ChemCatChem

Cover image for Vol. 4 Issue 10

Special Issue: Synthesis of Nanocatalysts

October 2012

Volume 4, Issue 10

Pages 1441–1682

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Communications
    9. Full Papers
    1. You have free access to this content
      Cover Picture: A Mechanistic Study on the Nucleation and Growth of Au on Pd Seeds with a Cubic or Octahedral Shape (ChemCatChem 10/2012) (page 1441)

      Guannan He, Dr. Jie Zeng, Mingshang Jin, Dr. Hui Zhang, Ning Lu, Dr. Jinguo Wang, Prof. Moon J. Kim and Prof. Younan Xia

      Version of Record online: 25 SEP 2012 | DOI: 10.1002/cctc.201290034

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      Shape-Controlled Synthesis of Pd–Au Bimetallic Nanocrystals The cover picture shows that Pd–Au bimetallic nanocrystals with a number of different morphologies, including hybrid dimers, core–shell nanocubes with flat faces, and core–shell nanocubes with concave faces, could all be synthesized by controlling the growth mode of Au on Pd cubic seeds. In their full paper on p. 1668 ff., Younan Xia et al. investigate the seed-mediated growth of Pd–Au bimetallic nanocrystals with a variety of controlled morphologies by manipulating the reaction kinetics through a set of experimental parameters, including the concentration of reductant, the amount of precursor, the temperature, and the Pd nanocrystals employed as the seeds. The high-index facets associated with a concave surface can potentially enhance the performance of Au-based nanocatalysts in a range of industrially important reactions.

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      Inside Cover: Size and Shape Control of Metal Nanoparticles for Reaction Selectivity in Catalysis (ChemCatChem 10/2012) (page 1442)

      Dr. Kwangjin An and Prof. Gabor A. Somorjai

      Version of Record online: 25 SEP 2012 | DOI: 10.1002/cctc.201290035

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      In the Search for Selectivity Catalysis in the 21st century is aiming for 100% selectivity to produce only one desired product at high turnover rates. The cover picture shows ships loading nanoparticles with different shapes in the search for selectivity. By using different shaped nanoparticles, catalytic selectivity can be achieved for many reactions. In the Minireview on page 1512 ff., K. An and G. A. Somorjai describe how the size and shape of nanoparticles affect reaction pathways, such as isomerization, aromatization, cyclization, and cracking to generate selective products. Combining in situ surface characterization techniques, real-time monitoring of nanoparticles can be performed under reaction environments to identify the molecular factors that affect catalysis.

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      Back Cover: Preparation of Inorganic Photocatalytic Materials for Overall Water Splitting (ChemCatChem 10/2012) (page 1684)

      Prof. Kazuhiro Takanabe and Prof. Kazunari Domen

      Version of Record online: 25 SEP 2012 | DOI: 10.1002/cctc.201290038

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      Water Splitting by Inorganic Photocatalyst Materials The back cover illustrates the crystalline powders that have extended absorption in visible light range (deep red color), being decorated by two different cocatalyst particles for hydrogen evolution and oxygen evolution, respectively. The picture shows the different scale of the materials, from a suspension of powders in water (bottom) to a designed cocatalyst with core–shell structure in nanometer-scale (left). A concept describing the charge separation of the excited charge carriers followed by electrocatalysis for water splitting is also schematically visualized (top-right). More details can be found in the Minireview on p. 1485 ff., in which K. Takanabe and K. Domen discuss the-state-of-the-art photocatalytic overall water splitting, as a solar energy conversion technology. A variety of synthetic techniques to generate the inorganic semiconductor powder materials have been reviewed.

  2. Editorial

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Communications
    9. Full Papers
    1. You have free access to this content
      Editorial: Catalyst Synthesis by Design for the Understanding of Catalysis (pages 1445–1447)

      Shu-Hong Yu, Franklin (Feng) Tao and Jimmy (Jingyue) Liu

      Version of Record online: 25 SEP 2012 | DOI: 10.1002/cctc.201200599

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      More than 50 shades of grey! The ultimate goal of research on heterogeneous catalysis is to provide a fundamental understanding of the nature of active sites toward the design of efficient heterogeneous catalysts that provide highest activity, 100 % selectivity, and long-term stability. This special issue on the Synthesis of Nanocatalysts builds towards that goal.

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Communications
    9. Full Papers
  4. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Communications
    9. Full Papers
  5. Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Communications
    9. Full Papers
    1. Composite Metal–Oxide Nanocatalysts (pages 1462–1484)

      Dr. Shuhua Liu, Dr. Shi-Qiang Bai, Dr. Yuangang Zheng, Dr. Kwok Wei Shah and Dr. Ming-Yong Han

      Version of Record online: 14 SEP 2012 | DOI: 10.1002/cctc.201200264

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      A gold star for nanocatalysis: We summarize the recent syntheses, structures, and compositions of diversified core–shell, yolk–shell, Janus, and their combined metal–oxide nanostructures. These functional nanocatalysts have been used for important catalytic applications, including organic reduction–oxidation, the water–gas shift reaction, CO2 conversion, biomass conversion, and water splitting.

  6. Minireviews

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Communications
    9. Full Papers
    1. Preparation of Inorganic Photocatalytic Materials for Overall Water Splitting (pages 1485–1497)

      Prof. Kazuhiro Takanabe and Prof. Kazunari Domen

      Version of Record online: 20 AUG 2012 | DOI: 10.1002/cctc.201200324

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      It′s all in the preparation: The preparation of the photocatalysts and the cocatalysts for overall water splitting using powder inorganic materials is listed and discussed. Based on the principle and the requirements for overall water splitting, the preparation techniques that have been commonly used in the literature are listed to present an overview of each method.

    2. Preparation and Catalysis of Carbon-Supported Iron Catalysts for Fischer–Tropsch Synthesis (pages 1498–1511)

      Bo Sun, Ke Xu, Luan Nguyen, Prof. Dr. Minghua Qiao and Prof. Dr. Franklin (Feng) Tao

      Version of Record online: 27 AUG 2012 | DOI: 10.1002/cctc.201200241

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      Carbon-supported Fe catalysts have attracted increasing interest in Fischer–Tropsch synthesis because of the unique properties of carbon materials, such as high surface area, high porosity, and ample electronic and topological structures. This Review focuses on the progress made in the synthesis and applications of these catalysts.

    3. Size and Shape Control of Metal Nanoparticles for Reaction Selectivity in Catalysis (pages 1512–1524)

      Dr. Kwangjin An and Prof. Gabor A. Somorjai

      Version of Record online: 27 AUG 2012 | DOI: 10.1002/cctc.201200229

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      Captain of the selectivity ship: Catalysis in 21st century is aiming for 100 % selectivity to produce only one desired product at high turnover rates. Recently, size and shape dependent selectivity in many catalytic reactions has been demonstrated. Combining in situ surface characterization techniques, real-time monitoring of nanoparticles is performed under reaction environments to identify the molecular factors that affect catalysis.

    4. Infrared Absorption Spectroscopy of Adsorbed CO: New Applications in Nanocatalysis for an Old Approach (pages 1525–1533)

      Prof. Francisco Zaera

      Version of Record online: 10 JUL 2012 | DOI: 10.1002/cctc.201200195

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      An oldie but goodie: The power of using well-established CO infrared absorption spectroscopy to characterize novel nanostructured catalysts is discussed.

    5. Functionalized Ionic Liquids for the Synthesis of Metal Nanoparticles and their Application in Catalysis (pages 1534–1546)

      Kylie L. Luska and Prof. Dr. Audrey Moores

      Version of Record online: 5 DEC 2011 | DOI: 10.1002/cctc.201100366

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      FIL me up before you nano: Functionalized ionic liquids (FILs) with a metal-binding moiety are useful ligands for the synthesis of metal nanoparticles (NPs), providing both steric and electrostatic stabilization. The tunability of this class of compounds allow for a control of the properties of the resulting NPs. This Minireview discusses the synthesis and application of NP:FIL systems, with an emphasis on catalysis.

  7. Communications

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Communications
    9. Full Papers
    1. A Highly Selective Catalyst for Partial Hydrogenation of 1,3-Butadiene: MgO-Supported Rhodium Clusters Selectively Poisoned with CO (pages 1547–1550)

      Dicle Yardimci, Dr. Pedro Serna and Prof.  B. C. Gates

      Version of Record online: 11 JUN 2012 | DOI: 10.1002/cctc.201200033

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      A gateway to partial hydrogenation: Supported rhodium species with an essentially molecular character were precisely designed for the selective partial hydrogenation of 1,3-butadiene to give n-butenes, transforming a metal that is traditionally considered unselective into one that is highly selective.

    2. Copper Ion Enhanced Synthesis of Nanostructured Cobalt Oxide Catalyst for Oxidation of Methane (pages 1551–1554)

      Yunzhe Feng and Prof. Xiaolin Zheng

      Version of Record online: 15 FEB 2012 | DOI: 10.1002/cctc.201100322

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      Cu can help Co3O4: The Cu2+ ions can improve the growth of a onedimensional Co3O4 catalyst on stainless steel mesh by facilitating the nucleation process. With higher mass loading and coverage density, the 1 D nanostructured Co3O4 grown with Cu2+ ions addition has larger catalytic surface area per unit area of support and, hence, exhibits higher catalytic activity for CH4 oxidation than the Co3O4 grown without Cu2+ added.

    3. Controlled Synthesis of PtRu/Graphene Nanocatalysts with Enhanced Methanol Oxidation Activity for Fuel Cells (pages 1555–1559)

      Dr. Huai-Ping Cong, Xiao-Chen Ren and Prof. Dr. Shu-Hong Yu

      Version of Record online: 5 SEP 2012 | DOI: 10.1002/cctc.201200403

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      Weigh the anchor! PtRu/graphene nanocatalysts with tunable and excellent electrochemical performance for methanol oxidation can be prepared through uniformly anchoring PtRu nanoparticles with small sizes onto graphene sheets through a simple one-step reduction method without surfactant. The graphene sheets are a promising support to optimize the electrocatalytic activity of fuel cells.

    4. Ternary PtPdCu Electrocatalyst Formed through Surface-Atomic Redistribution against Leaching (pages 1560–1563)

      Dr. Chun-Hua Cui, Xiao-Jing Liu, Hui-Hui Li, Dr. Min-Rui Gao, Dr. Hai-Wei Liang, Dr. Hong-Bin Yao and Prof. Dr. Shu-Hong Yu

      Version of Record online: 2 JUL 2012 | DOI: 10.1002/cctc.201200070

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      Good things come in threes: Ternary PtPdCu electrocatalysts were formed through surface-atomic redistribution under potential cycling. This redistribution modified the surface electronic structure and adsorbate bond energy, thus changing the electrocatalytic activity for the oxygen-reduction reaction.

  8. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Communications
    9. Full Papers
    1. Solvent-free Liquid-phase Oxidation of 1-Hexene using Supported Gold Catalysts (pages 1565–1571)

      Hamed Alshammari, Dr. Peter J. Miedziak, Dr. Salem Bawaked, Prof. David W. Knight and Prof. Graham J. Hutchings

      Version of Record online: 27 AUG 2012 | DOI: 10.1002/cctc.201200273

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      Winner takes it all: Gold supported on graphite is a promising catalyst for the oxidation of 1-hexene with the addition of a catalytic amount of a peroxy initiator. The same catalysts used for the oxidation of cyclcohexene and cyclooctene can also be applied to the oxidation of straight chain alkenes, with all the products identified. Furthermore, the catalyst is effective under mild, solvent-free conditions using oxygen from air as the oxidant.

    2. Study of the Durability of Faceted Pt3Ni Oxygen–Reduction Electrocatalysts (pages 1572–1577)

      Jianbo Wu and Prof. Hong Yang

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/cctc.201200242

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      Sticking around: The durability of truncated octahedral Pt3Ni (t,o-Pt3Ni) in the oxygen–reduction reaction (ORR) is reported. The catalyst lost 21 % of its initial electrochemical surface area and 40 % of its mass-current density after 30 000 potential cycles.

    3. A Multi-Yolk–Shell Structured Nanocatalyst Containing Sub-10 nm Pd Nanoparticles in Porous CeO2 (pages 1578–1586)

      Cheng Chen, Dr. Xiaoliang Fang, Binghui Wu, Liujun Huang and Prof. Nanfeng Zheng

      Version of Record online: 14 SEP 2012 | DOI: 10.1002/cctc.201200237

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      Nanoparticles engulfed, shell and all: Starting from monodisperse hydrophobic sub-10 nm Pd nanoparticles, a Pd@hm-CeO2 multi-yolk–shell nanocatalyst is prepared (h=hollow; m=mesoporous). Owing to the feature that fine Pd nanoparticles are individually encapsulated in hm-CeO2 compartments, the encapsulated catalyst exhibits enhanced catalytic activity and stability.

    4. Ordered Mesoporous Carbon Supported Colloidal Pd Nanoparticle Based Model Catalysts for Suzuki Coupling Reactions: Impact of Organic Capping Agents (pages 1587–1594)

      Ha Rim Choi, Hyunje Woo, Seongwan Jang, Jae Young Cheon, Chungho Kim, Prof. Jongnam Park, Prof. Kang Hyun Park and Prof. Sang Hoon Joo

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/cctc.201200220

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      The next top model: High-surface-area Pd/CMK-3 catalysts based on colloidal Pd nanoparticles (NPs) and mesoporous carbon were prepared and the effect of capping agents for Pd NPs on their catalytic activity in Suzuki reactions was investigated.

    5. Bimetallic Au–Pd Nanoparticles Confined in Tubular Mesoporous Carbon as Highly Selective and Reusable Benzyl Alcohol Oxidation Catalysts (pages 1595–1602)

      Yan Hao, Guang-Ping Hao, De-Cai Guo, Chun-Zao Guo, Prof. Wen-Cui Li, Dr. Ming-Run Li and Prof. An-Hui Lu

      Version of Record online: 31 JUL 2012 | DOI: 10.1002/cctc.201200207

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      The great confinement: CMK-5 with a bimodal mesoporous structure provides a good venue for the formation of highly dispersed Au–Pd nanoparticles confined in carbon channels. It exhibits high catalytic activity, selectivity, and reusability for benzyl alcohol oxidation. In particular, the investigation of impregnation sequences on catalytic activities could contribute to the understanding of the bimetallic synergistic effect on benzyl alcohol oxidation.

    6. Low-Temperature Gas-Phase Oxidation of Benzyl Alcohol on Mesoporous K-Cu-TiO2 through Oxidative Dehydrogenation (pages 1603–1610)

      Yihu Dai, Xiaoqing Yan, Yu Tang, Xiaonao Liu, Liping Xiao and Prof. Dr. Jie Fan

      Version of Record online: 17 JUL 2012 | DOI: 10.1002/cctc.201200196

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      Gas-tronomic meso soup: Highly selective, gas-phase benzyl alcohol-to-benzaldehyde transformation is achieved over mesoporous multi-component metal oxide K-Cu-TiO2 at a surprisingly low temperature—the b.p. of benzyl alcohol, 203 °C—through an oxidative dehydrogenation mechanism.

    7. Hydrogen Production through Water–Gas Shift Reaction over Supported Cu, Ni, and Cu[BOND]Ni Nanoparticle Catalysts Prepared from Metal Colloids (pages 1611–1621)

      Jiann-Horng Lin and Prof. Vadim V. Guliants

      Version of Record online: 6 MAR 2012 | DOI: 10.1002/cctc.201100435

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      Metal colloids acting shifty: We report the fabrication of supported catalysts by deposition of preformed colloidal Cu, Ni, and Cu[BOND]Ni nanoparticles on alumina. Supported Cu and Ni nanoparticles are 2.5 times more active in the water–gas shift reaction than conventional impregnated catalysts. Bimetallic Cu5Ni5 nanoparticles are more catalytically active in this reaction than Cu and Ni catalysts.

    8. Nanostructural Studies of Fresh and Road-Aged Practical Pt/SiO2 and Pt-Pd/Al2O3 Diesel Oxidation Catalysts by using Aberration-Corrected (Scanning) Transmission Electron Microscopy (pages 1622–1631)

      Michael R. Ward, Dr. Tim Hyde, Prof. Edward D. Boyes and Prof. Pratibha L. Gai

      Version of Record online: 21 AUG 2012 | DOI: 10.1002/cctc.201200333

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      What's up DOC? Atomic scale high-angle annular dark-field scanning TEM observations of fresh and road-aged bimetallic diesel oxidation catalyst (DOC) reveal that the fresh catalyst contains nanoscale particles and that the majority of aged DOC nanoparticles do not display segregation. The essentially spherical morphology of the majority of the nanoparticles reveals low symmetry atomic planes with atomic steps important for active sites.

    9. Support-dependent Performance of Size-selected Subnanometer Cobalt Cluster-based Catalysts in the Dehydrogenation of Cyclohexene (pages 1632–1637)

      Dr. Sungsik Lee, Dr. Marcel Di Vece, Dr. Byeongdu Lee, Dr. Sönke Seifert, Dr. Randall E. Winans and Dr. Stefan Vajda

      Version of Record online: 27 AUG 2012 | DOI: 10.1002/cctc.201200294

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      Assemble together, catalyze together: The catalytic activity and selectivity of subnanometer 27±4 atom cobalt clusters in the dehydrogenation of cyclohexene shows strong support dependency. The support-cluster interactions reflect in the evolution of the oxidation state of the clusters during the course of the reaction, as well as in the formation of a dynamically evolving nanoassembly on the MgO support.

    10. On the Effect of Atomic Structure on the Activity and Deactivation of Catalytic Gold Nanoparticles (pages 1638–1644)

      Michael J. Walsh, Dr. Kenta Yoshida, Dr. Mungo L. Pay, Prof. Pratibha L. Gai and Prof. Edward D. Boyes

      Version of Record online: 21 AUG 2012 | DOI: 10.1002/cctc.201200261

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      More than just a pretty surface: Through atomic resolution aberration-corrected in situ electron microscopy we show how the minimization of both surface and elastic energy leads to a loss of active sites as a result of heating. These results highlight the need to consider the stability of the identified active sites at the atomic scale under simulated reaction conditions for structurally sensitive nanocatalysts.

    11. Architecture of Pt[BOND]Co Bimetallic Catalysts for Catalytic CO Oxidation (pages 1645–1652)

      Hong Xu, Prof. Qiang Fu, Xiaoguang Guo and Prof. Xinhe Bao

      Version of Record online: 7 AUG 2012 | DOI: 10.1002/cctc.201200255

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      CoOl! A “CoO-on-Pt” structure was constructed in supported Pt[BOND]Co nanocatalysts, which exhibits superior performance in CO oxidation in the absence of H2 (COOX) and preferential oxidation of CO in excess H2 (PROX).

    12. A Raman Spectroscopic Study of the Speciation of Vanadia Supported on Ceria Nanocrystals with Defined Surface Planes (pages 1653–1661)

      Dr. Zili Wu, Dr. Meijun Li and Dr. Steven H. Overbury

      Version of Record online: 2 AUG 2012 | DOI: 10.1002/cctc.201200243

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      Shape matters: Nanoshaped ceria with defined surface planes offers a fairly homogeneous platform for anchoring vanadia species. The surface oxygen vacancy formation energy and amount of defect sites in these nanoshapes, determined by the surface plane of ceria, are found to control the reaction between ceria and vanadia to form CeVO4.

    13. Controlled Synthesis of Nanoscale Icosahedral Gold Particles at Room Temperature (pages 1662–1667)

      Dr. Lifang Chen, G. Jeremy Leong, Maxwell Schulze, Dr. Huyen N. Dinh, Dr. Bryan Pivovar, Prof. Juncheng Hu, Prof. Zhiwen Qi, Yunjin Fang, Dr. Sergey Prikhodko, Dr. Marta Pozuelo, Prof. Suneel Kodambaka and Prof. Ryan M. Richards

      Version of Record online: 2 AUG 2012 | DOI: 10.1002/cctc.201200230

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      Controlling icosahedra: Gold icosahedra are synthesized with glucose as reducing reagent and sodium dodecyl sulfate as directing agent in water at room temperature. The size of the icosahedra can be controlled in the range of 30–250 nm by altering reaction conditions. Comparison studies with spherical particles and poisoning experiments demonstrate the importance of shape on the catalytic properties.

    14. A Mechanistic Study on the Nucleation and Growth of Au on Pd Seeds with a Cubic or Octahedral Shape (pages 1668–1674)

      Guannan He, Dr. Jie Zeng, Mingshang Jin, Dr. Hui Zhang, Ning Lu, Dr. Jinguo Wang, Prof. Moon J. Kim and Prof. Younan Xia

      Version of Record online: 25 MAY 2012 | DOI: 10.1002/cctc.201200205

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      Among the seeds of gold: The seed-mediated growth of Pd–Au bimetallic nanocrystals can be controlled by manipulating the reaction kinetics. As a result, a range of controlled morphologies can be obtained. For the first time, Pd–Au crystals with concave faces are produced. These are found to have a higher catalytic activity than their counterparts with flat faces or cubic Pd seeds.

    15. Antisolvent Precipitation for the Synthesis of Monodisperse Mesoporous Niobium Oxide Spheres as Highly Effective Solid Acid Catalysts (pages 1675–1682)

      Cheng Chao Li, Jian Dou, Dr. Luwei Chen, Prof. Jianyi Lin and Prof. Hua Chun Zeng

      Version of Record online: 20 MAR 2012 | DOI: 10.1002/cctc.201100457

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      It′s raining mesospheres: A simple antisolvent precipitation approach is used to prepare monodisperse glycolated niobium oxide spheres, which are hydrothermally converted to mesoporous niobium oxide spheres and functionalized with sulfate anions or tungstophosphoric acid to produce recyclable solid acid catalysts with excellent performance in the Friedel–Crafts alkylation, esterification, and hydrolysis of acetates.

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