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ChemSusChem

Cover image for Vol. 8 Issue 2

January 2015

Volume 8, Issue 2

Pages 195–406

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Viewpoint
    8. Review
    9. Minireview
    10. Communications
    11. Full Papers
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      Cover Picture: Dye-Sensitized Solar Cells with Improved Performance using Cone-Calix[4]Arene Based Dyes (ChemSusChem 2/2015) (page 195)

      Li-Lin Tan, Dr. Jun-Min Liu, Dr. Shao-Yong Li, Prof. Li-Min Xiao, Prof. Dai-Bin Kuang and Prof. Cheng-Yong Su

      Article first published online: 15 JAN 2015 | DOI: 10.1002/cssc.201403047

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      The Front Cover image shows a new and efficient cone-calix[4]arene-based dye (Calix-3) with multiple donor–π–acceptor (D–π–A) moieties used in dye-sensitized solar cells (DSSCs). The conversion efficiency of Calix-3 is above 5 % under standard global 1.5 solar conditions. This compares well with a device using rod-shaped dye M-3 with a single D–π–A chain, which has an efficiency of 3.56 %. The cone-calix[4]arene-based dyes offer higher molar extinction coefficients, longer electron lifetimes, better stability, and stronger binding ability to a TiO2 film. To the best of our knowledge, this is the first example of the use of calixarene-based sensitizer in efficient dye-sensitized solar cells. More details can be found in the Full Paper by Tan and co-workers on page 280 (DOI: 10.1002/cssc.201402401), while more information about the research group is available in the Cover Profile (DOI: 10.1002/cssc.201403048).

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      Inside Cover: Effects of Hydrophobicity of Diffusion Layer on the Electroreduction of Biomass Derivatives in Polymer Electrolyte Membrane Reactors (ChemSusChem 2/2015) (page 196)

      Wei Chen, Prof. Gaohong He, Feilong Ge, Prof. Wu Xiao, Prof. Jay Benziger and Prof. Xuemei Wu

      Article first published online: 30 MAY 2014 | DOI: 10.1002/cssc.201400097

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      The Inside Cover picture shows a polymer electrolyte membrane reactor device used for the electroreduction of biomass derivatives, in which the hydrophobicity of the diffusion layer (DL) greatly influences the hydrogenation performance of two model biomass derivatives. Hydrophobic carbon paper repels aqueous solutions, but highly volatile butanone can permeate in vapor form and achieve a high hydrogenation rate, whereas for nonvolatile maleic acid high mass-transfer resistance prevents hydrogenation. With a hydrophilic DL, aqueous solutions of maleic acid can permeate in liquid form and the performance reaches a similar level as that of butanone. More details can be found in the Full Paper by Chen et al. on page 288 (DOI: 10.1002/cssc.201402302).

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      Inside Back Cover: Synthesis of Porous Inorganic Hollow Fibers without Harmful Solvents (ChemSusChem 2/2015) (page 407)

      Sushumna Shukla, Patrick de Wit, Dr. Mieke W. J. Luiten-Olieman, Emiel J. Kappert, Prof. Dr. Arian Nijmeijer and Prof. Dr. Nieck E. Benes

      Article first published online: 15 JAN 2015 | DOI: 10.1002/cssc.201403218

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      The Inside Back Cover image shows that high surface-area-to-volume ratio inorganic hollow fibers can be fabricated by a new route that completely avoids the use of harmful solvents. The approach is based on bio-ionic gelation of an aqueous mixture of inorganic particles and sodium alginate during dry-wet spinning. The route inherently avoids the manifestation of the so-called macro voids that are associated with solvent-based synthesis routes and allows the facile incorporation of additional metal oxides in the inorganic hollow fibers. More details are available in the Communication by Shukla et al. on page 251 (DOI: 10.1002/cssc.201402483).

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      Back Cover: Proton Conductivity of Naphthalene Sulfonate Formaldehyde Resin-Doped Mesoporous Niobium and Tantalum Oxide Composites (ChemSusChem 2/2015) (page 408)

      Jonathan P. Turley, Frederik Romer, Dr. Michel L. Trudeau, Prof. Marcos L. Dias, Prof. Mark E. Smith, Dr. John V. Hanna and Prof. David M. Antonelli

      Article first published online: 8 JAN 2015 | DOI: 10.1002/cssc.201403206

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      The Back Cover image shows the movement of protons along an enhanced proton-conducting pathway fabricated inside a mesoporous transition-metal oxide impregnated with naphthalene sulfonate formaldehyde resin. Ambient moisture and the sulfonate groups of the 4–6-unit oligomers bind to the Lewis acidic walls of the mesostructure, creating a channel for enhanced proton conduction at the interface. As protons enter the pores, they hop along the proximal oxygen sites, giving rise to proton conductivity values surpassing those of the Nafion standard used in the study. More details can be found in the Full Paper by Turley et al. on page 301 (DOI: 10.1002/cssc.201402546).

  2. Cover Profile

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Viewpoint
    8. Review
    9. Minireview
    10. Communications
    11. Full Papers
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      Performance Improvement for Dye-sensitized Solar Cells with Cone-calix[4]arene Based Dyes (page 197)

      Li-Lin Tan, Dr. Jun-Min Liu, Dr. Shao-Yong Li, Prof. Li-Min Xiao, Prof. Dai-Bin Kuang and Prof. Cheng-Yong Su

      Article first published online: 8 JAN 2015 | DOI: 10.1002/cssc.201403048

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      “The calix[4]arene dye flower itself is a beautiful, positive, and energetic plant.” This and more about the story behind the research that inspired the cover image can be found on page 280 (10.1002/cssc.201403048). View the Front Cover on page 195 (10.1002/cssc.201403047).

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Viewpoint
    8. Review
    9. Minireview
    10. Communications
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      Graphical Abstract: ChemSusChem 2/2015 (pages 198–205)

      Article first published online: 15 JAN 2015 | DOI: 10.1002/cssc.201590002

  4. Masthead

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
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    8. Review
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    10. Communications
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      Masthead: ChemSusChem 2/2015 (pages 206–207)

      Article first published online: 15 JAN 2015 | DOI: 10.1002/cssc.201590003

  5. News

    1. Top of page
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    3. Cover Profile
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    5. Masthead
    6. News
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      Spotlights on our sister journals: ChemSusChem 2/2015 (pages 208–211)

      Article first published online: 15 JAN 2015 | DOI: 10.1002/cssc.201580213

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  6. Viewpoint

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      Across the Board: Gabriele Centi (pages 212–216)

      Prof. Gabriele Centi

      Article first published online: 7 JAN 2015 | DOI: 10.1002/cssc.201403355

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      The complete picture: Gabriele Centi, one of the co-Chairpersons of our Editorial Board, analyses a recent Science paper by Bao and co-workers on non-oxidative conversion of methane to ethylene and aromatics. He discusses the exploitability of the approach from a technical, economic, and sustainability perspective, and briefly comments on the role of shale gas in future chemical production scenarios.

  7. Review

    1. Top of page
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      Chitosan as a Sustainable Organocatalyst: A Concise Overview (pages 217–244)

      Prof. Abdelkrim El Kadib

      Article first published online: 2 DEC 2014 | DOI: 10.1002/cssc.201402718

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      Go natural! Amino groups on the chitosan backbone form the basis of the extensive use of chitosan derivatives as organocatalysts. A concise overview of the use of chitosan derivatives in a various reactions are given for the advancement of sustainable chemistry.

  8. Minireview

    1. Top of page
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      Diazo Compounds in Continuous-Flow Technology (pages 245–250)

      Simon T. R. Müller and Prof. Dr. Thomas Wirth

      Article first published online: 8 DEC 2014 | DOI: 10.1002/cssc.201402874

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      Not off like a bomb! Diazo compounds are highly versatile building blocks in synthesis for the selective assembly of structurally complex molecules. Their safe in situ formation and subsequent handling in microstructured devices is discussed along with advances on handling diazomethane and ethyl diazoacetate.

  9. Communications

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Viewpoint
    8. Review
    9. Minireview
    10. Communications
    11. Full Papers
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      Synthesis of Porous Inorganic Hollow Fibers without Harmful Solvents (pages 251–254)

      Sushumna Shukla, Patrick de Wit, Dr. Mieke W. J. Luiten-Olieman, Emiel J. Kappert, Prof. Dr. Arian Nijmeijer and Prof. Dr. Nieck E. Benes

      Article first published online: 25 SEP 2014 | DOI: 10.1002/cssc.201402483

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      Fibers are good for you: A method that avoids harmful solvents (using water instead) is presented for the fabrication of porous inorganic hollow fibers with high surface-area-to-volume ratio. The method is based bio-ionic gelation of an aqueous particle loaded sodium alginate solution during wet spinning, enables fabrication of various inorganic fibers, including metals and ceramics, and completely avoids the use of malignant organic solvents and additives associated with the currently used fiber fabrication methods.

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      Enhancing the Stability of Porphyrin Dye-Sensitized Solar Cells by Manipulation of Electrolyte Additives (pages 255–259)

      Genevieve P. S. Lau, Dr. Hoi Nok Tsao, Dr. Chenyi Yi, Dr. Shaik M. Zakeeruddin, Prof. Michael Grätzel and Prof. Paul J. Dyson

      Article first published online: 8 DEC 2014 | DOI: 10.1002/cssc.201403225

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      The secret to long life: Porphyrin photosensitizers have enabled dye-sensitized solar cells to achieve impressive power conversion efficiencies in recent years. We investigate the long-term stability of such devices under real-world conditions, and show that certain electrolyte additives are vital for long-lived devices.

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      Preparation of Pd–Co-Based Nanocatalysts and Their Superior Applications in Formic Acid Decomposition and Methanol Oxidation (pages 260–263)

      Dr. Yu-ling Qin, Ya-cheng Liu, Fei Liang and Prof. Li-min Wang

      Article first published online: 11 DEC 2014 | DOI: 10.1002/cssc.201402926

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      Twin alloy—twin performance: A simple method is employed to prepare Pd–Co-based nanoparticles that exhibit high catalytic performance toward formic acid decomposition and methanol oxidation. The Pd 3d binding energy decreases owing to the presence of Co, which gives rise to the improved catalytic activity and selectivity toward FA dehydrogenation at room temperature and electrocatalytic performance in methanol oxidation.

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      Electrolytes Based on TEMPO–Co Tandem Redox Systems Outperform Single Redox Systems in Dye-sensitized Solar Cells (pages 264–268)

      Dr. Jiayan Cong, Dr. Yan Hao, Dr. Gerrit Boschloo and Prof. Lars Kloo

      Article first published online: 10 DEC 2014 | DOI: 10.1002/cssc.201402780

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      New Co-worker: A new TEMPO–Co tandem redox system with TEMPO and Co(bpy)32+/3+ was investigated in dye-sensitized solar cells (DSSCs). A large open-circuit voltage (VOC) increase was observed for the new tandem redox system, and the conversion efficiency was observed to increase from 7.1 % with the single Co(bpy)32+/3+ redox system to 8.4 % for DSSCs containing the TEMPO–Co tandem redox system.

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      Catalytic Dehydration of Carbohydrates Suspended in Organic Solvents Promoted by AlCl3/SiO2 Coated with Choline Chloride (pages 269–274)

      Jie Yang, Karine De Oliveira Vigier, Yanlong Gu and François Jérôme

      Article first published online: 17 NOV 2014 | DOI: 10.1002/cssc.201402761

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      Nice coat! Coating SiO2/AlCl3 with choline chloride is an efficient way to facilitate a better contact between a solid catalyst and carbohydrates suspended in a low boiling point organic solvent. Under optimized conditions, the coating of SiO2/AlCl3 with choline chloride resulted in an improvement of the initial production rate of 5-hydroxymethylfurfural by a factor of 12.

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      The Effect of Alkaline Pretreatment Methods on Cellulose Structure and Accessibility (pages 275–279)

      Dr. Garima Bali, Xianzhi Meng, Jacob I. Deneff, Qining Sun and Prof. Arthur J. Ragauskas

      Article first published online: 24 NOV 2014 | DOI: 10.1002/cssc.201402752

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      Back to basics: Biomass recalcitrance is the biggest obstacle in the development of large-scale second-generation use of cellulosic resources. The effects of different alkaline pretreatments on cellulose structural features and accessibility are compared and correlated with the enzymatic hydrolysis of Populus, revealing important cellulose structural features and parameters relevant to biomass recalcitrance.

  10. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Masthead
    6. News
    7. Viewpoint
    8. Review
    9. Minireview
    10. Communications
    11. Full Papers
    1. You have free access to this content
      Dye-Sensitized Solar Cells with Improved Performance using Cone-Calix[4]Arene Based Dyes (pages 280–287)

      Li-Lin Tan, Dr. Jun-Min Liu, Dr. Shao-Yong Li, Prof. Li-Min Xiao, Prof. Dai-Bin Kuang and Prof. Cheng-Yong Su

      Article first published online: 2 SEP 2014 | DOI: 10.1002/cssc.201402401

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      Sunny Cali: Novel and efficient cone-calix[4]arene-based dyes (Calix-1, Calix-2, and Calix-3) with multiple donor–π–acceptor (D–π–A) moieties are prepared and tested for use in dye-sensitized solar cells (DSSCs). The conversion efficiency of one of the dyes is above 5 %, compared to 3.56 % for a device using rod-shaped dye M-3 with a single D–π–A chain. The cone-calix[4]arene-based dyes offer higher molar extinction coefficients, longer electron lifetimes, and better thermostability.

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      Effects of Hydrophobicity of Diffusion Layer on the Electroreduction of Biomass Derivatives in Polymer Electrolyte Membrane Reactors (pages 288–300)

      Wei Chen, Prof. Gaohong He, Feilong Ge, Prof. Wu Xiao, Prof. Jay Benziger and Prof. Xuemei Wu

      Article first published online: 15 OCT 2014 | DOI: 10.1002/cssc.201402302

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      How volatile? The hydrophobicity of the diffusion layer (DL) is designed based on the volatility of aqueous solutions of hydrogenation reactants in polymer electrolyte membrane reactors. Volatile butanone permeates a hydrophobic DL in vapor form, whereas great mass transfer resistance prevents nonvolatile maleic acid from hydrogenation. Aqueous solutions can permeate a hydrophilic DL in liquid form and favor hydrogenation.

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      Proton Conductivity of Naphthalene Sulfonate Formaldehyde Resin-Doped Mesoporous Niobium and Tantalum Oxide Composites (pages 301–309)

      Jonathan P. Turley, Frederik Romer, Dr. Michel L. Trudeau, Prof. Marcos L. Dias, Prof. Mark E. Smith, Dr. John V. Hanna and Prof. David M. Antonelli

      Article first published online: 10 SEP 2014 | DOI: 10.1002/cssc.201402546

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      Use your membrane: A series of mesoporous Nb and Ta oxide polymer composites of naphthalene sulfonic acid formaldehyde resin is synthesized and characterized. The effect on proton conductivity of changing pore size and metal in the mesostructure of the polymer composite is studied. All composites exhibit conductivities that surpass that of the Nafion standard and may have promising applications in proton-exchange membrane fuel cells.

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      Ferrocene and Cobaltocene Derivatives for Non-Aqueous Redox Flow Batteries (pages 310–314)

      Byunghyun Hwang, Dr. Min-Sik Park and Prof. Ketack Kim

      Article first published online: 26 NOV 2014 | DOI: 10.1002/cssc.201403021

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      Back on the metallo-scene! Metallocenes are investigated as new redox materials in non-aqueous redox flow batteries. Several pairs of ferrocene and cobaltocene derivatives are studied. Modification with functional groups and integration of transition-metal ions can change the electrochemical properties of the redox materials, improving current density and discharge potential.

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      Guaiacol Hydrodeoxygenation Mechanism on Pt(111): Insights from Density Functional Theory and Linear Free Energy Relations (pages 315–322)

      Dr. Kyungtae Lee, Geun Ho Gu, Dr. Charles A. Mullen, Prof. Akwasi A. Boateng and Prof. Dionisios G. Vlachos

      Article first published online: 2 DEC 2014 | DOI: 10.1002/cssc.201402940

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      The how, the where, and the guaiacol: Density functional theory is used to study the adsorption of guaiacol and its initial hydrodeoxygenation reactions on Pt(111). Catechol is mainly produced via dehydrogenation of the methoxy functional group followed by the CHx(x<3) removal of the functional group and hydrogenation of the ring carbon. Dehydroxylation and demethoxylation are slow, implying that phenol is likely produced through paths other than direct scissions of guaiacol or catechol.

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      Photocatalytic Acceptorless Alkane Dehydrogenation: Scope, Mechanism, and Conquering Deactivation with Carbon Dioxide (pages 323–330)

      Dr. Abhishek Dutta Chowdhury, Dr. Jennifer Julis, Dr. Kathleen Grabow, Dr. Bernd Hannebauer, Dr. Ursula Bentrup, Martin Adam, Prof. Dr. Robert Franke, Dr. Ralf Jackstell and Prof. Dr. Matthias Beller

      Article first published online: 24 OCT 2014 | DOI: 10.1002/cssc.201402850

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      CO2 catalysis: A CO2-influenced, improved dehydrogenation protocol is described using trans-Rh(PMe3)2(CO)Cl as a catalyst. Alkanes and liquid organic hydrogen carriers are used as substrates under benign homogeneous reaction conditions. High catalyst turnover numbers as well as high yields are obtained because of the prevention of catalyst deactivation.

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      Enhanced Fill Factor of Tandem Organic Solar Cells Incorporating a Diketopyrrolopyrrole-Based Low-Bandgap Polymer and Optimized Interlayer (pages 331–336)

      Prof. Dong Hwan Wang, Dr. Aung Ko Ko Kyaw and Prof. Jong Hyeok Park

      Article first published online: 17 NOV 2014 | DOI: 10.1002/cssc.201402833

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      Advanced tandem organic solar cells: Tandem solar cells based on wide- and narrow-bandgap materials are prepared using an optimized interlayer and a simple process without thermal treatment. The layer consisting of ZnO nanoparticles (NPs) exhibits stable operation when the NPs are dispersed in 2-methoxyethanol and the neutral poly(3,4-ethylenedioxythiophene):polystyrene sulfonate is used as a second interlayer. The combination of these factors results in an enhanced fill factor and reproducible results from the tandem cells.

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      Bimolecular Crystals with an Intercalated Structure Improve Poly(p-phenylenevinylene)-Based Organic Photovoltaic Cells (pages 337–344)

      Kyung-Geun Lim, Jun-Mo Park, Dr. Hannah Mangold, Dr. Frédéric Laquai, Prof. Tae-Lim Choi and Prof. Tae-Woo Lee

      Article first published online: 27 NOV 2014 | DOI: 10.1002/cssc.201402813

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      Pretty Polly: Poly(2,5-dioctyloxy-p-phenylene vinylene-alt-2′,5′-thienylene vinylene) (PPVTV) is synthesized and applied to organic photovoltaic devices. We demonstrate a correlation between well-ordered bimolecular crystals of PPVTV:phenyl-C61-butyric acid methyl ester (PCBM) and an improved hole mobility of PPVTV:PCBM blends compared to pristine PPVTV films.

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      Bio-Based Nitriles from the Heterogeneously Catalyzed Oxidative Decarboxylation of Amino Acids (pages 345–352)

      Laurens Claes, Roman Matthessen, Dr. Ine Rombouts, Ivo Stassen, Trees De Baerdemaeker, Prof. Diederik Depla, Prof. Jan A. Delcour, Dr. Bert Lagrain and Prof. Dirk E. De Vos

      Article first published online: 3 DEC 2014 | DOI: 10.1002/cssc.201402801

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      Going the extra nitrile: A catalytic system that consists of a tungstate-exchanged layered double hydroxide and a bromide salt is developed for the oxidative decarboxylation of amino acids under mild conditions using H2O2 as a green oxidant. Several functional groups are tolerated, and the nitrile selectivity is often 99 %. This strategy offers opportunities for protein-rich biomass valorization.

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      Synergistic Effects of Mixing Sulfone and Ionic Liquid as Safe Electrolytes for Lithium Sulfur Batteries (pages 353–360)

      Dr. Chen Liao, Dr. Bingkun Guo, Dr. Xiao-Guang Sun and Dr. Sheng Dai

      Article first published online: 26 NOV 2014 | DOI: 10.1002/cssc.201402800

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      Optimum composition: Mixtures of an ionic liquid and sulfone show distinctly different physicochemical properties from either of the pure components, including thermal properties and crystallization behavior. Lithium sulfur batteries that are assembled from lithium and a mesoporous carbon composite have a good reversible capacity and excellent cycling stability.

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      Titanium Oxynitride Interlayer to Influence Oxygen Reduction Reaction Activity and Corrosion Stability of Pt and Pt–Ni Alloy (pages 361–376)

      XueHai Tan, Dr. Liya Wang, Dr. Beniamin Zahiri, Dr. Alireza Kohandehghan, Dr. Dimitre Karpuzov, Dr. Elmira Memarzadeh Lotfabad, Dr. Zhi Li, Prof. Michael H. Eikerling and Prof. David Mitlin

      Article first published online: 2 DEC 2014 | DOI: 10.1002/cssc.201402704

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      Support system: The efficacy of a new conductive support that comprises of a sub-nanometer titanium oxynitride film coated onto an array of carbon nanotubes through atomic layer deposition is described. The oxynitride has a positive impact on the electronic structure for pure platinum and changes the platinum particle size and spatial distribution.

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      On the Chemistry of Ethanol on Basic Oxides: Revising Mechanisms and Intermediates in the Lebedev and Guerbet reactions (pages 377–388)

      Alessandro Chieregato, Juliana Velasquez Ochoa, Claudia Bandinelli, Prof. Giuseppe Fornasari, Prof. Fabrizio Cavani and Dr. Massimo Mella

      Article first published online: 10 DEC 2014 | DOI: 10.1002/cssc.201402632

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      Lebedev and Guerbet: what's the difference? The multifaceted approach used to study the mechanism of the Lebedev and Guerbet reactions indicates that the two processes share the same anionic intermediate but evolve along different reaction pathways, which avoid the thermodynamically hampered aldolic route.

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      Enhanced Performance of Bioelectrochemical Hydrogen Production using a pH Control Strategy (pages 389–397)

      Yolanda Ruiz, Dr. Juan A. Baeza and Dr. Albert Guisasola

      Article first published online: 2 DEC 2014 | DOI: 10.1002/cssc.201403083

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      Bioelectrochemical hydrogen production with controlled pH: The control of the pH value in two-chamber microbial electrolysis cells allows us to offset potential losses caused by pH gradients across ion-exchange membranes. The adjustment of cathodic pH to different values to favor the process thermodynamically and the application of different electric potentials are tested and discussed.

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      Multielement Crystalline and Pseudocrystalline Oxides as Efficient Catalysts for the Direct Transformation of Glycerol into Acrylic Acid (pages 398–406)

      Alessandro Chieregato, Dr. M. Dolores Soriano, Prof. Dr. Ester García-González, Giuseppe Puglia, Dr. Francesco Basile, Dr. Patricia Concepción, Claudia Bandinelli, Prof. Dr. José M. López Nieto and Prof. Dr. Fabrizio Cavani

      Article first published online: 8 DEC 2014 | DOI: 10.1002/cssc.201402721

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      Better by design: Molybdenum-based catalysts are used industrially to oxidize acrolein into acrylic acid. The insertion of molybdenum in a W[BOND]V-oxide with hexagonal tungsten bronze structure makes it possible to obtain a new multifunctional material with improved acidic and redox properties for the one-pot oxydehydration of glycerol. Stable selective oxidation and high acrylic acid yield (51 %) are the main features of these new complex metal oxides.

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