere effects in asymmetric catalysis.

    2. Morphology and Crystal-Plane Effects of Nanoscale Ceria on the Activity of CuO/CeO2 for NO Reduction by CO (pages 978–989)

      Dr. Lianjun Liu, Zhijian Yao, Dr. Yu Deng, Dr. Fei Gao, Bin Liu and Prof. Lin Dong

      Article first published online: 26 APR 2011 | DOI: 10.1002/cctc.201000320

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      Cu2+ions were incorporated into surface lattice through occupying the vacant site in the nanostructure CeO2. The site geometry and coordination environment of Cu2+ ions are naturally different for each plane. Therefore, there is a strong synergistic interaction between CuO and the exposed (110) plane of the CeO2 nanorods, which in turn leads to high activity for NO reduction to N2. The weak interaction between CuO and (100) plane of CeO2 cubes determines its lowest activity at low temperature.

    3. Electron Microscopy of Cocatalyst Nanostructures on Semiconductor Photocatalysts (pages 990–998)

      Dr. Nicole S. Hondow, Dr. Yi-Hsin Chou, Dr. Kasim Sader, Dr. Richard E. Douthwaite and Prof. Rik Brydson

      Article first published online: 21 FEB 2011 | DOI: 10.1002/cctc.201000443

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      In vogue with microscopy: Evidence for the importance of chemical interactions between photocatalysts and metal cocatalysts investigated by using high resolution analytical electron microscopy.

    4. STEM HAADF Tomography of Molybdenum Disulfide with Mesoporous Structure (pages 999–1003)

      Feihong Nan, Dr. Chaojie Song, Dr. Jiujun Zhang, Dr. Rob Hui, Dr. Jinwen Chen, Dr. Craig Fairbridge and Prof. Gianluigi A. Botton

      Article first published online: 2 MAR 2011 | DOI: 10.1002/cctc.201000403

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      Not so heavy in the dark: Scanning transmission electron microscopy with high-angle annular dark field tomography to give spatial information on nanometre scale has been used to investigate the porous structure of a MoS2 catalyst developed for heavy oil refining, offering direct view of individual porous particles in three-dimensions.

    5. The Sintering of Supported Pd Automotive Catalysts (pages 1004–1014)

      Dr. Qing Xu, Dr. Karl C. Kharas, Brandon J. Croley and Prof. Dr. Abhaya K. Datye

      Article first published online: 17 MAY 2011 | DOI: 10.1002/cctc.201000392

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      Oh catalyst preserve us! Sintering of Pd/Al2O3 close coupled automotive catalysts show that metal particle size continues to grow with time with Ostwald ripening as the dominant mechanism. The alumina undergoes phase transformation into alpha alumina. These results have important implications for the design of thermally stable automotive catalysts.

    6. Advanced Electron Microscopy Investigation of Ceria–Zirconia-Based Catalysts (pages 1015–1027)

      M. López-Haro, Dr. J. A. Pérez-Omil, Dr. J. C. Hernández-Garrido, Dr. S. Trasobares, Dr. A. B. Hungría, J. M. Cíes, Prof. P. A. Midgley, Dr. P. Bayle-Guillemaud, Prof. A. Martínez-Arias, Prof. S. Bernal, Dr. J. J. Delgado and Dr. J. J. Calvino

      Article first published online: 29 NOV 2010 | DOI: 10.1002/cctc.201000306

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      Hail Ce–Zr: Advanced electron microscopies are systematically applied to the 2D and 3D structural and chemical characterization of ceria–zirconia systems of current interest in environmental catalysis. Relevant details concerning both the bulk and the surface of these materials are obtained, which allows us to establish a rational model to correlate redox properties, nanostructure, and thermochemical treatments.

    7. STEM HAADF Image Simulation of the Orthorhombic M1 Phase in the Mo-V-Nb-Te-O Propane Oxidation Catalyst (pages 1028–1033)

      Prof. Douglas A. Blom, Xin Li, Sonali Mitra, Prof. Thomas Vogt and Prof. Douglas J. Buttrey

      Article first published online: 1 JUN 2011 | DOI: 10.1002/cctc.201100049

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      You HAAD me at hello: Excellent agreement for most of the cation sites in the M1 structure was found between image simulations using the latest Rietveld-refined structure and experimental high angle annular dark field (HAADF) images. Discrepancies may be due to surface enrichment of Mo or V at certain cation sites.

    8. Quantitative Contrast Evaluation of an Industry-Style Rhodium Nanocatalyst with Single Atom Sensitivity (pages 1034–1037)

      Dr. Petra Specht, Dr. Robert J. Gulotty Jr., Dr. David Barton, Dr. Robert Cieslinski, Dr. Steve Rozeveld, Dr. Joo H. Kang, Prof. Oscar. D. Dubon and Dr. Christian Kisielowski

      Article first published online: 27 MAY 2011 | DOI: 10.1002/cctc.201000396

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      The atom counters: The figure shows a high-resolution image of a [110] Rh nanoparticle on alumina recorded with sub-Ångstrom resolution at 80 kV (peak width at full width half maximum=75 pm). After performing a quantitative contrast interpretation and various calculations, it becomes possible to count the number of atoms in each column. The recorded [110] Rh particle is a platelet with an aspect ratio of about 0.2, an average column height of 4 atoms, and a surface roughness of ±1 atom.

    9. Exploitation of Surface-Sensitive Electrons in Scanning Electron Microscopy Reveals the Formation Mechanism of New Cubic and Truncated Octahedral CeO2 Nanoparticles (pages 1038–1044)

      Shunsuke Asahina, Dr. Seiichi Takami, Takeshi Otsuka, Prof. Tadafumi Adschiri and Prof. Osamu Terasaki

      Article first published online: 21 APR 2011 | DOI: 10.1002/cctc.201000348

      Thumbnail image of graphical abstract

      Did it all for the crystals! We observed the detailed structure of cubic and truncated octahedral CeO2 nanoparticles comprising smaller primary nanocrystals by using a scanning electron microscope equipped with a newly designed secondary electron collector. The images suggest how the primary nanocrystals are assembled to form well-defined secondary structures and their growth mechanism.

    10. Aberration-corrected Analytical Microscopy Characterization of Double-Supported WO3/TiO2/SiO2 Solid Acid Catalysts (pages 1045–1050)

      Wu Zhou, Kevin F. Doura, Prof. Masashi Watanabe, Dr. Andrew A. Herzing, Dr. Eiji Okunishi, Dr. Elizabeth I. Ross-Medgaarden, Prof. Israel E. Wachs and Prof. Christopher J. Kiely

      Article first published online: 29 NOV 2010 | DOI: 10.1002/cctc.201000273

      Thumbnail image of graphical abstract

      Visualizing complex catalysts: In combining aberration-corrected scanning transmission electron microscope (STEM) imaging and electron energy-loss spectroscopy (EELS) analysis, it is possible to map out the atomic structure and relative distribution of various metal oxide components in complex double-supported metal oxide catalysts (see figure).

    11. Atomic-Scale Observation of the Ni Activation Process for Partial Oxidation of Methane Using In Situ Environmental TEM (pages 1051–1059)

      Santhosh Chenna, Ritubarna Banerjee and Prof. Peter A. Crozier

      Article first published online: 12 OCT 2010 | DOI: 10.1002/cctc.201000238

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      ETEM and smile: In situ environmental transmission electron microscopy (ETEM) is employed to develop an atomic-level understanding of the structure, composition, and morphologies that develop in a model Ni/SiO2 catalyst during ramp-up for partial oxidation of methane under high-conversion conditions. Gas composition along the catalyst bed varies in space and time during the ramp-up.

    12. Aryl Fluoride Reductive Elimination from PdII Complexes: a Descriptor to Guide Ligand Selection (pages 1060–1064)

      Luchao Cui and Prof. Dr. Mark Saeys

      Article first published online: 14 APR 2011 | DOI: 10.1002/cctc.201000461

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      Charge is the essence: Aryl fluoride reductive elimination from PdII complexes was analyzed by using DFT calculations. The reactivity of Ar[BOND]F reductive elimination is determined by the sum of the NPA charges on the Pd center and aryl α-carbon atom. Ar[BOND]F reductive elimination can be described as the nucleophilic attack of one of the fluorine lone pairs on the antibonding σ* Pd[BOND]C orbital.

    13. Engineered Bacterial Mimics of Human Drug Metabolizing Enzyme CYP2C9 (pages 1065–1071)

      Dr. Andrea Rentmeister, Tristan R. Brown, Dr. Christopher D. Snow, Dr. Martina N. Carbone and Prof. Frances H. Arnold

      Article first published online: 21 APR 2011 | DOI: 10.1002/cctc.201000452

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      Enzyme acrobatics: A highly destabilizing L75R mutation induces flexibility in helix B′ of a P450BM3 variant. The resulting enzyme's basal activity on charged substrates, naproxen and ibuprofen, is increased by directed evolution.

    14. Interfacial Impregnation Chemistry in the Synthesis of Chromium Catalysts Supported on Titania (pages 1072–1082)

      Dr. Theano Petsi, Dr. George D. Panagiotou, Dr. Kyriakos Bourikas, Prof. Christos Kordulis, Dr. George A. Voyiatzis and Prof. Alexis Lycourghiotis

      Article first published online: 10 MAY 2011 | DOI: 10.1002/cctc.201000446

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      Chromium on the catwalk: Local structures of the adsorbed CrVI oxo-species (CrO42−, HCrO4, and Cr2O72−) on the (101) crystal termination of anatase, which are electrostatically retained above the positively charged bridging hydroxyl groups by forming ion-pairs.

  11. Preview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Review
    8. Minireview
    9. Concept
    10. Communications
    11. Full Papers
    12. Preview
    1. You have free access to this content
      Preview: ChemCatChem 7/2011 (page 1083)

      Article first published online: 7 JUN 2011 | DOI: 10.1002/cctc.201190022

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