ChemSusChem

Cover image for Vol. 7 Issue 12

Early View (Online Version of Record published before inclusion in an issue)

Editor-in-Chief: Guido Kemeling; Editorial Board Chairs: Matthias Beller, Gabriele Centi, Licheng Sun

Impact Factor: 7.117

ISI Journal Citation Reports © Ranking: 2013: 17/148 (Chemistry Multidisciplinary)

Online ISSN: 1864-564X

Associated Title(s): Angewandte Chemie International Edition, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemCatChem, ChemElectroChem, ChemPhysChem, Energy Technology

VIEW

  1. 1 - 86
  1. Full Papers

    1. Pressure-Accelerated Azide–Alkyne Cycloaddition: Micro Capillary versus Autoclave Reactor Performance

      Svetlana Borukhova, Dr. Andreas D. Seeger, Dr. Timothy Noël, Qi Wang, Prof. Dr. Markus Busch and Prof. Dr. Volker Hessel

      Article first published online: 17 DEC 2014 | DOI: 10.1002/cssc.201403034

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      Press to access! The potential of pressure in chemical intensification of intrinsic kinetics of 1,3-dipolar cycloaddition is investigated along with high temperature and concentration effects. Two reactors are compared, a specialized autoclave batch reactor for high-pressure operation up to 1800 bar and a capillary flow reactor for up to 400 bar. Reaction speedup and increases in space-time yields are reached while widening process windows of favorable operation to selectively produce Rufinamide precursor in good yields.

    2. Selective Oxidation of n-Butanol Using Gold-Palladium Supported Nanoparticles Under Base-Free Conditions

      Dr. Inaki Gandarias, Dr. Peter J. Miedziak, Dr. Ewa Nowicka, Mark Douthwaite, Dr. David J. Morgan, Prof. Graham J. Hutchings and Prof. Stuart H. Taylor

      Article first published online: 17 DEC 2014 | DOI: 10.1002/cssc.201403190

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      Stabilize, catalyze, oxidize: Au-Pd nanoparticles supported on TiO2, prepared by sol immobilization using polyvinyl alcohol as the stabilizing ligand, produced a high yield of butyric acid by the base-free oxidation of n-butanol by molecular oxygen under mild conditions.

  2. Viewpoints

    1. Across the Board: Licheng Sun

      Prof. Licheng Sun

      Article first published online: 17 DEC 2014 | DOI: 10.1002/cssc.201403341

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      Three for hydrogen: Three from the group of Professor Xuping Sun at State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry recently published in Angew. Chem. Int. Ed. are recommended for reading. These include CoP nanocrystals decorated on carbon nanotubes, Cu3P nanowire arrays, and FeP nanowire arrays as electrocatalysts for hydrogen evolution from water using low overpotentials.

  3. Full Papers

    1. An Aqueous Zinc-Ion Battery Based on Copper Hexacyanoferrate

      Dr. Rafael Trócoli and Dr. Fabio La Mantia

      Article first published online: 15 DEC 2014 | DOI: 10.1002/cssc.201403143

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      1.7 V aqueous battery: A new zinc-ion battery based on copper hexacyanoferrate and zinc foil in a nontoxic, noncorrosive electrolyte has been developed. The system shows cyclability, rate capability, and specific energy values near to those of lithium-ion organic batteries based on Li4Ti5O12 and LiFePO4 at 10 C.

    2. Bifunctional Silver(I) Complex-Catalyzed CO2 Conversion at Ambient Conditions: Synthesis of α-Methylene Cyclic Carbonates and Derivatives

      Dr. Qing-Wen Song, Wei-Qiang Chen, Dr. Ran Ma, Prof. Ao Yu, Qiu-Yue Li, Yao Chang and Prof. Dr. Liang-Nian He

      Article first published online: 15 DEC 2014 | DOI: 10.1002/cssc.201402921

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      Catalytic fixation of CO2: [(PPh3)2Ag]2CO3 is proven to be a robust bifunctional catalyst for the chemical upgrading of CO2 at atmospheric pressure to produce valuable compounds at ambient conditions. [(PPh3)2Ag]2CO3 can activate both CO2 and propargylic alcohol, and promote the subsequent intramolecular nucleophilic cyclization.

  4. Communications

    1. Cyclic Stability Testing of Aminated-Silica Solid Sorbent for Post-Combustion CO2 Capture

      James C. Fisher II and McMahan Gray

      Article first published online: 15 DEC 2014 | DOI: 10.1002/cssc.201402423

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      Best flu treatment: An amine-based sorbent is examined for use in CO2 removal from flue gas streams in coal-fired power plants. Cyclic testing results show the stability of the amine-based sorbents over 100 cycles. Furthermore, a rapid method for measuring capture capacity using a tracer gas is developed and confirmed through quantification of the CO2 released during regeneration.

  5. Full Papers

    1. Selective Hydrogenation of Lactic Acid to 1,2-Propanediol over Highly Active Ruthenium–Molybdenum Oxide Catalysts

      Yasuyuki Takeda, Tomohiro Shoji, Dr. Hideo Watanabe, Dr. Masazumi Tamura, Dr. Yoshinao Nakagawa, Prof. Kazu Okumura and Prof. Keiichi Tomishige

      Article first published online: 15 DEC 2014 | DOI: 10.1002/cssc.201403011

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      Minor adjustment for major effects: Modification of supported ruthenium catalysts with a small amount of molybdenum oxide (Ru[BOND]MoOx/C, Ru[BOND]MoOx/SiO2) enhances the catalytic activity for the hydrogenation of L-lactic acid to give (S)-1,2-propanediol with high selectivity. The turnover frequency is roughly four times higher than over Ru/C. The results reported are encouraging for the design of selective hydrogenation catalysts and the development of synthesis methods of alcohols.

  6. Communications

    1. Methyl N-Phenyl Carbamate Synthesis from Aniline and Methyl Formate: Carbon Recycling to Chemical Products

      Dr. Mohammad S. Yalfani, Dr. Giulio Lolli, Dr. Thomas E. Müller, Dr. Aurel Wolf and Prof. Dr. Leslaw Mleczko

      Article first published online: 12 DEC 2014 | DOI: 10.1002/cssc.201402827

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      Polyurethane precursor: Methyl N-phenyl carbamate was synthesized from aniline by using methyl formate as a green and efficient carbonylating agent. Compared to the conventional CO/CH3OH route, high yields were obtained with milder reaction conditions. Studies on the reaction sequence suggest an alternative and more efficient route to the carbamate via formanilide as intermediate.

  7. Cover Profiles

    1. Doubly Renewable Cellulose Polymer for Water-Based Coatings

      Cameron J. Tristram, Jennifer M. Mason, Prof. Dr. D. Bradley G. Williams and Dr. Simon F. R. Hinkley

      Article first published online: 12 DEC 2014 | DOI: 10.1002/cssc.201402906

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      “The synthesis of novel materials that may have immediate utility in a commodity application…” This and more about the story behind the research that inspired the cover image can be found on page ▪▪ (10.1002/cssc.201402906). View the Front Cover on page ▪▪ (10.1002/cssc.201402905).

  8. Full Papers

    1. Synergistic Effect between Defect Sites and Functional Groups on the Hydrolysis of Cellulose over Activated Carbon

      Guo Shiou Foo and Prof. Carsten Sievers

      Article first published online: 12 DEC 2014 | DOI: 10.1002/cssc.201402928

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      Understanding the hydrolysis of cellulose: Activated carbon is treated chemically with hydrogen peroxide and sulfuric acid to understand the effects of functional groups and morphology on the hydrolysis of cellulose. Defect sites on the carbon surface have been identified as a particularly active environment. Through a synergistic effect with functional groups, glucan chains are hydrolyzed with an increased activity.

  9. Communications

    1. Singlet-Oxygen Oxidation of 5-Hydroxymethylfurfural in Continuous Flow

      Dr. Thomas S. A. Heugebaert, Prof. Dr. Christian V. Stevens and Prof. Dr.  C. Oliver Kappe

      Article first published online: 11 DEC 2014 | DOI: 10.1002/cssc.201403182

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      Rosy future: The selective, high yielding, singlet-oxygen-mediated oxidation of 5-hydroxymethylfurfural (5-HMF) is performed in continuous-flow mode using rose Bengal as photosensitizer. The resulting butenolide (H2MF) is shown to be a valuable bio-based polyester precursor and the procedure proved to be scalable and applicable to related bio-based furfurals.

  10. Full Papers

    1. Direct Alcohol Fuel Cells: Toward the Power Densities of Hydrogen-Fed Proton Exchange Membrane Fuel Cells

      Dr. Yanxin Chen, Marco Bellini, Dr. Manuela Bevilacqua, Dr. Paolo Fornasiero, Dr. Alessandro Lavacchi, Dr. Hamish A. Miller, Lianqin Wang and Dr. Francesco Vizza

      Article first published online: 11 DEC 2014 | DOI: 10.1002/cssc.201402999

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      Owed to an anode: The use of biomass-derived alcohols in direct fuel cells is an attractive way to transform their chemical energy into electrical power. To avoid the drawbacks of carbon-supported nanoparticle (NP) electrocatalysts, anodes consisting of Pd NPs supported on 3 D TiO2 nanotube arrays have been prepared. Fuel cells with these anodes produce power densities in direct fuel cells fed with bioalcohols that approach the level of H2-fed proton exchange membrane fuel cells.

    2. Effect of Component Distribution and Nanoporosity in CuPt Nanotubes on Electrocatalysis of the Oxygen Reduction Reaction

      Dr. Huizhang Guo, Xiang Liu, Dr. Chengdong Bai, Dr. Yuanzhi Chen, Dr. Laisen Wang, Prof. Mingsen Zheng, Prof. Quanfeng Dong and Prof. Dong-Liang Peng

      Article first published online: 11 DEC 2014 | DOI: 10.1002/cssc.201403037

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      Poring over the results: CuPt nanotubes and porous Cu3Pt intermetallic nanorods are prepared through a controlled galvanic replacement reaction and heat treatment process. The relationship among the geometric features, component distribution, and oxygen reduction reaction performance in these electrocatalysts are clarified.

  11. Communications

    1. Preparation of Pd–Co-Based Nanocatalysts and Their Superior Applications in Formic Acid Decomposition and Methanol Oxidation

      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.

    2. Electrolytes Based on TEMPO–Co Tandem Redox Systems Outperform Single Redox Systems in Dye-sensitized Solar Cells

      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.

  12. Full Papers

    1. Catalytic Hydrodechlorination of Benzyl Chloride Promoted by Rh–N-heterocyclic Carbene Catalysts

      Guillermo Lázaro, Dr. Víctor Polo, Dr. Francisco J. Fernández-Alvarez, Dr. Pilar García-Orduña, Prof. Fernando J. Lahoz, Dr. Manuel Iglesias, Prof. Jesús J. Pérez-Torrente and Prof. Luis A. Oro

      Article first published online: 10 DEC 2014 | DOI: 10.1002/cssc.201403036

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      What a clamp: The effective solvent-free hydrodechlorination of benzyl chloride using silanes as hydrogen source in the presence of homogeneous and heterogeneous Rh–N-heterocyclic carbene-based catalysts supported on MCM-41 is reported. The catalysts have been investigated thoroughly using several techniques. A reaction pathway is proposed based on DFT data and experimental insights.

    2. Decoupling HZSM-5 Catalyst Activity from Deactivation during Upgrading of Pyrolysis Oil Vapors

      Dr. Shaolong Wan, Christopher Waters, Adam Stevens, Abhishek Gumidyala, Prof. Rolf Jentoft, Prof. Lance Lobban, Prof. Daniel Resasco, Prof. Richard Mallinson and Prof. Steven Crossley

      Article first published online: 10 DEC 2014 | DOI: 10.1002/cssc.201402861

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      Divide and conquer: We demonstrate the use of a second catalytic reactor to study the role of zeolite catalyst temperature and the density of acid sites on catalytic activity and stability independently upon contact with pulses of biomass pyrolysis vapors.

  13. Concepts

    1. Electrifying White Biotechnology: Engineering and Economic Potential of Electricity-Driven Bio-Production

      Dr. Falk Harnisch, Dr. Luis F. M. Rosa, Frauke Kracke, Dr. Bernardino Virdis and Dr. Jens O. Krömer

      Article first published online: 10 DEC 2014 | DOI: 10.1002/cssc.201402736

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      En route to electricity-driven bio-production: Microbial electrochemical technology is an interdisciplinary field that is devoted to the development of applications based on processes interfacing microbiology and electrochemistry. One of the most promising fields is the electricity-driven biosynthesis. We show that there is a significant market potential if technical obstacles can be overcome.

  14. Full Papers

    1. On the Chemistry of Ethanol on Basic Oxides: Revising Mechanisms and Intermediates in the Lebedev and Guerbet reactions

      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.

  15. Communications

    1. Enhancing the Stability of Porphyrin Dye-Sensitized Solar Cells by Manipulation of Electrolyte Additives

      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.

  16. Minireviews

    1. Diazo Compounds in Continuous-Flow Technology

      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.

  17. Full Papers

    1. Multielement Crystalline and Pseudocrystalline Oxides as Efficient Catalysts for the Direct Transformation of Glycerol into Acrylic Acid

      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.

  18. Cover Pictures

    1. You have free access to this content
      Upgrading Carbon Dioxide by Incorporation into Heterocycles

      Dr. Bing Yu and Prof. Dr. Liang-Nian He

      Article first published online: 8 DEC 2014 | DOI: 10.1002/cssc.201403171

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      The Inside Back Cover picture shows the chemical transformation of CO2 as an appealing tool for heterocycle synthesis through rationally designed substrates and subsequent intramolecular cyclization. This pattern of CO2 fixation can be regarded as a “nucleophilic pathway”, avoiding use of stoichiometric organometallic reagents. With this strategy, either the entire “CO2” moiety or “C[DOUBLE BOND]O” fragment could be incorporated into a variety of heterocycles including cyclic carbamates, benzoxazine-2-one, 4-hydroxyquinolin-2-one, quinazoline-2,4(1H,3H)-diones, benzimidazolones, and α-alkylidene cyclic carbonate. In their Minireview on page ▪▪ (DOI: 10.1002/cssc.201402837), Yu et al. discuss strategies for upgrading CO2 into value-added heterocycles under mild conditions and potential utilization of CO2 as an alternative and ideal sustainable C1 synthon in organic synthesis rather than just being wasted.

    2. You have free access to this content
      Catalytic Oxidation of Biorefinery Lignin to Value-added Chemicals to Support Sustainable Biofuel Production

      Ruoshui Ma, Prof. Dr. Yan Xu and Prof. Xiao Zhang

      Article first published online: 8 DEC 2014 | DOI: 10.1002/cssc.201403127

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      The Back Cover image visualizes the 3D phenolic skeleton of lignin and displays the three target platform chemicals to be produced from biorefinery lignin: phenolic compounds, dicarboxylic acids, and quinones. The background images correspond to the potential value-added products for each platform chemical and serve to illustrate how the successful realization of biorefinery lignin conversion will result in a diverse and versatile portfolio of consumer products across many different industries. More details can be found in the Review by Ma et al. on page ▪▪ (DOI: 10.1002/cssc.201402503).

    3. You have free access to this content
      Doubly Renewable Cellulose Polymer for Water-Based Coatings

      Cameron J. Tristram, Jennifer M. Mason, Prof. Dr. D. Bradley G. Williams and Dr. Simon F. R. Hinkley

      Article first published online: 8 DEC 2014 | DOI: 10.1002/cssc.201402905

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      The Front Cover image shows the passage of plant material into paint. First comes cellulose, which is esterified with the bio-derived levulinic acid, forming a novel cellulosic ester. Additional chemical manipulations modify the physical properties of the polymer, such that self-dispersion and formation of a stable aqueous colloid is achieved. The precipitated particles are spontaneously film-forming at ambient temperature, which allows the product to be formulated into paint. More details can be found in the Communication by Hinkley and co-workers on page ▪▪ (DOI: 10.1002/cssc.201402590), while more information about the research group is available in the Cover Profile (DOI: 10.1002/cssc.201402906).

  19. Minireviews

    1. Rhenium-Catalyzed Deoxydehydration of Diols and Polyols

      Dr. Johannes R. Dethlefsen and Dr. Peter Fristrup

      Article first published online: 4 DEC 2014 | DOI: 10.1002/cssc.201402987

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      Taking a shortcut! Recent developments in the rhenium-catalyzed deoxydehydration reaction are reviewed. Although the reaction is formally a deoxygenation and a dehydration, the use of transition metal catalysis opens up new possibilities. The focus is on recent developments of the substrate scope, alternative reductants, and mechanistic investigations.

  20. Communications

    1. Functionalized Fe3O4@Silica Core–Shell Nanoparticles as Microalgae Harvester and Catalyst for Biodiesel Production

      Ya-Dong Chiang, Dr. Saikat Dutta, Ching-Tien Chen, Prof. Dr. Yu-Tzu Huang, Prof. Dr. Kuen-Song Lin, Prof. Dr. Jeffrey C. S. Wu, Dr. Norihiro Suzuki, Prof. Dr. Yusuke Yamauchi and Prof. Dr. Kevin C.-W. Wu

      Article first published online: 4 DEC 2014 | DOI: 10.1002/cssc.201402996

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      Harvesting and fuelling: Core–shell Fe3O4@silica magnetic nanoparticles functionalized with a strong base, triazabicyclodecene (TBD), were successfully synthesized for harvesting microalgae and for one-pot microalgae-to-fatty acid methyl ester (FAME, or so-called biodiesel) conversion. Covalently functionalized core–shell nanoparticles have a large potential for the production of liquid transportation fuels from algal biomass.

    2. Metal-Catalyst-Free Carbohydrazide Fuel Cells with Three-Dimensional Graphene Anodes

      Ji Qi, Neeva Benipal, Dr. Hui Wang, David J. Chadderdon, Yibo Jiang, Wei Wei, Prof. Yun Hang Hu and Prof. Wenzhen Li

      Article first published online: 3 DEC 2014 | DOI: 10.1002/cssc.201403032

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      We had met before: The commercialization of fuel cells is hindered by the limited reserves of metals. Metal-catalyst-free fuel cells powered by the carbohydrazide oxidation reaction over 3D graphene as anode catalyst and nitrogen-doped carbon nanotubes as cathode are demonstrated. The average number of electrons electrochemically extracted from a single carbohydrazide molecule indicates activation of carbon–nitrogen bonds, a key factor contributing to high fuel utilization efficiency.

    3. Cross-Metathesis of Biosourced Fatty Acid Derivatives: A Step Further Toward Improved Reactivity

      Dr. Paul Vignon, Tom Vancompernolle, Dr. Jean-Luc Couturier, Dr. Jean-Luc Dubois, Prof. André Mortreux and Dr. Régis M. Gauvin

      Article first published online: 3 DEC 2014 | DOI: 10.1002/cssc.201403170

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      Howdy, partner! The use of internal functionalized olefins as partners in the cross-metathesis of biosourced fatty acid methyl esters affords a monomer for polyester synthesis with high efficiency, despite low catalytic loading and minimal substrate purification.

  21. Full Papers

    1. Bio-Based Nitriles from the Heterogeneously Catalyzed Oxidative Decarboxylation of Amino Acids

      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.

    2. Vectorial Electron Transfer for Improved Hydrogen Evolution by Mercaptopropionic-Acid-Regulated CdSe Quantum-Dots–TiO2–Ni(OH)2 Assembly

      Dr. Shan Yu, Dr. Zhi-Jun Li, Xiang-Bing Fan, Jia-Xin Li, Fei Zhan, Xu-Bing Li, Prof. Ye Tao, Prof. Chen-Ho Tung and Prof. Li-Zhu Wu

      Article first published online: 3 DEC 2014 | DOI: 10.1002/cssc.201402885

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      Dotty about hydrogen: If mercaptopropionic acid is used as the linker, a turnover frequency of 5140 h−1 based on CdSe quantum dots (QDs) for photocatalytic hydrogen evolution is achieved by a CdSe QDs–TiO2–Ni(OH)2 ternary assembly at pH 11. Vectorial electron transfer from CdSe QDs to TiO2 and then to Ni(OH)2 is crucial for this high efficiency.

    3. Enhanced Performance of Bioelectrochemical Hydrogen Production using a pH Control Strategy

      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.

  22. Viewpoints

    1. Across the Board: Jairton Dupont

      Prof. Dr. Jairton Dupont 

      Article first published online: 2 DEC 2014 | DOI: 10.1002/cssc.201403276

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      CO2 activation: Our board member Jairton Dupont highlights how the fine-tuning of the electronic and steric properties of ruthenium and rhodium complexes and reaction conditions generates efficient homogeneous transition-metal catalysts for the transformation of CO2 under hydrogen pressure. The catalysts find use in the methylation of amines, amides, and C[BOND]H bonds as well as for the hydroformylation, alkoxycarbonylation, and hydrocarboxylation of alkenes.

  23. Full Papers

    1. Titanium Oxynitride Interlayer to Influence Oxygen Reduction Reaction Activity and Corrosion Stability of Pt and Pt–Ni Alloy

      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.

    2. Guaiacol Hydrodeoxygenation Mechanism on Pt(111): Insights from Density Functional Theory and Linear Free Energy Relations

      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.

    3. Synthesis of Lithium Iron Phosphate/Carbon Microspheres by Using Polyacrylic Acid Coated Iron Phosphate Nanoparticles Derived from Iron(III) Acrylate

      Dongwei Xu, Prof. Yan-Bing He, Xiaodong Chu, Dr. Zhaojun Ding, Prof. Baohua Li, Jianfu He, Prof. Hongda Du, Xianying Qin and Prof. Feiyu Kang

      Article first published online: 2 DEC 2014 | DOI: 10.1002/cssc.201403060

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      Under cover: Lithium iron phosphate/carbon (LiFePO4/C) microspheres with high rate and cycling performances are synthesized from nanoparticles. A complete carbon coating on the surface of the primary nanoparticles, derived from carbonation of the in situ polymerized PAA layer, controls the grain growth effectively and greatly enhances the electronic and ionic conductivities of the LiFePO4/C electrode.

  24. Reviews

    1. Chitosan as a Sustainable Organocatalyst: A Concise Overview

      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.

  25. Full Papers

    1. Alkaline Stability of Quaternary Ammonium Cations for Alkaline Fuel Cell Membranes and Ionic Liquids

      M. G. Marino and Dr. K. D. Kreuer

      Article first published online: 27 NOV 2014 | DOI: 10.1002/cssc.201403022

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      Twice thwarted: The hydroxide-induced decomposition of 26 different quaternary ammonium (QA) groups reveals a piperidine-based heterocycle and its spiro compound as the most stable QAs. Their ring structure makes them highly resistant against both elimination and substitution reaction This is counterintuitive in view of the common assumption that avoidance of β-protons is essential for reducing degradation rates. This is fundamentally intriguing as well as relevant for the development of OH exchange membranes and ionic liquids.

    2. Bimolecular Crystals with an Intercalated Structure Improve Poly(p-phenylenevinylene)-Based Organic Photovoltaic Cells

      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.

    3. Ferrocene and Cobaltocene Derivatives for Non-Aqueous Redox Flow Batteries

      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.

    4. Synergistic Effects of Mixing Sulfone and Ionic Liquid as Safe Electrolytes for Lithium Sulfur Batteries

      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.

    5. Copper-Doped Dual Phase Li4Ti5O12–TiO2 Nanosheets as High-Rate and Long Cycle Life Anodes for High-Power Lithium-Ion Batteries

      Dr. Chengcheng Chen, Yanan Huang, Dr. Cuihua An, Hao Zhang, Prof. Yijing Wang, Prof. Lifang Jiao and Prof. Huatang Yuan

      Article first published online: 25 NOV 2014 | DOI: 10.1002/cssc.201402886

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      Copper is the dope of the party! Cu-doped Li4Ti5O12–TiO2 nanosheets are synthesized by a facile, cheap, and environmentally friendly solution-based method. These nanostructures are investigated as an anode material for lithium-ion batteries and excellent rate performance is found. Copper doping builds fast channels in the nanosheets and enhances transportation of Li+ and electrons.

    6. Plasticizer and Surfactant Formation from Food-Waste- and Algal Biomass-Derived Lipids

      Dr. Daniel Pleissner, Kin Yan Lau, Prof. Chengwu Zhang and Dr. Carol Sze Ki Lin

      Article first published online: 25 NOV 2014 | DOI: 10.1002/cssc.201402888

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      Establishment of a green society by waste utilization: A sustainable process is introduced for the formation of plasticizers and surfactants from food-waste and algal lipids. Plasticizer was formed by epoxidation of unsaturated fatty acids extracted from food-waste and algal biomass, heterotrophically produced from food-waste hydrolysate. Surfactant was produced by transesterification of epoxidized and saturated fatty acid methyl esters with polyglycerol for the formation of surfactants.

    7. Shewanella-mediated Biosynthesis of Manganese Oxide Micro-/Nanocubes as Efficient Electrocatalysts for the Oxygen Reduction Reaction

      Congcong Jiang, Zhaoyan Guo, Prof. Ying Zhu, Dr. Huan Liu, Prof. Meixiang Wan and Prof. Lei Jiang

      Article first published online: 25 NOV 2014 | DOI: 10.1002/cssc.201402759

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      Shewie­ here tells me you′re lookin′ for manganese oxide cubes? Mn2O3 micro-/nanocubes are prepared by calcination of MnCO3 precursors, fabricated by dissimilatory metal-reducing Shewanella loihica PV-4 in the presence of MnO4 as sole electron accepter in anaerobic condition. The Mn2O3 micro-/nanocubes, calcinated at 500 °C and 700 °C serve as intrinsic electrocatalysts, and exhibit promising catalytic activities towards the oxygen reduction reaction (ORR), outstanding methanol crossover resistance, as well as long-term operational stability.

  26. Communications

    1. The Effect of Alkaline Pretreatment Methods on Cellulose Structure and Accessibility

      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.

  27. Full Papers

    1. Highly Functionalized Biaryls via Suzuki–Miyaura Cross-Coupling Catalyzed by Pd@MOF under Batch and Continuous Flow Regimes

      Vlad Pascanu, Peter R. Hansen, Dr. Antonio Bermejo Gómez, Dr. Carles Ayats, Dr. Ana E. Platero-Prats, Dr. Magnus J. Johansson, Prof. Miquel À. Pericàs and Prof. Belén Martín-Matute

      Article first published online: 24 NOV 2014 | DOI: 10.1002/cssc.201402858

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      MOFember: A robust heterogeneous catalytic system is proposed for the Suzuki–Miyaura cross-coupling reaction, and consists of palladium nanoparticles immobilized on the metal–organic framework MIL-101-NH2. A set of highly functionalized biaryls is synthesized under mild reaction conditions. By packing Pd@MIL-101-NH2 in a micro-flow reactor, the system can be successfully adapted for operation under continuous-flow conditions.

  28. Communications

    1. Effects of Catalyst Pore Structure and Acid Properties on the Dehydration of Glycerol

      Youngbo Choi, Hongseok Park, Yang Sik Yun and Prof. Dr. Jongheop Yi

      Article first published online: 21 NOV 2014 | DOI: 10.1002/cssc.201402925

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      Combined action: Hierarchically mesoporous acidic nanocatalysts with different acidic properties are used for the dehydration of glycerol. A comparison of the nanocatalysts with microporous and mesoporous acid-catalysts verifies the benefits of hierarchical pores on enhancing the apparent activity and stability of the catalyst, but also highlights that overall catalytic performance is determined by the combined action of porous and acidic properties.

  29. Full Papers

    1. Ternary Ag/MgO-SiO2 Catalysts for the Conversion of Ethanol into Butadiene

      Wout Janssens, Dr. Ekaterina V. Makshina, Pieter Vanelderen, Dr. Filip De Clippel, Kristof Houthoofd, Stef Kerkhofs, Prof. Dr. Johan A. Martens, Prof. Dr. Pierre A. Jacobs and Prof. Dr. Bert F. Sels

      Article first published online: 19 NOV 2014 | DOI: 10.1002/cssc.201402894

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      Renewable route to butadiene: A silver-loaded MgO-SiO2 catalyst is active in the direct formation of butadiene from ethanol. Preparation steps have significant impact on internal organization of the final catalyst in terms of redox-acid/base properties. Based on extensive characterizations, a model is constructed to describe the catalytic activity of this system.

    2. Selective Modulation of Charge-Carrier Transport of a Photoanode in a Photoelectrochemical Cell by a Graphitized Fullerene Interfacial Layer

      Sun-Young Park, Dr. Dong Chan Lim, Eun Mi Hong, Joo-Yeoul Lee, Jinhee Heo, Jae Hong Lim, Dr. Chang-Lyoul Lee, Prof. Young Dok Kim and Prof. Dr. Guido Mul

      Article first published online: 19 NOV 2014 | DOI: 10.1002/cssc.201402577

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      Layer it up: A graphitic carbon interfacial layer, derived from C70 by annealing at 500 °C, results in a significant increase in the attainable photocurrent of a photoelectrochemical cell that contains a WO3-functionalized fluorine-doped tin oxide photoanode. Modification of interfaces using graphitized carbon materials is favorable for production of cheap and highly efficient large-area solar-to-fuel devices.

    3. A New Class of Single-Component Absorbents for Reversible Carbon Dioxide Capture under Mild Conditions

      Dr. Francesco Barzagli, Dr. Sarah Lai and Prof. Fabrizio Mani

      Article first published online: 19 NOV 2014 | DOI: 10.1002/cssc.201402421

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      Solvent not required: Neat secondary amines were reversibly reacted with CO2 in the absence of any solvent because they were liquid before and after CO2 uptake. Good absorption efficiency was attained in continuous cycles of absorption and desorption performed in packed columns.

  30. Communications

    1. Catalytic Dehydration of Carbohydrates Suspended in Organic Solvents Promoted by AlCl3/SiO2 Coated with Choline Chloride

      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.

  31. Full Papers

    1. Anthracene/Phenothiazine π-Conjugated Sensitizers for Dye-Sensitized Solar Cells using Redox Mediator in Organic and Water-based Solvents

      Dr. Ryan Yeh-Yung Lin, Tzu-Man Chuang, Feng-Ling Wu, Pei-Yu Chen, Te-Chun Chu, Dr. Jen-Shyang Ni, Miao-Syuan Fan, Prof. Yih-Hsing Lo, Prof. Kuo-Chuan Ho and Prof. Jiann T. Lin

      Article first published online: 17 NOV 2014 | DOI: 10.1002/cssc.201403016

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      DSSCs get wet: Metal-free dyes containing an anthracene/phenothiazine unit in the spacer are synthesized. Aqueous dye-sensitized solar cells using these sensitizers and a dual electrolyte that comprises 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and imidazolium iodide exhibit promising light-to-electricity conversion efficiencies and excellent Voc values.

    2. Enhanced Fill Factor of Tandem Organic Solar Cells Incorporating a Diketopyrrolopyrrole-Based Low-Bandgap Polymer and Optimized Interlayer

      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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      Both ends meet in the middle: 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 result in an enhanced fill factor and reproducible results from the tandem cells.

  32. Communications

    1. Selective Electrocatalytic Oxidation of Sorbitol to Fructose and Sorbose

      Dr. Youngkook Kwon, Dr. Ed de Jong, Dr. Jan Kees van der Waal and Prof. Dr. Marc T. M. Koper

      Article first published online: 14 NOV 2014 | DOI: 10.1002/cssc.201402880

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      New cats on the block: A new electrocatalytic method for the selective electrochemical oxidation of sorbitol to fructose and sorbose is developed by using a platinum electrode promoted by p-block metal atoms. By studying a range of C4, C5, and C6 polyols, it is found that the promoter interferes with the stereochemistry of the polyol and thereby modifies its reactivity.

  33. Full Papers

    1. Superior Ion-Conducting Hybrid Solid Electrolyte for All-Solid-State Batteries

      Prof. Dr. Jae-Kwang Kim, Prof. Johan Scheers, Prof. Tae Joo Park and Prof. Youngsik Kim

      Article first published online: 13 NOV 2014 | DOI: 10.1002/cssc.201402969

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      Solid-state battery: A hybrid solid electrolyte prepared by novel facile method has high room temperature ionic conductivity, excellent thermal stability, and low interface resistance with good contact. With the hybrid solid electrolyte, the pouch-type solid-state battery exhibits high initial discharge capacity, especially at room temperature.

    2. Cobalt–Manganese-Based Spinels as Multifunctional Materials that Unify Catalytic Water Oxidation and Oxygen Reduction Reactions

      Dr. Prashanth W. Menezes, Dr. Arindam Indra, Dr. Nastaran Ranjbar Sahraie, Arno Bergmann, Prof. Dr. Peter Strasser and Prof. Dr. Matthias Driess

      Article first published online: 13 NOV 2014 | DOI: 10.1002/cssc.201402699

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      All-in-one: Porous cobalt-manganese-based spinels are prepared from their respective carbonate precursors and are used as highly effective multifunctional catalysts for the unification of electrochemical, oxidant-driven, and photochemical oxygen evolution as well as the oxygen reduction reaction.

    3. Towards High Water Permeability in Triazine-Framework-Based Microporous Membranes for Dehydration of Ethanol

      Dr. Yu Pan Tang, Dr. Huan Wang and Prof. Tai Shung Chung

      Article first published online: 13 NOV 2014 | DOI: 10.1002/cssc.201402816

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      Try a triazine: Triazine-framework-based membranes are synthesized via a facile method and tailored for dehydration of biofuel with extremely high water permeability. Pervaporation and vapor sorption performance of the membranes is closely correlated with microstructural evolution, shedding light on the mass-transport properties of the microporous membranes.

    4. Enhanced Performance of Mixed-Matrix Membranes through a Graft Copolymer-Directed Interface and Interaction Tuning Approach

      Won Seok Chi, Sang Jin Kim, Seung-Joon Lee, Prof. Youn-Sang Bae and Prof. Jong Hak Kim

      Article first published online: 13 NOV 2014 | DOI: 10.1002/cssc.201402677

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      Restricted access: A large improvement in gas permeability and selectivity are simultaneously obtained through an interface and interaction tuning approach based on an amphiphilic poly(vinyl chloride)-g-poly(oxyethylene methacrylate) (PVC-g-POEM). This approach maximizes the gas permeation of zeolite imidazole frameworks-8 (ZIF-8).

    5. Cyanogel-Derived Formation of 3 D Nanoporous SnO2–MxOy (M=Ni, Fe, Co) Hybrid Networks for High-Performance Lithium Storage

      Qingyun Zhu, Dr. Ping Wu, Jinjing Zhang, Weiyu Zhang, Prof. Yiming Zhou, Prof. Yawen Tang and Prof. Tianhong Lu

      Article first published online: 11 NOV 2014 | DOI: 10.1002/cssc.201402829

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      Things are starting to gel: A facile, scalable, and versatile cyanogel-derived method for the construction of 3 D nanoporous SnO2–MxOy (M=Ni, Fe, Co) hybrid networks is developed. The 3 D nanoporous SnO2–MxOy hybrid networks possess unique compositional and structural features that are beneficial to lithium storage. Furthermore, these networks might serve as ideal anodes in advanced lithium-ion batteries.

    6. Hierarchically Superstructured Prussian Blue Analogues: Spontaneous Assembly Synthesis and Applications as Pseudocapacitive Materials

      Dr. Yanfeng Yue, Dr. Zhiyong Zhang, Andrew J. Binder, Dr. Jihua Chen, Dr. Xianbo Jin, Dr. Steven H. Overbury and Prof. Dr. Sheng Dai

      Article first published online: 10 NOV 2014 | DOI: 10.1002/cssc.201402520

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      Analogue is back! Hierarchically superstructured Prussian blue analogues were fabricated through a spontaneous assembly technique. These Prussian blue analogues, showing capacitance comparable with conventional hybrid graphene/MnO2 nanostructured textiles, possess the advantage that they can be used with more environmentally neutral electrolytes, making Prussian blue analogues a great contender for applications as pseudocapacitive materials.

  34. Communications

    1. Semi-Aromatic Polyesters Based on a Carbohydrate-Derived Rigid Diol for Engineering Plastics

      Dr. Jing Wu, Pieter Eduard, Dr. Shanmugam Thiyagarajan, Dr. Bart A. J. Noordover, Dr. Daan S. van Es and Prof. Cor E. Koning

      Article first published online: 7 NOV 2014 | DOI: 10.1002/cssc.201402935

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      Diol P for Polymers: Carbohydrate-derived, semi-crystalline polyesters based on isoidide-2,5-dimethanol and furan-2,5-dicarboxylic acid or terephthalic acid are prepared and characterized. These new semi-aromatic polymers display high melting and glass transition temperatures and crystallize from the melt. The reactivity, stability, and characteristics make the diol a promising monomer for the synthesis of engineering polymers.

    2. Synthesis of Cellulose Methylcarbonate in Ionic Liquids using Dimethylcarbonate

      Sara R. Labafzadeh, K. Juhani Helminen, Prof. Dr. Ilkka Kilpeläinen and Dr. Alistair W. T. King

      Article first published online: 6 NOV 2014 | DOI: 10.1002/cssc.201402794

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      The neste-best thing: Cellulose methylcarbonate is prepared in ionic liquid by transesterification with dimethylcarbonate, a cheap and low-toxicity reagent. There is minimal degradation of the cellulose backbone during modification. Its chemical, mechanical, and barrier properties are determined, revealing the material′s potential as a fully biobased polymer for future applications.

    3. Advanced Biorefinery based on the Fractionation of Biomass in γ-Valerolactone and Water

      Wenwen Fang and Prof. Herbert Sixta

      Article first published online: 4 NOV 2014 | DOI: 10.1002/cssc.201402821

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      Advanced biorefinery: We suggest for the first time the use of γ-valerolactone (GVL)/H2O as solvent and reaction medium for the fractionation of wood to recover pure cellulose, uniform sugar components from hemicellulose, and a pure lignin fraction. As all components of the biomass could be utilized, this method could give rise to products that are competitive to those obtained from petroleum.

  35. Full Papers

    1. Production of Renewable Hexanols from Mechanocatalytically Depolymerized Cellulose by Using Ir-ReOx/SiO2 catalyst

      Sibao Liu, Yasuyo Okuyama, Dr. Masazumi Tamura, Dr. Yoshinao Nakagawa, Akio Imai and Prof. Keiichi Tomishige

      Article first published online: 3 NOV 2014 | DOI: 10.1002/cssc.201403010

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      Let′s talk about hexanol: A high yield of renewable hexanols was obtained from depolymerized cellulose by using Ir-ReOx/SiO2 catalyst in biphasic system (n-decane+H2O). The cellulose is depolymerized by mechanocatalysis with the aid of H2SO4. The influence of solvent amount, reaction temperature, and hydrogen pressure is systematically investigated.

  36. Communications

    1. Cellulose Amorphization by Swelling in Ionic Liquid/Water Mixtures: A Combined Macroscopic and Second-Harmonic Microscopy Study

      Daan Glas, Rik Paesen, Daphne Depuydt, Prof. Koen Binnemans, Prof. Marcel Ameloot, Prof. Dirk E. De Vos and Prof. Rob Ameloot

      Article first published online: 31 OCT 2014 | DOI: 10.1002/cssc.201402776

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      Soaking as the solution: Soaking of cellulose ionic liquid/water mixtures results in a reduced crystallinity (amorphization). The evolution of cellulose crystallinity is studied in situ by second-harmonic generation (SHG) microscopy. These results show the potential of soaking in ionic liquid/water mixtures as an alternative cellulose pretreatment method, with the main advantage of avoiding energy-intensive IL purification, as required in dissolution–precipitation.

  37. Full Papers

    1. Photogeneration of Hydrogen from Water by Hybrid Molybdenum Sulfide Clusters Immobilized on Titania

      David Recatalá, Prof. Rosa Llusar, Dr. Artem L. Gushchin, Dr. Ekaterina A. Kozlova, Yuliya A. Laricheva, Dr. Pavel A. Abramov, Prof. Maxim N. Sokolov, Prof. Roberto Gómez and Prof. Teresa Lana-Villarreal

      Article first published online: 30 OCT 2014 | DOI: 10.1002/cssc.201402773

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      Mo magic: Two new hybrid Mo3S7 molybdenum(IV) cluster complexes derivatized with diimino ligands are prepared. In these Mo3 units, disulfide ligands bridge adjacent metal atoms and the outer positions on one of the metal atoms are functionalized with substituted bipyridines. The Mo3S7 cores are adsorbed on TiO2 and reduced to generate an electrocatalyst that reduces the overpotential for the H2 evolution reaction considerably.

  38. Communications

    1. Compatibility between Cellulose and Hydrophobic Polymer Provided by Microfibrillated Lignocellulose

      Prof. Wolfgang Gindl-Altmutter, Michael Obersriebnig, Dr. Stefan Veigel and Prof. Falk Liebner

      Article first published online: 27 OCT 2014 | DOI: 10.1002/cssc.201402742

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      The strength lies in the residue: Microfibrillated cellulose (MFC), a bio-based nanoscale high-strength reinforcement for polymers, lacks compatibility with hydrophobic polymer. It is shown that residual lignin in microfibrillated lignocellulose (MFLC) is of amphiphilic character, which provides compatibility with the hydrophobic polymers polycaprolactone and polystyrene.

    2. You have free access to this content
      “Nanorust”-catalyzed Benign Oxidation of Amines for Selective Synthesis of Nitriles

      Dr. Rajenahally V. Jagadeesh, Dr. Henrik Junge and Prof. Dr. Matthias Beller

      Article first published online: 24 OCT 2014 | DOI: 10.1002/cssc.201402613

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      Next steps towards an iron age in catalysis: A “nanorust”-based material is produced by the pyrolysis of iron acetate-phenanthroline complex on carbon. The material, comprising nanoscale iron oxide covered by layers of nitrogen-doped graphene on carbon (Fe2O3/NGr@C), is a stable, active, and reusable catalyst system for environmentally benign oxidation processes. The selective synthesis of structurally diverse nitriles from amines using molecular oxygen is performed.

  39. Full Papers

    1. Photocatalytic Acceptorless Alkane Dehydrogenation: Scope, Mechanism, and Conquering Deactivation with Carbon Dioxide

      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.

    2. CO2 Hydrogenation to Methanol on Supported Au Catalysts under Moderate Reaction Conditions: Support and Particle Size Effects

      Yeusy Hartadi, Dr. Daniel Widmann and Prof. Dr. R. Jürgen Behm

      Article first published online: 22 OCT 2014 | DOI: 10.1002/cssc.201402645

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      Golden times for methanol: The production of “green methanol” from CO2 and H2 represents an attractive approach for chemical energy conversion in renewable energy concepts. Oxide-supported Au catalysts are highly active for this reaction under moderate conditions, and we show how their catalytic performance (activity, selectivity) is correlated to their physical and chemical properties (nature of the support, Au particle size).

  40. Communications

    1. Controlling Porosity in Lignin-Derived Nanoporous Carbon for Supercapacitor Applications

      Ju-Won Jeon, Libing Zhang, Prof. Jodie L. Lutkenhaus, Dr. Dhrubojyoti D. Laskar, Dr. John P. Lemmon, Dr. Daiwon Choi, Dr. Manjula I. Nandasiri, Ali Hashmi, Prof. Jie Xu, Dr. Radha K. Motkuri, Dr. Carlos A. Fernandez, Dr. Jian Liu, Dr. Melvin P. Tucker, Peter B. McGrail, Prof. Bin Yang and Dr. Satish K. Nune

      Article first published online: 22 OCT 2014 | DOI: 10.1002/cssc.201402621

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      Low-cost renewable lignin is used as a precursor to produce high surface area, graphitized porous carbons for supercapacitor applications. Molecular weight and oxygen consumption during carbonization are critical factors in controlling the structure and, consequently, capacitor performance. The carbonized residues exhibit good electrochemical performance in terms of high specific capacitance, high energy density and power, and good capacity retention.

  41. Full Papers

    1. Electron-Acceptor-Dependent Light Absorption, Excited-State Relaxation, and Charge Generation in Triphenylamine Dye-Sensitized Solar Cells

      Dr. Renzhi Li, Dr. Min Zhang, Cancan Yan, Zhaoyang Yao, Jing Zhang and Prof. Peng Wang

      Article first published online: 16 OCT 2014 | DOI: 10.1002/cssc.201402806

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      A lifetime of excitation: Electron-acceptor-dependent excited-state torsional relaxation and multiple-state electron injection at the dye/titania interface are investigated by broadband femtosecond transient spectroscopy measurements in conjunction with theoretical calculations. Results indicate the crucial role of a long excited-state lifetime in maintaining a high electron-injection yield.

    2. Effects of Hydrophobicity of Diffusion Layer on the Electroreduction of Biomass Derivatives in Polymer Electrolyte Membrane Reactors

      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.

  42. Communications

    1. Cost-Effective Synthesis of Amine-Tethered Porous Materials for Carbon Capture

      Dr. Weigang Lu, Mathieu Bosch, Prof. Dr. Daqiang Yuan and Prof. Dr. Hong-Cai Zhou

      Article first published online: 14 OCT 2014 | DOI: 10.1002/cssc.201402622

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      Energy-efficient carbon capture: A truly cost-efficient strategy for the synthesis of amine-tethered porous polymer networks has been developed. A network containing diethylenetriamine exhibits a high working capacity comparable to current state-of-art technology (30 % monoethanolamine solution), yet it requires only one third as much energy for regeneration. It has also been demonstrated that no capacity loss occurs after 50 adsorption–desorption cycles of CO2 in a temperature-swing adsorption process.

  43. Full Papers

    1. The Role of Hydroxyl Group Acidity on the Activity of Silica-Supported Secondary Amines for the Self-Condensation of n-Butanal

      Dr. Sankaranarayanapillai Shylesh, David Hanna, Joseph Gomes, Dr. Christian G. Canlas, Prof. Martin Head-Gordon and Prof. Alexis T. Bell

      Article first published online: 14 OCT 2014 | DOI: 10.1002/cssc.201402443

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      Co-operative effect: Self-condensation of n-butanal to 2-ethylhexenal can be significantly enhanced by controlling the Brønsted acidity of M[BOND]OH groups present on the surface of amine-tethered silica supports. The spacing between the amines and M[BOND]OH groups is crucial to maximize their co-operative action and to minimize acid-base neutralization. The reaction pathway is analyzed by DFT calculations.

  44. Reviews

    1. Catalytic Oxidation of Biorefinery Lignin to Value-added Chemicals to Support Sustainable Biofuel Production

      Ruoshui Ma, Prof. Dr. Yan Xu and Prof. Xiao Zhang

      Article first published online: 1 OCT 2014 | DOI: 10.1002/cssc.201402503

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      Running on the environment platform: Lignin valorization to value-added platform chemicals may play a pivotal role in the sustainable production of biofuel from renewable biomass. This paper reviews oxidative lignin depolymerization chemistries employed in the papermaking process and oxidative catalysts that can be applied to biorefinery lignin to produce platform chemicals. The potential synergies of integrating new catalysts with commercial delignification chemistries are discussed.

  45. Communications

    1. Synthesis of Porous Inorganic Hollow Fibers without Harmful Solvents

      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.

  46. Cover Pictures

    1. You have free access to this content
      A Combinatorial Approach towards Water-Stable Metal–Organic Frameworks for Highly Efficient Carbon Dioxide Separation

      Zhigang Hu, Kang Zhang, Mei Zhang, Dr. Zhengang Guo, Prof. Jianwen Jiang and Prof. Dan Zhao

      Article first published online: 18 SEP 2014 | DOI: 10.1002/cssc.201402892

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      The Inside Back Cover shows the crystal structure of an ionized Zr metal–organic framework (MOF) and its selective adsorption of CO2 over N2 and CH4 for applications in clean energy and environmental sustainability. A library of 20 UiO-66-derived MOFs is synthesized in a combinatorial approach involving mixed ligand copolymerization and two post-synthetic modifications in tandem. These MOFs exhibit excellent water stabilities in a pH range of 1 to 12, together with high CO2 uptake capacities and selectivities as revealed by the analysis of 147 isotherms. This approach paves a way towards the systematic study of water-stable and affordable MOFs as highly efficient adsorbents for CO2 separation in the applications of post-combustion CO2 capture and natural gas upgrading. More details can be found in the Communication by Hu et al. on page ▪▪ (DOI: 10.1002/cssc.201402378).

  47. Minireviews

    1. Upgrading Carbon Dioxide by Incorporation into Heterocycles

      Dr. Bing Yu and Prof. Dr. Liang-Nian He

      Article first published online: 10 SEP 2014 | DOI: 10.1002/cssc.201402837

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      CO2 in heterocycles: Direct incorporation of CO2 as the entire “CO2” moiety or “C[DOUBLE BOND]O” fragments into organic substrates can be successfully performed by carbonylative/carboxylative cyclization of the nitrogen/oxygen/carbon-nucleophilic species with CO2 or initiated by C[BOND]H bond activation, resulting in the formation of various heterocycles. These techniques stimulate further interest in upgrading CO2 from a waste into an ideal and sustainable chemical feedstock in organic synthesis.

  48. Full Papers

    1. Proton Conductivity of Naphthalene Sulfonate Formaldehyde Resin-Doped Mesoporous Niobium and Tantalum Oxide Composites

      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.

    2. Dye-Sensitized Solar Cells with Improved Performance using Cone-Calix[4]Arene Based Dyes

      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.

  49. Communications

    1. Doubly Renewable Cellulose Polymer for Water-Based Coatings

      Cameron J. Tristram, Jennifer M. Mason, Prof. Dr. D. Bradley G. Williams and Dr. Simon F. R. Hinkley

      Article first published online: 28 AUG 2014 | DOI: 10.1002/cssc.201402590

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      Pulp Nonfiction: Wood pulp modified with cellulose-derived levulinic acid generates a “doubly-renewable” biopolymer—with >75 % renewable content—for industrial applications. The process is scalable and the polymer may be modified to improve its physical characteristics. The utility of this biobased polymer is demonstrated by the production of a novel coating formulation.

  50. Cover Pictures

    1. You have free access to this content
      Design and Functionalization of Photocatalytic Systems within Mesoporous Silica

      Dr. Xufang Qian, Dr. Kojirou Fuku, Dr. Yasutaka Kuwahara, Prof. Takashi Kamegawa, Prof. Kohsuke Mori and Prof. Hiromi Yamashita

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

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      The Front Cover image shows various photocatalysts such as nano-sized TiO2, transition-metal-oxide moieties (single-site photocatalysts), plasmonic metal nanostructures, and metal complexes displaying various light-excited photocatalytic processes. All of the processes occur in the nanospace of mesoporous silica-based materials, which possess high surface areas, transparency to UV and visible light as well as easily modified surfaces. More details can be found in the Minireview by Yamashita et al. on page ▪▪ (DOI: 10.1002/cssc.201400111), while more information about the research group is available in the Cover Profile (DOI: 10.1002/cssc.201400098).

    2. You have free access to this content
      Seaweed-Derived Heteroatom-Doped Highly Porous Carbon as an Electrocatalyst for the Oxygen Reduction Reaction

      Min Young Song, Hyean Yeol Park, Dae-Soo Yang, Dhrubajyoti Bhattacharjya and Prof. Jong-Sung Yu

      Article first published online: 27 MAY 2014 | DOI: 10.1002/cssc.201400099

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      The Back Cover picture shows how porous carbon with a high surface area and which is naturally doped with nitrogen and sulfur heteroatoms, can be prepared from the easily available seaweed Undaria pinnatifida (U. pinnatifida) as a single precursor for obtaining carbon with heteroatoms. U. pinnatifida is highly abundant, available at a low price, and proves to be a prime choice precursor for heteroatom-rich highly porous carbon materials as efficient metal-free electrocatalyst for the oxygen reduction reaction. More details can be found in the Full Paper by Yu et al. on page ▪▪ (DOI: 10.1002/cssc.201400049).

    3. You have free access to this content
      Rapid Trifluoromethylation and Perfluoroalkylation of Five-Membered Heterocycles by Photoredox Catalysis in Continuous Flow

      Natan J. W. Straathof, Hannes P. L. Gemoets, Dr. Xiao Wang, Prof. Dr. Jaap C. Schouten, Prof. Dr. Volker Hessel and Dr. Timothy Noël

      Article first published online: 27 MAY 2014 | DOI: 10.1002/cssc.201400100

      Thumbnail image of graphical abstract

      The Inside Cover picture shows how trifluoromethylated and perfluoroalkylated heterocycles can be prepared by continuous-flow photoredox catalysis utilizing [Ru(bpy)3] and blue light irradiation. Spectacular accelerations are observed in microreactors because of the homogeneous irradiation of the reaction sample and the optimal gas–liquid mass transfer. The mild reaction conditions should facilitate the implementation of this methodology in both academia and industry. More details can be found in the Full Paper by Noël et al. on page ▪▪ (DOI: 10.1002/cssc.201301282).

    4. You have free access to this content
      Electron-Acceptor-Dependent Light Absorption, Excited-State Relaxation, and Charge Generation in Triphenylamine Dye-Sensitized Solar Cells

      Dr. Renzhi Li, Dr. Min Zhang, Cancan Yan, Zhaoyang Yao, Jing Zhang and Prof. Peng Wang

      Article first published online: 12 FEB 2014 | DOI: 10.1002/cssc.201400088

      Thumbnail image of graphical abstract

      The Inside Cover picture underlines the dynamic torsional motions of excited-state dye molecules in dye-sensitized solar cells (DSCs), which mimic the photosynthesis of a green leaf for a sustainable energy supply. The enhancement of DSC performance can be facilitated through a combined theoretical and experimental investigation, exemplified here by changing the electron acceptor of light absorbers from cyanoacryclic acid to benzothiadiazole benzoic acid. More details can be found in the Full Paper by Wang et al. on page ▪▪ (DOI: 10.1002/cssc.201402806).

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