ChemSusChem

Cover image for Vol. 5 Issue 8

August 2012

Volume 5, Issue 8

Pages 1321–1639

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Minireviews
    7. Highlight
    8. Communications
    9. Full Papers
    10. Book Review
    11. Preview
    1. Cover Picture: A General and Efficient Heterogeneous Gold-Catalyzed Hydration of Nitriles in Neat Water under Mild Atmospheric Conditions (ChemSusChem 8/2012) (page 1321)

      Dr. Yong-Mei Liu, Lin He, Miao-Miao Wang, Prof. Dr. Yong Cao, Prof. Dr. He-Yong He and Prof. Kang-Nian Fan

      Article first published online: 7 AUG 2012 | DOI: 10.1002/cssc.201290031

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      The power of gold: The hydration of nitriles is a very important transformation to access amides, one of the most significant functional groups in chemistry. In their Communication on page 1392, Yong Cao and co-workers from Fudan University describe the extraordinary performance of air-stable and recyclable solid Au-based catalysts for aqueous hydration of nitriles into amides under mild, neutral conditions in an air atmosphere. The cover image illustrates the catalytic potential of heterogeneous gold for efficient and clean hydration of nitriles to produce useful amides. This finding may have tremendous conceptual and practical implications because traditional approaches to this reaction are air-sensitive or make use ofnon-recyclable catalysts, as well as requiring organic solvents.

    2. Inside Cover: Solvent-Free Catalytic Depolymerization of Cellulose to Water-Soluble Oligosaccharides (ChemSusChem 8/2012) (page 1322)

      Niklas Meine, Dr. Roberto Rinaldi and Prof. Dr. Ferdi Schüth

      Article first published online: 7 AUG 2012 | DOI: 10.1002/cssc.201290032

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      Several key factors that govern the catalytic conversion of lignin into smaller molecules have been neglected. In the report by Rinaldi et al. on page 1449, some of the many different facets of solvents in the hydrogenolysis of diphenyl ether and, ultimately, of organosolv lignin with Raney nickel are uncovered. Most importantly, solvents are not bystanders in these reactions. The Lewis basicity of solvents very much affects the catalytic activity of Raney nickel, so in nonbasic solvents the catalyst is an extremely active catalyst for hydrogenolysis and hydrogenation, leading then to saturates. In basic solvents, however, Raney nickel is a less active, but much more selective catalyst for hydrogenolysis while preserving the aromatic products. As a result, the conversion of lignin with Raney Ni in methanol results mainly in phenols, even when performed at temperatures as high as 300 °C.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Minireviews
    7. Highlight
    8. Communications
    9. Full Papers
    10. Book Review
    11. Preview
    1. You have free access to this content
      Graphical Abstract: ChemSusChem 8/2012 (pages 1323–1335)

      Article first published online: 7 AUG 2012 | DOI: 10.1002/cssc.201290033

  3. Corrigenda

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Minireviews
    7. Highlight
    8. Communications
    9. Full Papers
    10. Book Review
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    1. You have free access to this content
      Corrigendum: A Highly Stable Anode, Carbon-Free, Catalyst Support Based on Tungsten Trioxide Nanoclusters for Proton-Exchange Membrane Fuel Cells (page 1335)

      Meiling Dou , Prof. Ming Hou, Huabing Zhang , Guangfu Li , Wangting Lu , Prof. Zidong Wei, Prof. Zhigang Shao and Prof. Baolian Yi

      Article first published online: 7 AUG 2012 | DOI: 10.1002/cssc.201200361

      This article corrects:
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  4. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Minireviews
    7. Highlight
    8. Communications
    9. Full Papers
    10. Book Review
    11. Preview
  5. Minireviews

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Minireviews
    7. Highlight
    8. Communications
    9. Full Papers
    10. Book Review
    11. Preview
    1. Platinum-Free Catalysts as Counter Electrodes in Dye-Sensitized Solar Cells (pages 1343–1357)

      Dr. Mingxing Wu and Prof. Tingli Ma

      Article first published online: 7 AUG 2012 | DOI: 10.1002/cssc.201100676

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      Sun sans Pt: This Minireview summarizes the development of platinum-free catalysts for use as counter electrodes in dye-sensitized solar cells. These catalysts comprise various metals, carbon materials, conductive polymers, and inorganic materials (transition metal carbides, nitrides, oxides, sulfides, and phosphides). The research work reported so far highlights the importance of a proper match between counter electrode catalyst and redox couple.

    2. Biomass-Based Polyols through Oxypropylation Reaction (pages 1358–1368)

      José P. S. Aniceto, Dr. Inês Portugal and Dr. Carlos M. Silva

      Article first published online: 16 JUL 2012 | DOI: 10.1002/cssc.201200032

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      Liquefying and foaming biomass waste: The oxypropylation of biomass residues, reviewed in this paper, is connected to sustainability as a biorefinery process for the synthesis of bio-based polyols, allowing partial substitution of the propylene oxide utilized by the conventional route. Such polyols exhibit similar properties to their petrochemical counterparts, making polyols an economical alternative for the production of, for example, polyurethane foams.

    3. 2-Methyltetrahydrofuran (2-MeTHF): A Biomass-Derived Solvent with Broad Application in Organic Chemistry (pages 1369–1379)

      Dr. Vittorio Pace, Dr. Pilar Hoyos, Laura Castoldi, Dr. Pablo Domínguez de María and Prof. Dr. Andrés R. Alcántara

      Article first published online: 7 AUG 2012 | DOI: 10.1002/cssc.201100780

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      The choice of a new generation: 2-Methyltetrahydrofuran (2-MeTHF) is a biomass-derived chemical that finds widespread use as alternative (co)solvent for organic reactions, both in industry and academia. 2-MeTHF has applications in organometallics, organocatalysis, biotransformations, and biomass processing. This Minireview describes current applications of 2-MeTHF, and gives a prognosis for future uses.

  6. Highlight

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Minireviews
    7. Highlight
    8. Communications
    9. Full Papers
    10. Book Review
    11. Preview
    1. Electrolysis of Water and Common Salt Solutions (pages 1381–1382)

      Pingyu Wan and X. Jin Yang

      Article first published online: 3 AUG 2012 | DOI: 10.1002/cssc.201100789

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      Pass the salt please: The electrolysis of water and aqueous solutions of common salts (NaCl, Na2CO3, and Na2SO4) with renewable electricity is potentially the best pathway to move towards a hydrogen economy and sustainable environment, but its cost-effectiveness is a major challenge. This Highlight looks at hurdles and opportunities for the large-scale production of hydrogen through electrolysis.

  7. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Minireviews
    7. Highlight
    8. Communications
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    10. Book Review
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    1. One-Pot Selective Conversion of Hemicellulose (Xylan) to Xylitol under Mild Conditions (pages 1383–1387)

      Dr. Guangshun Yi and Dr. Yugen Zhang

      Article first published online: 4 JUL 2012 | DOI: 10.1002/cssc.201200290

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      Something from nothing: Hemicellulose is selectively converted into valuable xylitol via a mild hydrogen transfer reaction, with a xylitol yield above 80 %. Instead of using high-pressure H2, isopropanol is used as hydrogen source in the presence of a Ru/C catalyst. Furthermore, a selective step-by-step conversion of hemicellulose and cellulose to different polyols in a one-pot process is described.

    2. An Integrated Approach for the Production and Isolation of 5-Hydroxymethylfurfural from Carbohydrates (pages 1388–1391)

      Svilen P. Simeonov , Jaime A. S. Coelho  and Prof. Carlos A. M. Afonso 

      Article first published online: 27 JUN 2012 | DOI: 10.1002/cssc.201200236

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      Crystal clear: An integrated, simple, efficient, reusable, and scalable methodology for the dehydration of fructose to HMF offers outstanding yields and high purities. The method uses wet tetraethylammonium bromide as reaction medium, allowing the isolation of HMF by crystallization from the reaction medium. The process is also feasible starting from other carbohydrates, such as glucose, sucrose, or inulin.

    3. A General and Efficient Heterogeneous Gold-Catalyzed Hydration of Nitriles in Neat Water under Mild Atmospheric Conditions (pages 1392–1396)

      Dr. Yong-Mei Liu, Lin He, Miao-Miao Wang, Prof. Dr. Yong Cao, Prof. Dr. He-Yong He and Prof. Kang-Nian Fan

      Article first published online: 5 JUN 2012 | DOI: 10.1002/cssc.201200203

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      Mild, efficient and general: Titania decorated with nanometer-sized gold particles acts as an efficient catalyst for the selective hydration of a wide range of chemically diverse nitriles into valuable amides in neutral water, under mild atmospheric conditions (see image). The process shows promise for a facile and direct one-pot synthesis of ε-caprolactam, an industrially important molecule, starting from 6-aminocapronitrile.

    4. Fe3O4 Anchored onto Helical Carbon Nanofibers as High-Performance Anode in Lithium-Ion Batteries (pages 1397–1400)

      Dr. Shuhua Ren, Dr. Raju Prakash, Dr. Di Wang, Dr. Venkata Sai Kiran Chakravadhanula and Dr. Maximilian Fichtner

      Article first published online: 26 JUN 2012 | DOI: 10.1002/cssc.201200139

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      Feeling the fiber: A composite material comprising Fe3O4 particles anchored onto carbon nanofibers is formed through a simple, solvent-free, two-step process. The carbon fibers self-organize in a helical manner during the pyrolysis process. Synergistic effects between the Fe3O4 and the carbon support lead to a composite with high capacity, and good cycling stability and rate capability.

    5. Rhenium-Catalyzed Transfer Hydrogenation and Deoxygenation of Biomass-Derived Polyols to Small and Useful Organics (pages 1401–1404)

      Jing Yi, Shuo Liu and Prof. Dr. Mahdi M. Abu-Omar

      Article first published online: 12 JUN 2012 | DOI: 10.1002/cssc.201200138

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      Hello MTO: Efficient and environmentally responsible conversion methods are needed to deal with excess glycerol production. The catalytic conversion of glycerol to allyl alcohol under neat conditions is catalyzed by methyltrioxorhenium (MTO). The yields of volatile products and selectivity for allyl alcohol are very good. Mechanistic studies reveal transfer hydrogenation via bifunctional catalysis.

    6. Phosphate-Functionalized Carbon Monoliths from Deep Eutectic Solvents and their Use as Monolithic Electrodes in Supercapacitors (pages 1405–1409)

      Dr. Daniel Carriazo, Dr. María C. Gutiérrez, Dr. Fernando Picó, Dr. José M. Rojo, Prof. José L. G. Fierro, Dr.  M. Luisa Ferrer and Dr. Francisco del Monte

      Article first published online: 4 JUL 2012 | DOI: 10.1002/cssc.201200136

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      Synthetic approaches based on deep eutectic solvents allow the preparation of phophate-functionalized carbon monoliths with a hierarchical structure. Both functionalization and hierarchy—combining macropores and high surface areas while preserving high monolith densities—are critical for the ahievement of remarkable energy densities in supercapacitor cells.

    7. Tandem Catalytic Acrylonitrile Cross-Metathesis and Hydrogenation of Nitriles with Ruthenium Catalysts: Direct Access to Linear α,ω-Aminoesters from Renewables (pages 1410–1414)

      Dr. Xiaowei Miao, Dr. Cédric Fischmeister, Dr. Christian Bruneau, Prof. Pierre H. Dixneuf, Dr. Jean-Luc Dubois and Dr. Jean-Luc Couturier

      Article first published online: 15 JUN 2012 | DOI: 10.1002/cssc.201200086

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      Fraternité, Solidarité & complémentarité en Catalyse: Tandem alkene cross-metathesis of acrylonitrile with long-chain alkene and hydrogenation catalysis is performed by using a single ruthenium-alkylidene catalyst precursor. The protocol allows the catalytic transformation of unsaturated fatty acids, derivatives of plant oils, into α,ω-aminoesters. A key step involves the reduction of nitrile-ester intermediates into aminoesters, the precursors of polyamides, with alkene metathesis catalyst residue under mild conditions.

    8. Iridium-EDTA as an Efficient and Readily Available Catalyst for Water Oxidation (pages 1415–1419)

      Arianna Savini, Prof. Gianfranco Bellachioma, Prof. Dr. Sandra Bolaño, Dr. Luca Rocchigiani, Dr. Cristiano Zuccaccia, Dr. Daniele Zuccaccia and Prof. Dr. Alceo Macchioni

      Article first published online: 11 JUL 2012 | DOI: 10.1002/cssc.201200067

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      It′s so easy: The readily available and highly water-soluble [IrCl(Hedta)]Na complex is an efficient and robust catalyst for water oxidation to molecular oxygen. The reaction is driven by the reduction of Ce4+ to Ce3+. Its performances (TOF=6.8 min−1 and TON>12 000) are derived by UV/Vis spectroscopic, volumetric and electrochemical measurements, and compare favorably with those of the best catalysts reported so far.

    9. Efficient Water Splitting via a Heteroepitaxial BiVO4 Photoelectrode Decorated with Co-Pi Catalysts (pages 1420–1425)

      Min Zhou, Jian Bao, Wentuan Bi, Yongquan Zeng, Rui Zhu, Minshan Tao and Prof. Yi Xie

      Article first published online: 30 JUL 2012 | DOI: 10.1002/cssc.201200287

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      Co-Pi cat: The surface of a BiVO4 film obtained by heteroepitaxy, displaying a morphology akin to interconnected walls, is decorated with Co-Pi catalysts in order to obtain an efficient water-splitting catalyst. Qualitative analysis confirms an increased efficiency of photon use, attributable to the suppression of both bulk and surface recombination owing to the combined effects of heteroepitaxy and surface modification, respectively.

  8. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Minireviews
    7. Highlight
    8. Communications
    9. Full Papers
    10. Book Review
    11. Preview
    1. Acid-Catalyzed Conversion of Xylose in Methanol-Rich Medium as Part of Biorefinery (pages 1427–1434)

      Dr. Xun Hu, Dr. Caroline Lievens and Prof. Chun-Zhu Li

      Article first published online: 22 JUN 2012 | DOI: 10.1002/cssc.201100745

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      Methanolysis makes the difference: In a methanol/water medium, the conversion of xylose to methyl xylosides protects the C1 hydroxyl group of xylose, which stabilizes xylose and suppresses the formation of sugar oligomers and polymerization reactions.

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      Spectroscopic Investigation into Oxidative Degradation of Silica-Supported Amine Sorbents for CO2 Capture (pages 1435–1442)

      Chakravartula S. Srikanth and Prof. Steven S. C. Chuang

      Article first published online: 28 JUN 2012 | DOI: 10.1002/cssc.201100662

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      Supporting the mix: Oxidative degradation of tetraethylenepentamine (TEPA) occurs through oxidation of the methylene groups in TEPA to C[DOUBLE BOND]O, forming imides/amides or amines, or to O[BOND]N[DOUBLE BOND]O, forming nitrite species (see picture). The presence of polyethylene glycol (PEG) slowed down the oxidative degradation of TEPA by hydrogen bonding.

    3. Recovery of Methane from Gas Hydrates Intercalated within Natural Sediments Using CO2 and a CO2/N2 Gas Mixture (pages 1443–1448)

      Dong-Yeun Koh, Hyery Kang, Dae-Ok Kim, Juwoon Park, Minjun Cha and Prof. Huen Lee

      Article first published online: 22 JUN 2012 | DOI: 10.1002/cssc.201100644

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      Fuel from rocks: Methane is successfully extracted, and CO2 is fixed in natural gas hydrate (NGH) sediments through a swapping mechanism, using either CO2 or a CO2/N2 gas mixture (see figure). Methane is recovered in yields that are nearly identical for pure methane hydrates, intercalated methane hydrates in clay, and NGH sediments, but recovery rates differ for the three samples.

    4. Solvent-Free Catalytic Depolymerization of Cellulose to Water-Soluble Oligosaccharides (pages 1449–1454)

      Niklas Meine, Dr. Roberto Rinaldi and Prof. Dr. Ferdi Schüth

      Article first published online: 5 APR 2012 | DOI: 10.1002/cssc.201100770

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      Reactive milling: The impregnation of cellulosic substrates with catalytic amounts of strong acid minimizes the contact problems encountered in mechanically assisted, solid-state reactions. As a result, full conversion of cellulose into water-soluble oligosaccharides is achieved by milling within 2 h. Water-soluble products are easily hydrolyzed at 130 °C in 1 h, leading to 91 % conversion of the glucan fraction of the substrate into glucose, and 96 % of the xylans into xylose (see picture).

    5. Solvent Effects on the Hydrogenolysis of Diphenyl Ether with Raney Nickel and their Implications for the Conversion of Lignin (pages 1455–1466)

      Xingyu Wang and Dr. Roberto Rinaldi

      Article first published online: 30 APR 2012 | DOI: 10.1002/cssc.201200040

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      Solvents are not bystanders: The Lewis basicity of the solvent very much affects the catalytic activity of Raney nickel, so in nonbasic solvents the catalyst is an extremely active catalyst for hydrogenolysis and hydrogenation. In basic solvents, however, Raney nickel is a less active, but much more selective catalyst for hydrogenolysis while preserving the aromatic products.

    6. Transesterification of Diethyl Oxalate with Phenol over Sol–Gel MoO3/TiO2 Catalysts (pages 1467–1473)

      Trupti Kotbagi, Duy Luan Nguyen, Prof. Dr. Christine Lancelot, Carole Lamonier, Kaew-Arpha Thavornprasert, Zhu Wenli, Dr. Mickaël Capron, Dr. Louise Jalowiecki-Duhamel, Dr. Shubhangi Umbarkar, Dr. Mohan Dongare and Prof. Dr. Franck Dumeignil

      Article first published online: 23 JUL 2012 | DOI: 10.1002/cssc.201100802

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      Catalyze this: The transesterification of diethyl oxalate with phenol to form diphenyl oxalate was carried out in the liquid phase over very efficient MoO3/TiO2 solid-acid sol–gel catalysts, with a remarkable selectivity of 100 % at a conversion of 88 %.

    7. Design of a Highly Nanodispersed Pd–MgO/SiO2 Composite Catalyst with Multifunctional Activity for CH4 Reforming (pages 1474–1481)

      Dr. Hyun You Kim, Dr. Jung-Nam Park, Prof. Graeme Henkelman and Prof. Ji Man Kim

      Article first published online: 15 JUN 2012 | DOI: 10.1002/cssc.201100798

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      Power capsule: A catalyst for the chemical conversion of greenhouse gases into hydrogen and valuable chemicals as well as a design scheme for advanced catalysts for complicated multistep reaction is described (see picture). This SiO2-encapsulated, oxide-modified metal catalyst model can be a new standard for multistep heterogeneous catalysts.

    8. A Light-Assisted Biomass Fuel Cell for Renewable Electricity Generation from Wastewater (pages 1482–1487)

      Rachel L. Chamousis and Prof. Frank E. Osterloh

      Article first published online: 23 APR 2012 | DOI: 10.1002/cssc.201200016

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      Power from waste: Treatment of municipal waste water in the US consumes $25 Billion annually and a significant fraction of US energy. Here, we describe systematic studies on TiO2/Pt and WO3/Pt photoelectrochemical cells that can oxidize organic water contaminants with artificial light or with sunlight while generating electricity at the same time.

    9. Tolerant Chalcogenide Cathodes of Membraneless Micro Fuel Cells (pages 1488–1494)

      Dr. Aldo Saul Gago, Dr. Yadira Gochi-Ponce, Dr. Yong-Jun Feng, Dr. Juan Pablo Esquivel, Dr.  Neus Sabaté, Dr. Joaquin Santander and Prof. Nicolas Alonso-Vante

      Article first published online: 27 JUN 2012 | DOI: 10.1002/cssc.201200009

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      Crossover to more power: Two novel tolerant cathodes, PtxSy and CoSe2, are developed and tested in a membraneless micro fuel cell. Working under total methanol fuel crossover, the maximum power density achieved with PtxSy is 2.1 times higher than that of Pt (see picture).

    10. Monodisperse Iron Phosphate Nanospheres: Preparation and Application in Energy Storage (pages 1495–1500)

      Junmei Zhao, Zelang Jian, Jie Ma, Fuchun Wang, Yong-Sheng Hu, Wen Chen, Liquan Chen, Huizhou Liu and Sheng Dai

      Article first published online: 12 JUN 2012 | DOI: 10.1002/cssc.201100844

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      Monodisperse iron phosphate nanospheres with a nanoporous structure are synthesized by a solvent extraction approach, using a newly developed acid–base-coupled extractant. Importantly, the extractant used in this approach can be recovered after synthesis. The synthetic procedure is simple and can be extended to synthesize other water-insoluble inorganic metal salts.

    11. Unusual Catalysts from Molasses: Synthesis, Properties and Application in Obtaining Biofuels from Algae (pages 1501–1512)

      Dr. Chiara Samorì, Dr. Cristian Torri, Prof. Daniele Fabbri, Prof. Giuseppe Falini, Dr. Cecilia Faraloni, Dr. Paola Galletti, Dr. Silvia Spera, Prof. Emilio Tagliavini and Dr. Giuseppe Torzillo

      Article first published online: 8 JUN 2012 | DOI: 10.1002/cssc.201100822

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      Burning down the sugars: We report the synthesis and characterization of new acid catalysts prepared from pyrolysis and sulfonation of sugar beet molasses, an inexpensive and viscous byproduct of the processing of sugar beets into sugar. Pyrolysis conditions for the preparation of molasses carbons are important factors determining the performance of the catalysts.

    12. Sustainable Production of Syngas from Biomass-Derived Glycerol by Steam Reforming over Highly Stable Ni/SiC (pages 1513–1522)

      Sung Min Kim and Prof. Seong Ihl Woo

      Article first published online: 29 JUN 2012 | DOI: 10.1002/cssc.201100821

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      Steam-reforming of biomass-derived glycerol is important sustainable production of fuels and chemicals. Neutral SiC promotes intrinsic nickel contributions, dehydrogenation and decarbonylation, without the deactivation caused by coke deposition and side reactions, such as dehydrationand condensation. Nonoxide SiC is less active in the water–gas-shift reaction than the oxide supports Al2O3 and CeO2. Syngas with a H2/CO ratio of approximately 2.0 can be produced over Ni/SiC.

    13. Waste-Slag Hydrocalumite and Derivatives as Heterogeneous Base Catalysts (pages 1523–1532)

      Dr. Yasutaka Kuwahara, Keita Tsuji, Dr. Tetsutaro Ohmichi, Dr. Takashi Kamegawa, Dr. Kohsuke Mori and Prof. Dr. Hiromi Yamashita

      Article first published online: 22 JUN 2012 | DOI: 10.1002/cssc.201100814

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      All your slag are belong to us: A Ca-based layered double hydroxide, hydrocalumite, and its derivatives synthesized from waste iron-making slag are useful heterogeneous base catalysts for multiple chemical reactions, including the Knoevenagel condensation, the oxidation of alkylaromatics with O2, transesterification, and CO2 fixation (see scheme). Slag-derived impurities effectively act either as active sites or catalyst promoters.

    14. A Highly Active Bagasse-Derived Solid Acid Catalyst with Properties Suitable for Production of Biodiesel (pages 1533–1541)

      Dr. Wen-Yong Lou, Qiang Guo, Wen-Jing Chen, Prof. Dr. Min-Hua Zong, Hong Wu and Prof. Dr. Thomas J. Smith

      Article first published online: 12 JUN 2012 | DOI: 10.1002/cssc.201100811

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      Value-added waste: A new sulfonated-carbon solid acid catalyst, made from renewable biomass waste bagasse, shows excellent catalytic activity and stability for the production of biodiesel. The prepared bagasse-derived catalyst is capable of efficiently converting cooking waste oils with high free fatty acid contents into biodiesel.

    15. Dialkylimidazolium Ionic Liquids Hydrolyze Cellulose Under Mild Conditions (pages 1542–1548)

      Oz M. Gazit and Prof. Alexander Katz

      Article first published online: 30 APR 2012 | DOI: 10.1002/cssc.201100803

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      Break it down: The average molecular weight of cellulose derived from different sources (filter paper, poplar, and Avicel) decreases by up to two orders of magnitude during typical mild dissolution protocols using ionic liquids (ILs). Counter-intuitively, greater IL purity results in greater cellulose depolymerization. The data suggest an acid-catalyzed cellulose hydrolysis mechanism, in which the acid is presumably synthesized via IL decomposition to generate a carbene and proton.

    16. Tuning the Acid/Metal Balance of Carbon Nanofiber-Supported Nickel Catalysts for Hydrolytic Hydrogenation of Cellulose (pages 1549–1558)

      Dr. Stijn Van de Vyver, Dr. Jan Geboers, Wouter Schutyser, Michiel Dusselier, Pierre Eloy, Dr. Emmie Dornez, Prof. Dr. Jin Won Seo, Prof. Dr. Christophe M. Courtin, Prof. Dr. Eric M. Gaigneaux, Prof. Dr. Pierre A. Jacobs and Prof. Dr. Bert F. Sels

      Article first published online: 22 JUN 2012 | DOI: 10.1002/cssc.201100782

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      Hanging in the balance: With the potential of cellulose as an alternative resource in the production of sugar alcohols, developing inexpensive non-precious catalysts is an essential requirement to reduce the overall system cost. This study evaluates the impact of preparation conditions on the acid/metal balance (see picture) and catalytic performance of a series of well-characterized carbon nanofiber supported nickel catalysts.

    17. Solvent-Free Palladium-Catalyzed Direct Arylation of Heteroaromatics with Aryl Bromides (pages 1559–1567)

      Souhila Bensaid and Dr. Henri Doucet

      Article first published online: 25 JUL 2012 | DOI: 10.1002/cssc.201100771

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      Dry, with some palladium overcast: Several palladium-catalyzed direct arylations of heteroaromatics, performed without solvent, proceeded nicely (see scheme). The yield in coupling products strongly depended on the nature of heteroaromatics and aryl bromide substituents.

    18. Diketopyrrolopyrrole–Porphyrin Conjugates as Broadly Absorbing Sensitizers for Dye-Sensitized Solar Cells (pages 1568–1577)

      Julien Warnan, Ludovic Favereau, Dr. Frédéric Meslin, Dr. Marjorie Severac, Dr. Errol Blart, Dr. Yann Pellegrin, Prof. Denis Jacquemin and Dr. Fabrice Odobel

      Article first published online: 12 JUL 2012 | DOI: 10.1002/cssc.201100764

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      Panoptic porphyrin: We present the synthesis, the electronic properties, the time dependent DFT calculations and the photovoltaic performances of new porphyrin sensitizers in a TiO2 dye-sensitized solar cell. Porphyrin dyes represent the most efficient sensitizer in DSSC, but they exhibit a weak absorbance around 550 nm. The bichromophoric system presented (see picture) is synthesized by connecting a diketopyrrolopyrrole with a push–pull porphyrin to obtain a real panchromatic dye.

    19. Synthesis of Five-Membered Cyclic Ethers by Reaction of 1,4-Diols with Dimethyl Carbonate (pages 1578–1586)

      Dr. Fabio Aricò, Prof. Pietro Tundo, Dr. Andrea Maranzana and Prof. Glauco Tonachini

      Article first published online: 22 JUN 2012 | DOI: 10.1002/cssc.201100755

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      High-yielding green syntheses of distinctive and industrially relevant five-membered cyclic ethers are achieved by reaction of 1,4-diols with dimethyl carbonate in the presence of a base (see figure). The reaction mechanism is investigated in detail, and computational studies demonstrate that the cyclization reaction was entropically driven.

    20. Ethylene Production by ODHE in Catalytically Modified Ba0.5Sr0.5Co0.8Fe0.2O3−δ Membrane Reactors (pages 1587–1596)

      Dr. M. Pilar Lobera, Sonia Escolástico, Julio Garcia-Fayos and Dr. José M. Serra

      Article first published online: 12 JUL 2012 | DOI: 10.1002/cssc.201100747

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      Thin skinned: The oxidative dehydrogenation of ethane at 850 °C on a catalytic membrane reactor based on a mixed ionic–electronic conducting membrane is studied. Ethylene selectivity and productivity is improved by using different catalytic coatings, which modify/functionalize the membrane surface: The surface of the membrane made of Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) is activated by using different porous catalytic layers based on perovskites (see figure).

    21. Temperature-/Pressure-Dependent Selective Separation of CO2 or Benzene in a Chiral Metal–Organic Framework Material (pages 1597–1601)

      Yan-Xi Tan, Yan-Ping He and Prof. Dr. Jian Zhang

      Article first published online: 15 JUN 2012 | DOI: 10.1002/cssc.201100702

      Thumbnail image of graphical abstract

      Pores for thought: A chiral microporous framework material, which has a three-fold interpenetrating diamond-type structural topology, shows a high storage capacity for CO2, a high H2 adsorptive density uptake, and temperature-/pressure-dependent selectivity for CO2 over N2 or C6H6 over C6H12.

    22. Catalytic Lignin Valorization Process for the Production of Aromatic Chemicals and Hydrogen (pages 1602–1609)

      Dr. Joseph Zakzeski, Anna L. Jongerius, Dr. Pieter C. A. Bruijnincx and Prof. Bert M. Weckhuysen

      Article first published online: 27 JUN 2012 | DOI: 10.1002/cssc.201100699

      Thumbnail image of graphical abstract

      A catalytic approach to valorize lignin by using a mixture of cheap, biorenewable ethanol and water as solvent is reported. Liquid-phase reforming of the solubilized lignin over Pt/Al2O3/co-catalyst yields monomeric aromatic oxygenates and hydrogen as a useful byproduct. The solvated lignin can also be subjected to a subsequent conversion step, for example, using an appropriate reduction catalyst and hydrogen to yield a different slate of hydrocarbons and aromatics.

    23. Coprecipitated, Copper-Based, Alumina-Stabilized Materials for Carbon Dioxide Capture by Chemical Looping Combustion (pages 1610–1618)

      Qasim Imtiaz, Dr. Agnieszka Marta Kierzkowska and Dr. Christoph Rüdiger Müller

      Article first published online: 28 JUN 2012 | DOI: 10.1002/cssc.201100694

      Thumbnail image of graphical abstract

      Tag along: Chemical looping combustion (CLC) is an emerging technology for electricity generation with inherent CO2 capture. However, the development of oxygen carriers that possess excellent cyclic redox characteristics is one of the main challenges. A fundamental understanding of the preparation–structure–performance relationships is crucial for the rational design of highly efficient synthetic oxygen-carrier materials (see picture).

    24. Supportless Silver Nanowires as Oxygen Reduction Reaction Catalysts for Hydroxide-Exchange Membrane Fuel Cells (pages 1619–1624)

      Dr. Shaun M. Alia, Kathlynne Duong, Toby Liu, Kurt Jensen and Prof. Yushan Yan

      Article first published online: 30 JUL 2012 | DOI: 10.1002/cssc.201100684

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      Down to the wire: Silver nanowires (AgNWs) are studied as oxygen reduction reaction (ORR) catalysts for hydroxide exchange membrane fuel cells (HEMFCs). The 25 nm AgNWs (see picture) have a specific ORR activity 5.3 times greater than that of 2.4 nm Ag nanoparticles (AgNPs). Therefore, AgNWs are clearly the future of HEMFC catalyst development.

    25. Efficient Fractionation of Spruce by SO2-Ethanol-Water Treatment: Closed Mass Balances for Carbohydrates and Sulfur (pages 1625–1637)

      Mikhail Iakovlev and Prof. Adriaan van Heiningen

      Article first published online: 27 JUN 2012 | DOI: 10.1002/cssc.201100600

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      Spruced up: Material balances of the SO2-ethanol-water treatment of spruce show the complete recovery of carbohydrates and sulfur, with the effective dissolution of lignin and hemicelluloses without notable dehydration or oxidation of the latter. The SO2 consumption is only 1.3–2.3 % on wood, whereas the remaining excess of SO2 is recoverable by evaporation.

  9. Book Review

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    1. Sustainability of the Sugar and Sugar–Ethanol Industries. Edited by Gillian Eggleston (page 1638)

      Dr. Y.-H. Percival Zhang

      Article first published online: 7 AUG 2012 | DOI: 10.1002/cssc.201200066

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      American Chemical Society, Washington, DC, 2010, 301 pp., hardcopy US$150—ISBN-13: 9780841225985

  10. Preview

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    2. Cover Pictures
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    4. Corrigenda
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    6. Minireviews
    7. Highlight
    8. Communications
    9. Full Papers
    10. Book Review
    11. Preview
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      Preview: ChemSusChem 9/2012 (page 1639)

      Article first published online: 7 AUG 2012 | DOI: 10.1002/cssc.201290035

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