ChemSusChem

Cover image for Vol. 7 Issue 9

September 2014

Volume 7, Issue 9

Pages 2367–2754

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Review
    8. Highlight
    9. Communications
    10. Full Papers
    1. You have free access to this content
      Cover Picture: Energy and Chemicals from the Selective Electrooxidation of Renewable Diols by Organometallic Fuel Cells (ChemSusChem 9/2014) (page 2367)

      Marco Bellini, Dr. Manuela Bevilacqua, Dr. Jonathan Filippi, Dr. Alessandro Lavacchi, Dr. Andrea Marchionni, Dr. Hamish A. Miller, Dr. Werner Oberhauser, Dr. Francesco Vizza, Samuel P. Annen and Prof. Dr.  H. Grützmacher

      Article first published online: 19 AUG 2014 | DOI: 10.1002/cssc.201402749

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      The Front Cover image is an allegorical representation of the organometallic fuel cell (OMFC) system described in the paper of F. Vizza, H. Grützmacher et al. The dance of the three graces is the fulcrum: they dance together forming a circle representing the three organometallic complexes of the catalytic cycle for the selective electro-oxidation of diols obtained from renewable resources to the corresponding carboxylate compounds. Simultaneously, the electrons (Eros) move towards the cathode electrode (Flora and Zephyr), where oxygen is reduced to OH producing energy. More details can be found in the Communication on page 2432 (DOI: 10.1002/cssc.201402316), while more information about the research group is available in the Cover Profile (DOI: 10.1002/cssc.201402750).

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      Inside Cover: Coupled Near- and Far-Field Scattering in Silver Nanoparticles for High-Efficiency, Stable, and Thin Plasmonic Dye-Sensitized Solar Cells (ChemSusChem 9/2014) (page 2368)

      Gede Widia Pratama Adhyaksa, Se-Woong Baek, Dr. Ga In Lee, Dong Ki Lee, Prof. Jung-Yong Lee and Prof. Jeung Ku Kang

      Article first published online: 22 AUG 2014 | DOI: 10.1002/cssc.201402687

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      The Inside Cover picture shows the plasmonically enhanced thin dye-sensitized solar cells developed by Kang et al. through synergistic near-field and far-field coupling of size-controlled plasmonic nanoparticles. Molecular complex dyes absorb photons with roughly 100 times lower adsorption intensities than those of other inorganic sensitizers. This approach prevents realization of thin solar cells for efficient photon collection. The group of Prof. Jeung Ku Kang present a strategy for efficient photon absorption on a thin solar cell. This approach results in substantially improved power conversion efficiencies through a synergistic arrangement of plasmonic particles in the electrolyte and the photoelectrode; strong far-field scattering is critical in the electrolyte and near-field scattering is efficient in the photoelectrode. It also shows that a non-volatile ionic liquid electrolyte provides this thin plasmonic solar cell with good stability. More details can be found in the Full Paper on page 2461 (DOI: 10.1002/cssc.201402146).

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      Inside Back Cover: Advances in Asymmetric Borrowing Hydrogen Catalysis (ChemSusChem 9/2014) (page 2755)

      Dr. Dirk Hollmann

      Article first published online: 19 AUG 2014 | DOI: 10.1002/cssc.201402731

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      The Inside Back Cover image shows two simple methods for the production of chiral alcohols and amines starting from racemic alcohols. A powerful strategy is the borrowing hydrogen methodology, which combines transfer hydrogenation (avoidance of direct usage of hydrogen) with an intermediate reaction, such as condensation or α-alkylation, without necessary separation processes. Depending on the conditions, either subsequent asymmetric organocatalysis or asymmetric reduction of imines takes place. More details can be found in the Highlight by Dirk Hollmann on page 2411 (DOI: 10.1002/cssc.201402320).

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      Back Cover: Unveiling the Chemistry behind the Green Synthesis of Metal Nanoparticles (ChemSusChem 9/2014) (page 2756)

      Dr. Sónia A. O. Santos, Dr. Ricardo J. B. Pinto, Prof. Dr. Sílvia M. Rocha, Dr. Paula A. A. P. Marques, Prof. Dr. Carlos Pascoal Neto, Prof. Dr. Armando J. D. Silvestre and Dr. Carmen S. R. Freire

      Article first published online: 28 AUG 2014 | DOI: 10.1002/cssc.201402781

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      The Back Cover picture illustrates the green synthesis of metal nanoparticles using an Eucalyptus globulus bark extract. Santos et al. elucidated, through the use of advanced chromatographic techniques, the precise role of each family of compounds present in the plant extracts used in the bio-based synthesis of gold and silver nanoparticles. Phenolic compounds clearly had a pronounced impact on metal ion reduction while the sugars played a central role in their stabilization. More details can be found in the Full Paper on page 2704 (DOI: 10.1002/cssc.201302126).

  2. Cover Profile

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Review
    8. Highlight
    9. Communications
    10. Full Papers
    1. You have free access to this content
      Energy and Chemicals from the Selective Electrooxidation of Renewable Diols by Organometallic Fuel Cells (page 2369)

      Marco Bellini, Dr. Manuela Bevilacqua, Dr. Jonathan Filippi, Dr. Alessandro Lavacchi, Dr. Andrea Marchionni, Dr. Hamish A. Miller, Dr. Werner Oberhauser, Dr. Francesco Vizza, Samuel P. Annen and Prof. Dr.  H. Grützmacher

      Article first published online: 19 AUG 2014 | DOI: 10.1002/cssc.201402750

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      “The objective is to produce hydrogen while spending as little electrical energy as possible…‥” This and more about the story behind the research that inspired the cover image can be found on page 2369 (10.1002/cssc.201402316). View the Front Cover on page 2367 (10.1002/cssc.201402749).

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Review
    8. Highlight
    9. Communications
    10. Full Papers
    1. Graphical Abstract: ChemSusChem 9/2014 (pages 2370–2384)

      Article first published online: 5 SEP 2014 | DOI: 10.1002/cssc.201490032

  4. Masthead

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Review
    8. Highlight
    9. Communications
    10. Full Papers
    1. Masthead: ChemSusChem 9/2014 (pages 2386–2387)

      Article first published online: 5 SEP 2014 | DOI: 10.1002/cssc.201490033

  5. News

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Review
    8. Highlight
    9. Communications
    10. Full Papers
  6. Review

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Review
    8. Highlight
    9. Communications
    10. Full Papers
    1. Cascade Reactions Catalyzed by Metal Organic Frameworks (pages 2392–2410)

      Dr. Amarajothi Dhakshinamoorthy and Prof. Dr. Hermenegildo Garcia

      Article first published online: 31 JUL 2014 | DOI: 10.1002/cssc.201402148

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      One MOF—two opportunities: Metal–organic frameworks (MOFs) have attracted considerable attention in heterogeneous catalysis due to flexibility in synthesis, large porosity, and presence of active sites. The use of MOFs as solid catalysts is progressing fast and as result the number of papers reporting MOF catalysts for cascade, tandem, or domino processes in which two or more individual reactions are carried out simultaneously has increased considerably. Herein, the current state of the art is summarized.

  7. Highlight

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Review
    8. Highlight
    9. Communications
    10. Full Papers
    1. Advances in Asymmetric Borrowing Hydrogen Catalysis (pages 2411–2413)

      Dr. Dirk Hollmann

      Article first published online: 30 MAY 2014 | DOI: 10.1002/cssc.201402320

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      Borrowing extends opportunities: Borrowing hydrogen (BH) catalysis represents a powerful and environmental alternative to known C[BOND]C, C[BOND]N, and C[BOND]O formation schemes. Recently, two important approaches have been published that extended this methodology to asymmetric catalysis. A short discussion combined with a perspective for the asymmetric BH is presented in this highlight.

  8. Communications

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Review
    8. Highlight
    9. Communications
    10. Full Papers
    1. Tungsten Carbide–Nitride on Graphene Nanoplatelets as a Durable Hydrogen Evolution Electrocatalyst (pages 2414–2418)

      Dr. Wei-Fu Chen, Jonathan M. Schneider, Dr. Kotaro Sasaki, Chiu-Hui Wang, Dr. Jacob Schneider, Shilpa Iyer, Shweta Iyer, Dr. Yimei Zhu, Dr. James T. Muckerman and Dr. Etsuko Fujita

      Article first published online: 24 JUL 2014 | DOI: 10.1002/cssc.201402454

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      Win–WN situation: A graphene nanoplatelet-supported electrocatalyst comprised of nanostructured tungsten carbide (W2C) and tungsten nitride (WN) generates hydrogen efficiently in acidic water. Anchoring the W2C–WN onto graphene nanoplatelets greatly reduces the charge transfer resistance and accelerates the proton discharge kinetics. The overpotential (η10) is 120 mV, which is among the best of non-noble metal catalysts reported to date.

    2. Efficient and Selective Hydrogen Generation from Bioethanol using Ruthenium Pincer-type Complexes (pages 2419–2422)

      Peter Sponholz, Dörthe Mellmann, Christoph Cordes, Dr. Pamela G. Alsabeh, Bin Li, Dr. Yang Li, Dr. Martin Nielsen, Dr. Henrik Junge, Prof. Pierre Dixneuf and Prof. Matthias Beller

      Article first published online: 1 AUG 2014 | DOI: 10.1002/cssc.201402426

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      Pinch out H2: Hydrogen is produced through aqueous phase dehydrogenation of bioethanol using ruthenium pincer-type complexes as catalysts. The complexes are highly active in a broad range of water concentrations and at mild reaction temperatures, demonstrating that hydrogen production from fermented bioethanol is feasible. A long-term reaction reaches excellent catalytic productivities with 80 000 turnover numbers.

    3. Vitamin B1-Catalyzed Acetoin Formation from Acetaldehyde: A Key Step for Upgrading Bioethanol to Bulk C4 Chemicals (pages 2423–2426)

      Dr. Ting Lu, Dr. Xiukai Li, Dr. Liuqun Gu and Dr. Yugen Zhang

      Article first published online: 18 JUL 2014 | DOI: 10.1002/cssc.201402396

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      Take your vitamins: A highly selective process for the conversion of bioethanol to C4 bulk chemicals, such as 2,3-butanediol and butene, is reported. The process involves the use of a vitamin B1 (thiamine)-derived N-heterocyclic carbene (NHC)-catalyzed acetoin condensation as the key step to assemble two C2 acetaldehydes into a C4 product. The environmentally benign and cheap natural catalyst vitamin B1 demonstrates high selectivity, high efficiency, and high tolerance toward ethanol and water impurities in the acetoin reaction.

    4. Visible-Light-Enhanced Electrocatalysis and Bioelectrocatalysis Coupled in a Miniature Glucose/Air Biofuel Cell (pages 2427–2431)

      Dr. Lingling Zhang, Dr. Zhikun Xu, Dr. Baohua Lou, Dr. Lei Han, Dr. Xiaowei Zhang and Prof. Shaojun Dong

      Article first published online: 24 JUN 2014 | DOI: 10.1002/cssc.201402325

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      BFCs forever: A miniature glucose/air biofuel cell (BFC) converts both chemical and light energy into electricity. The power output of the BFC exhibits an enhancement by a factor of ca. 22 upon visible-light illumination, with excellent stability and a fast photoresponse. Fabricating a BFC in this manner provides an energy conversion model that offers high efficiency at low cost, paving an avenue for practical solar energy conversion on a large scale.

    5. Energy and Chemicals from the Selective Electrooxidation of Renewable Diols by Organometallic Fuel Cells (pages 2432–2435)

      Marco Bellini, Dr. Manuela Bevilacqua, Dr. Jonathan Filippi, Dr. Alessandro Lavacchi, Dr. Andrea Marchionni, Dr. Hamish A. Miller, Dr. Werner Oberhauser, Dr. Francesco Vizza, Samuel P. Annen and Prof. Dr.  H. Grützmacher

      Article first published online: 31 JUL 2014 | DOI: 10.1002/cssc.201402316

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      Cellmates: Organometallic fuel cells (OMFC) catalyze the selective electrooxidation of renewable diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,4-butanediol, simultaneously providing high power densities and chemicals of industrial importance. [Rh(OTf)(trop2NH)(PPh3)], an organometallic complex, is employed as molecular active site in an anode of an OMFC and its electrochemical performance is evaluated.

    6. The Mechanisms of Oxygen Reduction and Evolution Reactions in Nonaqueous Lithium–Oxygen Batteries (pages 2436–2440)

      Dr. Ruiguo Cao, Dr. Eric D. Walter, Dr. Wu Xu, Dr. Eduard N. Nasybulin, Dr. Priyanka Bhattacharya, Dr. Mark E. Bowden, Mark H. Engelhard and Dr. Ji-Guang Zhang

      Article first published online: 8 JUL 2014 | DOI: 10.1002/cssc.201402315

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      Chasing radicals: The fundamental understanding of the mechanisms for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in nonaqueous Li-O2 batteries is essential for the further development of these batteries. Here, we systematically investigated the ORR/OER reaction mechanisms in nonaqueous Li-O2 batteries using electron paramagnetic resonance spectroscopy.

    7. Regioselective Air Oxidation of Sulfides to O,S-Acetals in a Bubble Column (pages 2441–2444)

      Fabian Brockmeyer and Prof. Dr. Jürgen Martens

      Article first published online: 30 JUL 2014 | DOI: 10.1002/cssc.201402310

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      Unusual bubbles: A bubble column, which is an uncommon apparatus on laboratory scale, is used in the selective oxidation of α-alkylthio-imines to O,S-acetals with the aid of atmospheric oxygen. Activated carbon is necessary as catalyst only. On that account, the use of metals or photosensitizer is abdicable. By performing the reaction in a bubble column the yield could be increased while the reaction time is reduced in comparison to common laboratory techniques.

    8. Chemocatalytic Upgrading of Tailored Fermentation Products Toward Biodiesel (pages 2445–2448)

      Dr. Sanil Sreekumar, Zachary C. Baer, Dr. Elad Gross, Dr. Sasisanker Padmanaban, Konstantinos Goulas, Gorkem Gunbas, Dr. Selim Alayoglu, Prof. Harvey W. Blanch, Prof. Douglas S. Clark and Prof. F. Dean Toste

      Article first published online: 15 JUL 2014 | DOI: 10.1002/cssc.201402244

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      Free upgrade: By tailoring both biological and chemocatalytic processes, the production of sustainable biodiesel from lignocellulosic sugar is maximized. Hydrotalcite-supported copper(II) and palladium(0) catalysts are combined with a modification of the process of fermentation of acetone–butanol–ethanol to isopropanol–butanol–ethanol, producing higher concentrations of diesel-range components in the alkylation reaction.

    9. Post-Synthetic Modification of Hangman Porphyrins Synthesized on the Gram Scale (pages 2449–2452)

      Daniel J. Graham, Dr. Shao-Liang Zheng and Dr. Daniel G. Nocera

      Article first published online: 27 JUN 2014 | DOI: 10.1002/cssc.201402242

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      Not a noose-ance anymore! Hangman porphyrins can now be synthesized on the gram scale from inexpensive starting materials. Using these hangman porphyrins as ligands for transition metals allows control of the nature of the secondary coordination sphere. Post-synthetic modification is used to introduce a wide range of hanging groups with tailored characteristics that facilitate proton delivery during electrocatalysis.

    10. Photocatalytic Water Oxidation by Molecular Assemblies Based on Cobalt Catalysts (pages 2453–2456)

      Xu Zhou, Dr. Fei Li, Hua Li, Biaobiao Zhang, Fengshou Yu and Prof. Licheng Sun

      Article first published online: 8 AUG 2014 | DOI: 10.1002/cssc.201402195

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      Cycling is good for you: Ruthenium chromophore–cobalt catalyst assemblies in linear and macrocyclic configurations are prepared by a simple method. In buffer solution (NaHCO3, pH 7) the macrocyclic assembly exhibits a remarkably enhanced activity towards photocatalytic water oxidation compared to linear and multicomponent systems: the Ru–Co metallocycle′s activity is one order of magnitude higher than that of a multicomponent system and exceeds that of a linear assembly by a factor of five.

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      Paving the Way for Using Li2S Batteries (pages 2457–2460)

      Dr. Rui Xu, Dr. Xiaofeng Zhang, Cun Yu, Dr. Yang Ren, Prof. James C. M. Li and Dr. Ilias Belharouak

      Article first published online: 8 JUL 2014 | DOI: 10.1002/cssc.201402177

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      Electrolyte my fire: Lithium disulfide (Li2S) cathode has gained great attention in Li–S battery research recently. However, Li2S does not provide the full extent of its capacity in the cell because it is barely active due to its highly insulating character. The use of a non-conventional electrolyte in a Li2S battery is described. This electrolyte significantly improved the electrochemical activity of Li2S by delivering high capacity and good cycling.

    12. Coupled Near- and Far-Field Scattering in Silver Nanoparticles for High-Efficiency, Stable, and Thin Plasmonic Dye-Sensitized Solar Cells (pages 2461–2468)

      Gede Widia Pratama Adhyaksa, Se-Woong Baek, Dr. Ga In Lee, Dong Ki Lee, Prof. Jung-Yong Lee and Prof. Jeung Ku Kang

      Article first published online: 11 JUN 2014 | DOI: 10.1002/cssc.201402146

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      Near, far, wherever you are: Synergy through coupling of near- and far-field scattering of size-controlled silver nanoparticles (AgNPs) improves the efficiency of thin dye-sensitized solar cell (DSSCs). Far-field scattering is critical in the electrolyte while near-field scattering is efficient in the photo-electrode. The size of the AgNPs affects both the photon-to-current efficiency in the electrolyte and in the photo-electrode. Use of a nonvolatile ionic liquid prevents corrosion of the nanoparticles. In addition, the DSSCs show excellent stability.

    13. Metal–Organic Frameworks at Interfaces in Dye-Sensitized Solar Cells (pages 2469–2472)

      Dr. Yafeng Li, Caiyun Chen, Xun Sun, Jie Dou and Prof. Mingdeng Wei

      Article first published online: 2 JUL 2014 | DOI: 10.1002/cssc.201402143

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      Timing is everything: ZIF-8, a widely studied metal–organic framework material, is used to modify titania/dye/electrolyte interfaces in dye-sensitized solar cells. The use of a facile post-treatment strategy, instead of a pretreatment one, solves the problem of severely decreased short-circuit photocurrents. The tight adsorption of dyes onto the TiO2 surface is a key point for efficient photocurrent output, and leads to an improved performance.

    14. Efficient Conversion of Polyamides to ω-Hydroxyalkanoic Acids: A New Method for Chemical Recycling of Waste Plastics (pages 2473–2477)

      Dr. Akio Kamimura, Kosuke Ikeda, Shuzo Suzuki, Kazunari Kato, Yugo Akinari, Dr. Tsunemi Sugimoto, Dr. Kohichi Kashiwagi, Dr. Kouji Kaiso, Hiroshi Matsumoto and Dr. Makoto Yoshimoto

      Article first published online: 8 JUL 2014 | DOI: 10.1002/cssc.201402125

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      Pay for it with plastic: Polyamides were directly converted to hydroxylcarboxylic esters or diols, chemicals that are more highly valued than simple monomeric materials, by treatment with supercritical MeOH in the presence of glycolic acid. Simple depolymerization along with efficient conversion of the amino group to hydroxyl group provides these compounds in high yields. This strategy may provide a new and economical solution for chemical recycling of waste plastics.

    15. Biological Production of Muconic Acid via a Prokaryotic 2,3-Dihydroxybenzoic Acid Decarboxylase (pages 2478–2481)

      Xinxiao Sun, Yuheng Lin, Qipeng Yuan and Yajun Yan

      Article first published online: 17 JUL 2014 | DOI: 10.1002/cssc.201402092

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      Germ of an idea: Muconic acid is an important bulk chemical which is currently manufactured from unsustainable petroleum feedstocks. An artificial pathway is designed to enable the biosynthesis of muconic acid from renewable carbon sources. This pathway employs 2,3-dihydroxybenzoic acid (2,3-DHBA) decarboxylase from Klebsiella pneumoniae.

  9. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Review
    8. Highlight
    9. Communications
    10. Full Papers
    1. Selective Conversion of Cellulose in Corncob Residue to Levulinic Acid in an Aluminum Trichloride–Sodium Chloride System (pages 2482–2488)

      Dr. Jianmei Li, Zhicheng Jiang, Libin Hu and Prof. Dr. Changwei Hu

      Article first published online: 15 JUL 2014 | DOI: 10.1002/cssc.201402384

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      With a pinch of salt: Levulinic acid is obtained in high yield and selectivity directly from the selective conversion of cellulose in corncob residue in an AlCl3–NaCl system. NaCl shows a notable performance, being involved in the enhancement of yield and selectivity to levulinic acid, promoting the separation of levulinic acid from aqueous solution, and solubilizing cellulose allowing to replace expensive ionic-liquid solvents.

    2. Unconventional Pore and Defect Generation in Molybdenum Disulfide: Application in High-Rate Lithium-Ion Batteries and the Hydrogen Evolution Reaction (pages 2489–2495)

      Kan Zhang, Hwan-Jin Kim, Jeong-Taik Lee, Gee-Woo Chang, Xinjian Shi, Wanjung Kim, Ming Ma, Ki-jeong Kong, Jae-Man Choi, Min-Sang Song and Prof. Jong Hyeok Park

      Article first published online: 25 JUL 2014 | DOI: 10.1002/cssc.201402372

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      Improved through imperfection: Electrochemically active 3D MoS2 nanomesh/reduced graphene oxide (RGO) foam is obtained based on unconventional defect and porosity generation. The foam has a high rate performance and excellent stable cyclability for use in lithium-ion batteries (LIBs) and superior activity for the hydrogen evolution reaction (HER).

    3. Carbon Nanofibers Modified with Heteroatoms as Metal-Free Catalysts for the Oxidative Dehydrogenation of Propane (pages 2496–2504)

      Yanila Marco, Dr. Laura Roldán, Dr. Edgar Muñoz and Dr. Enrique García-Bordejé

      Article first published online: 19 AUG 2014 | DOI: 10.1002/cssc.201402363

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      Turn on, tune in: Doping carbon nanofibers with heteroatoms (B, P, N) tunes the selectivity to the alkene in the oxidative dehydrogenation of propane. The selectivity is affected by the type of heteroatom and also by the compound used as the precursor as they lead to different deactivation of unselective oxygenated sites on carbon.

    4. Effect of Preparation Method and CuO Promotion in the Conversion of Ethanol into 1,3-Butadiene over SiO2–MgO Catalysts (pages 2505–2515)

      Carlo Angelici, Marjolein E. Z. Velthoen, Prof. Bert M. Weckhuysen and Dr. Pieter C. A. Bruijnincx

      Article first published online: 14 JUL 2014 | DOI: 10.1002/cssc.201402361

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      It′s a matter of kneading: The morphology strongly influences the activity of SiO2–MgO catalyst for ethanol-to-butadiene conversion. Of the catalysts tested, those obtained by wet-kneading give rise to the best catalytic performance and their structure can be correlated to activity. CuO-promotion furthermore leads to much improved yields for all SiO2–MgO catalysts. Based on UV/Vis characterization, isolated species and small clusters of CuO are proposed to be responsible for the increased selectivity towards butadiene.

    5. Methanol Steam Reforming Promoted by Molten Salt-Modified Platinum on Alumina Catalysts (pages 2516–2526)

      Matthias Kusche, Dr. Friederike Agel, Dr. Nollaig Ní Bhriain, Andre Kaftan, Dr. Mathias Laurin, Prof. Dr. Jörg Libuda and Prof. Dr. Peter Wasserscheid

      Article first published online: 14 AUG 2014 | DOI: 10.1002/cssc.201402357

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      Molten salts might have a new life: Platinum-on-alumina catalysts are boosted in their selectivity and activity for methanol steam reforming by a surface coating with basic and hygroscopic alkali salts. As evidenced by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies, alkali doping through the salt coating is an important factor for this enhanced performance.

    6. Design of a Metal-Promoted Oxide Catalyst for the Selective Synthesis of Butadiene from Ethanol (pages 2527–2536)

      Vitaly L. Sushkevich, Prof. Irina I. Ivanova, Vitaly V. Ordomsky and Dr. Esben Taarning

      Article first published online: 14 AUG 2014 | DOI: 10.1002/cssc.201402346

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      Losing H2: Metal-promoted oxides supported on silica are efficient catalysts for butadiene synthesis from ethanol. The metal promoters allow ethanol dehydrogenation, the metal oxide components are efficient in acetaldehyde condensation and reduction of crotonaldehyde with ethanol, whereas the silica support allows the dehydration steps. The optimized catalyst provides 74 mol % selectivity to butadiene at 88 % ethanol conversion at 593 K.

    7. Cadmium Sulfide Quantum Dots Supported on Gallium and Indium Oxide for Visible-Light-Driven Hydrogen Evolution from Water (pages 2537–2544)

      Dr. Yun-xiang Pan, Huaqiang Zhuang, Jindui Hong, Dr. Zheng Fang, Hai Liu, Prof. Bin Liu, Prof. Yizhong Huang and Prof. Rong Xu

      Article first published online: 18 JUL 2014 | DOI: 10.1002/cssc.201402334

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      Dotty about H2: CdS quantum dots (QDs) supported on Pt/Ga2O3 and Pt/In2O3 enhance the photocatalytic activity for H2 evolution under visible light significantly. The surface properties of the oxide supports play important roles for the highly efficient H2 evolution, which include (i) the anchoring of CdS QDs and Pt nanoparticles and (ii) the efficient trapping of photogenerated electrons from CdS QDs in the presence of surface defects.

    8. Free-Standing Nitrogen-doped Graphene Paper as Electrodes for High-Performance Lithium/Dissolved Polysulfide Batteries (pages 2545–2553)

      Kai Han, Dr. Jingmei Shen, Dr. Shiqiang Hao, Prof. Hongqi Ye, Prof. Christopher Wolverton, Prof. Mayfair C. Kung and Prof. Harold H. Kung

      Article first published online: 22 JUL 2014 | DOI: 10.1002/cssc.201402329

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      Get out of a bind: A binder-free N-doped graphene has been synthesized to use as electrodes for Li/dissolved polysulfides battery. The N-doped graphene was found to have a larger capacity to adsorb polysulfide, lower electrolyte resistance, and much slower growth of passivation film resistance. The cell exhibited superior electrochemical performance with high specific capacities and coulombic efficiencies.

    9. Enhanced Oxygen Separation through Robust Freeze-Cast Bilayered Dual-Phase Membranes (pages 2554–2561)

      Cyril Gaudillere, Julio Garcia-Fayos, María Balaguer and Prof. José M. Serra

      Article first published online: 28 JUL 2014 | DOI: 10.1002/cssc.201402324

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      Permeating through: Dual-phase oxygen-permeable asymmetric membranes with enhanced oxygen permeation are prepared by combining freeze-casting, screen-printing, and constraint-sintering techniques. The membranes are evaluated under oxyfuel operating conditions. This membrane exhibits a promising oxygen permeation value of 4.8 mL min−1 cm−2 at 1000 °C upon using Ar and air as the sweep and feed gases, respectively.

    10. Preventing the Dissolution of Lithium Polysulfides in Lithium–Sulfur Cells by using Nafion-coated Cathodes (pages 2562–2566)

      Soo Jung Oh, Jun Kyu Lee and Prof. Woo Young Yoon

      Article first published online: 25 JUL 2014 | DOI: 10.1002/cssc.201402318

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      My humble anode: A new system for lithium–sulfur batteries is reported. The cells comprise Nafion-coated NiCrAl/S as cathode and lithium powder as anode material. The materials hamper the dissolution of long-chain lithium polysulfides into the electrolyte, thereby improving cycling performance. Electrochemical analysis shows high initial discharge capacities, coupled to good capacity retention values after 100 cycles.

    11. Highly Crystalline Lithium Titanium Oxide Sheets Coated with Nitrogen-Doped Carbon enable High-Rate Lithium-Ion Batteries (pages 2567–2574)

      Cuiping Han, Prof. Yan-Bing He, Prof. Baohua Li, Hongfei Li, Dr. Jun Ma, Prof. Hongda Du, Dr. Xianying Qin, Prof. Quan-Hong Yang and Prof. Feiyu Kang

      Article first published online: 8 JUL 2014 | DOI: 10.1002/cssc.201402305

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      Between the sheets: Thick sheets of Li4Ti5O12 (LTO) with high crystallinity are prepared by a controlled hydrothermal reaction route. In a subsequent chemical vapor deposition (CVD) step, the surfaces of the LTO sheets are coated with a nitrogen-doped carbon layer. The uniform layer serves to preserve the sheet morphology and improves surface stability, as in addition greatly enhances the rate and cycling performance of the LTO electrode.

    12. Tethering Metal Ions to Photocatalyst Particulate Surfaces by Bifunctional Molecular Linkers for Efficient Hydrogen Evolution (pages 2575–2583)

      Dr. Weili Yu, Dr. Tayirjan Isimjan, Dr. Silvano Del Gobbo, Dr. Dalaver H. Anjum, Dr. Safwat Abdel-Azeim, Prof. Luigi Cavallo, Angel T. Garcia-Esparza, Prof. Kazunari Domen, Dr. Wei Xu and Prof. Kazuhiro Takanabe

      Article first published online: 19 AUG 2014 | DOI: 10.1002/cssc.201402297

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      A white-nickel ride: Modifying CdS surfaces with trace amounts of a non-noble, earth-abundant Ni complex led to enhancements in the rates of photocatalytic hydrogen evolution from aqueous solutions of Na2S-Na2SO3. The methodology used to link the Ni complex to the particle surface may be universally employed in the decoration of photocatalyst surfaces for improved performance.

    13. Low temperature Hydrogen Reduction of High Surface Area Anatase and Anatase/β-TiO2 for High-Charging-Rate Batteries (pages 2584–2589)

      Dr. Edgar Ventosa, Anna Tymoczko, Kunpeng Xie, Dr. Wei Xia, Prof. Martin Muhler and Prof. Wolfgang Schuhmann

      Article first published online: 8 JUL 2014 | DOI: 10.1002/cssc.201402279

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      Kill two birds with one stone: A strategy to simultaneously tackle the two main limitations of TiO2 as negative electrode material in lithium-ion batteries, namely poor electrical conductivity and low lithium-ion mobility, is achieved by low temperature (275–300 °C) hydrogen annealing of TiO2 with a high surface area or a β-phase, as oxygen vacancies enhance the former issue and the high surface area or the β-phase addresses the latter.

    14. Mesoporous Carbon-TiO2 Beads with Nanotextured Surfaces as Photoanodes in Dye-Sensitized Solar Cells (pages 2590–2596)

      Li Na Quan, Yoon Hee Jang, Yu Jin Jang, Jihyeon Kim, Prof. Wonmok Lee, Prof. Jun Hyuk Moon and Prof. Dong Ha Kim

      Article first published online: 6 AUG 2014 | DOI: 10.1002/cssc.201402277

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      Pores having a ball: A new and creative strategy for the fabrication of hierarchical mesoporous TiO2 (mTiO2) and mesoporous carbon-TiO2 (mC-TiO2) beads has been developed. Based on complementary colloid self-assembly and direct conversion of triblock copolymer P123 containing inorganic precursors, beads with highly roughened surfaces at the nanoscale have been obtained. In addition, their role as modifier of photoanodes in the efficiency enhancement in dye-sensitized solar cells has been discussed.

    15. Compositional Insights and Valorization Pathways for Carbonaceous Material Deposited During Bio-Oil Thermal Treatment (pages 2597–2608)

      Aitor Ochoa, Borja Aramburu, María Ibáñez, Dr. Beatriz Valle, Prof. Dr. Javier Bilbao, Prof. Dr. Ana G. Gayubo and Dr. Pedro Castaño

      Article first published online: 23 JUL 2014 | DOI: 10.1002/cssc.201402276

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      Differences flashed out: Carbonaceous material deposited during the thermal treatment of bio-oil (obtained in the flash pyrolysis of biomass) is an attractive solid for the biorefinery concept. Results identify the differences between the pyrolytic lignins deposited under diverse temperatures. Based on these differences, tailored valorization pathways for each lignin are proposed. In addition, specific protocols for analyzing the properties of pyrolytic lignins and solids alike are set.

    16. Toward New Fuel Cell Support Materials: A Theoretical and Experimental Study of Nitrogen-Doped Graphene (pages 2609–2620)

      Dr. Min Ho Seo, Dr. Sung Mook Choi, Eun Ja Lim, In Hye Kwon, Joon Kyo Seo, Seung Hyo Noh, Prof. Won Bae Kim and Prof. Byungchan Han

      Article first published online: 10 JUL 2014 | DOI: 10.1002/cssc.201402258

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      Design of new support materials: By applying integrated first-principles calculation and experimental measurement approaches to well-defined model systems of N-doped graphene supports, fundamental mechanisms controlling the catalytic activity and structural stability of nanoscale platinum particles used for fuel cells are unveiled. This forms the basis for innovative ideas enhancing catalytic performance through a new design of support materials.

    17. Ion Distribution in Quaternary-Ammonium-Functionalized Aromatic Polymers: Effects on the Ionic Clustering and Conductivity of Anion-Exchange Membranes (pages 2621–2630)

      E. Annika Weiber and Prof. Patric Jannasch

      Article first published online: 8 JUL 2014 | DOI: 10.1002/cssc.201402223

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      Location, location, location: The water uptake and ionic conductivity of polymers with different contents and locations of cationic groups are investigated. The synthetic strategy enables careful control of the position of precisely two, three, or four ionic groups on single aromatic rings in the polymer. The close proximity of the ionic groups promotes ionic clustering, which improves the anion-exchange membrane properties significantly.

    18. An Innovative Approach for Highly Selective Direct Conversion of CO2 into Propanol using C2H4 and H2 (pages 2631–2639)

      Stefan J. Ahlers, Dr. Ursula Bentrup, Dr. David Linke and Dr. Evgenii V. Kondratenko

      Article first published online: 10 JUL 2014 | DOI: 10.1002/cssc.201402212

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      A flowing conversion: CO2 can be continuously converted into propanol with a near 100 % selectivity through H2-assisted coupling with C2H4 over K-promoted Au/TiO2 in a single continuous-flow reactor. Thorough kinetic and mechanistic studies reveal the overall reaction scheme of products formation. The activity and selectivity strongly depend on nanoparticle size, which can be tuned by the method of Au deposition and by doping with K.

    19. Efficient Organic Sensitizers with Pyridine-N-oxide as an Anchor Group for Dye-Sensitized Solar Cells (pages 2640–2646)

      Dr. Lei Wang, Prof. Xichuan Yang, Dr. Jianghua Zhao, Dr. Fuguo Zhang, Prof. Xiuna Wang and Prof. Licheng Sun

      Article first published online: 25 JUL 2014 | DOI: 10.1002/cssc.201402208

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      Dye another day: Five organic dyes with pyridine-N-oxide as the anchor group and electron acceptor have been synthesized and applied in dye-sensitized solar cells. WL307, which has 2-ethylhexyloxy chains in the donor part and benzothiadiazole as an electron-withdrawing bridge, showed an efficiency of 6.08 % under 100 mW cm−2 light illumination. The series of dyes showed a fairly good stability during the one month test period.

    20. Porous Anionic Indium–Organic Framework with Enhanced Gas and Vapor Adsorption and Separation Ability (pages 2647–2653)

      Dr. Yuanbiao Huang, Zujin Lin, Hongru Fu, Dr. Fei Wang, Min Shen, Xusheng Wang and Prof. Dr. Rong Cao

      Article first published online: 11 JUL 2014 | DOI: 10.1002/cssc.201402206

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      Use MOFs, spur on sorption: A highly porous anionic metal–organic framework based on 4,4′,4′′-s-triazine-2,4,6-triyltribenzoate not only shows very high adsorption uptakes of C2 and C3 hydrocarbons, but also separates propane, acetylene, ethane, and ethylene highly selectively from methane at room temperature. Furthermore, the material demonstrates high separation selectivity for benzene over cyclohexane.

    21. Synthesis of Potassium-Modified Graphitic Carbon Nitride with High Photocatalytic Activity for Hydrogen Evolution (pages 2654–2658)

      Ming Wu, Dr. Jun-Min Yan, Xian-nian Tang, Dr. Ming Zhao and Dr. Qing Jiang

      Article first published online: 14 JUL 2014 | DOI: 10.1002/cssc.201402180

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      Visible superiority in hydrogen production! Potassium-modified graphitic carbon nitride (g-C3N4) nanosheets are synthesized by a facile KCl-template method using no hazardous chemicals. The resultant architecture has a high photocatalytic activity (thirteen times higher than that of pure g-C3N4) as well as good stability for hydrogen evolution under visible light irradiation.

    22. Enhancing Dye-Sensitized Solar Cell Performances by Molecular Engineering: Highly Efficient π-Extended Organic Sensitizers (pages 2659–2669)

      Dr. Roberto Grisorio, Dr. Luisa De Marco, Dr. Rita Agosta, Dr. Rosabianca Iacobellis, Dr. Roberto Giannuzzi, Dr. Michele Manca, Prof. Piero Mastrorilli, Prof. Giuseppe Gigli and Prof. Gian Paolo Suranna

      Article first published online: 23 JUL 2014 | DOI: 10.1002/cssc.201402164

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      Can I have an extension please? Two new π-extended D–A–π–A dyes are synthesized for application in dye-sensitized solar cells (DSSCs). The introduction of an ethynylene–phenylene moiety in the π-bridge leads to remarkably higher efficiency in DSSCs compared to the sensitizer with the ethynylene–thienylene spacer due to higher electron injection, inhibition of back electron-transfer as well as dark current.

    23. One-Pot Transformation of Cellobiose to Formic Acid and Levulinic Acid over Ionic-Liquid-based Polyoxometalate Hybrids (pages 2670–2677)

      Dr. Kaixin Li, Linlu Bai, Prince Nana Amaniampong, Dr. Xinli Jia, Prof. Jong-Min Lee and Prof. Yanhui Yang

      Article first published online: 8 AUG 2014 | DOI: 10.1002/cssc.201402157

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      Efficient biomass conversion by ionic liquid-based hybrids: Multifunctional ionic liquid-based polyoxometalate (IL-POM) hybrids are found to markedly promote the one-pot transformation of cellobiose into levulinic acid (LA) and formic acid (FA) and to be easily recovered and reused due to their self-separation behavior. A green and efficient synthesis of LA and FA from biomass materials is developed for the production of high-value chemicals.

    24. Recycling of Carbon Dioxide and Acetate as Lactic Acid by the Hydrogen-Producing Bacterium Thermotoga neapolitana (pages 2678–2683)

      Dr. Giuliana d'Ippolito, Dr. Laura Dipasquale and Dr. Angelo Fontana

      Article first published online: 12 AUG 2014 | DOI: 10.1002/cssc.201402155

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      Bacterial sequestration: A new pathway for the capture of carbon dioxide in the hydrogen-producing bacterium Thermotoga neapolitana is described. The cells operate as micro-bioreactors to produce lactic acid from acetate and carbon dioxide. Lactic acid is released in the medium and can be easily retrieved. The process does not affect the production of hydrogen; thus achieving carbon sequestration, production of the energy vector, and lactic acid synthesis.

    25. Laccase-Mediator System for Alcohol Oxidation to Carbonyls or Carboxylic Acids: Toward a Sustainable Synthesis of Profens (pages 2684–2689)

      Dr. Paola Galletti, Dr. Matteo Pori, Federica Funiciello, Roberto Soldati, Alberto Ballardini and Prof. Daria Giacomini

      Article first published online: 13 JUL 2014 | DOI: 10.1002/cssc.201402136

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      Enzyme exploitation: Laccase from Trametes versicolor (TvL) is used in a chemoenzymatic system with 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) in water for the environmentally friendly oxidation of primary alcohols into the corresponding carboxylic acids or aldehydes and of selected secondary alcohols to ketones.

    26. Conversion of Toluene and Water to Methylcyclohexane and Oxygen using Niobium-Doped Strontium Titanate Photoelectrodes (pages 2690–2694)

      Dr. Vit Kalousek, Dr. Peng Wang, Prof. Tsutomu Minegishi, Prof. Takashi Hisatomi, Dr. Kojiro Nakagawa, Shinji Oshima, Yoshihiro Kobori, Prof. Jun Kubota and Prof. Kazunari Domen

      Article first published online: 11 JUL 2014 | DOI: 10.1002/cssc.201402133

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      No Bias! A high Faradaic efficiency is achieved for the direct photoelectrochemical conversion of toluene and water to methylcyclohexane and oxygen using light energy alone. The photoelectrochemical system consists of a Nb:SrTiO3 photoelectrode and Pt/C electrode. This is the first demonstration of the production of methylcyclohexane from toluene and water using only light energy.

    27. Aerobic Oxidation of Alkylaromatics using a Lipophilic N-Hydroxyphthalimide: Overcoming the Industrial Limit of Catalyst Solubility (pages 2695–2703)

      Dr. Manuel Petroselli, Dr. Paola Franchi, Prof. Marco Lucarini, Dr. Carlo Punta and Dr. Lucio Melone

      Article first published online: 14 JUL 2014 | DOI: 10.1002/cssc.201402132

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      Lipophilic and selective: A new lipophilic analogous of N-hydroxyphthalimide, operating with reduced amounts of polar cosolvent, reaches the goal of promoting the aerobic oxidation of alkylaromatics to the corresponding hydroperoxides with good yields and high selectivity. The catalyst is selected on the basis of a study on the influence of substituents on the aromatic ring of N-hydroxyphthalimide.

    28. Unveiling the Chemistry behind the Green Synthesis of Metal Nanoparticles (pages 2704–2711)

      Dr. Sónia A. O. Santos, Dr. Ricardo J. B. Pinto, Prof. Dr. Sílvia M. Rocha, Dr. Paula A. A. P. Marques, Prof. Dr. Carlos Pascoal Neto, Prof. Dr. Armando J. D. Silvestre and Dr. Carmen S. R. Freire

      Article first published online: 1 AUG 2014 | DOI: 10.1002/cssc.201402126

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      How to reach GreenChemNano: We address the role of the different components of a plant extract in the reduction/stabilization of metal ions during the green synthesis of metal nanoparticles, a phenomenon that is not yet understood clearly. The behavior of the components of a Eucalyptus aqueous extract during metal-ion reduction is followed by advanced chromatographic techniques, which establishes their specific role in this process.

    29. Synthesis of Bio-Based Methacrylic Acid by Decarboxylation of Itaconic Acid and Citric Acid Catalyzed by Solid Transition-Metal Catalysts (pages 2712–2720)

      Dr. Jérôme Le Nôtre, Susan C. M. Witte-van Dijk, Dr. Jacco van Haveren, Dr. Elinor L. Scott and Prof. Johan P. M. Sanders

      Article first published online: 13 JUL 2014 | DOI: 10.1002/cssc.201402117

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      Plastic from decarboxylated lemonade: Citric acid and itaconic acid can be used as feedstocks for the production of methacrylic acid. Pd, Pt, and Ru catalysts allow the decarboxylation reaction to occur in water under relatively mild conditions. This process provides an opportunity to access bio-based poly(methyl methacrylate) materials.

    30. You have free access to this content
      Simulated Performance of Reactor Configurations for Hot-Water Pretreatment of Sugarcane Bagasse (pages 2721–2727)

      Dr. Véronique Archambault-Léger, Prof. Dr. Xiongjun Shao and Prof. Dr. Lee R. Lynd

      Article first published online: 1 AUG 2014 | DOI: 10.1002/cssc.201402087

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      Bagasse bonus: The production of fuel from lignocellulosic biomass is of interest to develop a sustainable global energy system. Sugarcane residues such as bagasse are a particularly promising feedstock, but bagasse requires pretreatment. Simulated results show that a variety of promising flow-through pretreatment configurations result in very low sugar degradation and very high fiber digestibility for subsequent microbial or enzymatic processing to biofuel.

    31. Green Acetylation of Solketal and Glycerol Formal by Heterogeneous Acid Catalysts to Form a Biodiesel Fuel Additive (pages 2728–2734)

      Dr. Jennifer R. Dodson, Thays d C. M. Leite, Nathália S. Pontes, Dr. Bianca Peres Pinto and Prof. Claudio J. A. Mota

      Article first published online: 8 JUL 2014 | DOI: 10.1002/cssc.201402070

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      One man's waste is another's treasure: Acetylated acetals from solketal and glycerol formal can act as useful additives for biodiesel from the upgrading of waste glycerol. A solventless, heterogeneously catalyzed route for the production of acetylated additives with high conversions and selectivities is described. Reaction variables are examined and explained in terms of reactivity, thermodynamics, and reaction mechanisms.

    32. SBA-15-Functionalized 3-Oxo-ABNO as Recyclable Catalyst for Aerobic Oxidation of Alcohols under Metal-Free Conditions (pages 2735–2741)

      Prof. Dr. Babak Karimi, Dr. Elham Farhangi, Prof. Hojatollah Vali and Saleh Vahdati

      Article first published online: 22 JUL 2014 | DOI: 10.1002/cssc.201402059

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      SABNO aerobics: The nitroxyl radical 3-oxo-9-azabicyclo[3.3.1]nonane-N-oxyl (3-oxo-ABNO) and its SBA-15-supported form (SABNO) are highly efficient catalysts in comparison with (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO) for the aerobic oxidation of a wide range of alcohols under metal-free conditions. Furthermore, SABNO can be conveniently recovered and subsequently reused at least seven times without affecting its catalytic efficiency.

    33. From Furfural to Fuel: Synthesis of Furoins by Organocatalysis and their Hydrodeoxygenation by Cascade Catalysis (pages 2742–2747)

      Dr. Benjamin L. Wegenhart, Dr. Linan Yang, Soon Cheong Kwan, Remi Harris, Prof. Dr. Hilkka I. Kenttämaa and Prof. Dr. Mahdi M. Abu-Omar

      Article first published online: 1 AUG 2014 | DOI: 10.1002/cssc.201402056

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      Fuelling innovation: The synthesis of furoins from furfurals in high yields is demonstrated in green and renewable solvents by N-heterocyclic carbene organocatalysts. The resulting furoins are used as fuel precursors using a Pd/C catalyst with acidic cocatalysts under mild conditions. With a Pd/Zeolite-β catalyst, 5,5′-dimethylfuroin is deoxygenated fully to dodecanes in high yields (76 %) and exceptional selectivity (96 %) for n-dodecane.

    34. Cobalt-Phosphate-Assisted Photoelectrochemical Water Oxidation by Arrays of Molybdenum-Doped Zinc Oxide Nanorods (pages 2748–2754)

      Dr. Yan-Gu Lin, Prof. Yu-Kuei Hsu, Ying-Chu Chen, Bing-Wei Lee, Prof. Jih-Shang Hwang, Dr. Li-Chyong Chen and Dr. Kuei-Hsien Chen

      Article first published online: 8 JUL 2014 | DOI: 10.1002/cssc.201402025

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      Molybdenum and Co: A photocatalytic system comprising an array of zinc oxide nanorods (NRs) doped with molybdenum is reported. The addition of cobalt phosphate (Co-Pi) further enhances the performance of the Zn1−xMoxO NR-array photoanodes. The results demonstrate that the system can serve as visible-light-sensitive photofunctional electrodes to fundamentally improve the performance of ZnO-based photoanodes for photoelectrochemical water oxidation.

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