ChemSusChem

Cover image for Vol. 8 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: 7.657

ISI Journal Citation Reports © Ranking: 2014: 18/157 (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

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  1. Communications

    1. N-Doped Carbon-Coated Tungsten Oxynitride Nanowire Arrays for Highly Efficient Electrochemical Hydrogen Evolution

      Qun Li, Wei Cui, Dr. Jingqi Tian, Dr. Zhicai Xing, Qian Liu, Prof. Wei Xing, Prof. Abdullah M. Asiri and Prof. Xuping Sun

      Article first published online: 29 JUN 2015 | DOI: 10.1002/cssc.201500398

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      Who WON the race? N-Doped carbon-coated tungsten oxynitride nanowire arrays on carbon cloth (WON@NC NAs/CC) are prepared by annealing the WO3 NAs/CC precursor under an Ar atmosphere in the presence of dicyandiamide and are used as a 3 D hydrogen evolution cathode with superior activity and stability over the pH 0–14 range. PBS=phosphate-buffered saline, RHE=reversible hydrogen electrode.

  2. Cover Profiles

    1. Mild and Robust Redox-Neutral Pd/C-Catalyzed Lignol β-O-4′ Bond Cleavage Through a Low-Energy-Barrier Pathway

      Maxim V. Galkin, Dr. Christian Dahlstrand and Dr. Joseph S. M. Samec

      Article first published online: 26 JUN 2015 | DOI: 10.1002/cssc.201500750

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      “A better understanding of the lignin depolymerization mechanism opens an opportunity…” This and more about the story behind the research that inspired the Cover image is presented in the Cover Profile. More details can be found in the Communication by Galkin et al.: 10.1002/cssc.201500117. View the Front Cover here: 10.1002/cssc.201500751.

  3. Full Papers

    1. Nanocomposite Semi-Solid Redox Ionic Liquid Electrolytes with Enhanced Charge-Transport Capabilities for Dye-Sensitized Solar Cells

      Dr. Iwona A. Rutkowska, Dr. Magdalena Marszalek, Justyna Orlowska, Weronika Ozimek, Dr. Shaik M. Zakeeruddin, Prof. Pawel J. Kulesza and Prof. Michael Grätzel

      Article first published online: 26 JUN 2015 | DOI: 10.1002/cssc.201403475

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      Apple of my I: Iodine-modified Pt nanoparticles promote I[BOND]I bond splitting and enhance electron transfer in an I3/I ionic liquid electrolyte. If the nanoparticles are utilized together with carbon nanotubes, the electrolyte becomes more solid but is still characterized by a fast charge-transport coefficient of 1×10−6 cm2 s−1. Good power-conversion efficiencies are achieved using this semisolid electrolyte in dye-sensitized solar cells.

    2. Highly Stable Na2/3(Mn0.54Ni0.13Co0.13)O2 Cathode Modified by Atomic Layer Deposition for Sodium-Ion Batteries

      Dr. Karthikeyan Kaliyappan, Dr. Jian Liu, Andrew Lushington, Ruying Li and Prof. Xueliang Sun

      Article first published online: 26 JUN 2015 | DOI: 10.1002/cssc.201500155

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      Put a coat on! Atomic layer deposition (ALD) is adopted to increase the cyclic stability of Na2/3(Mn0.54Ni0.13Co0.13)O2 cathodes for high-cutoff-voltage cycling. Cathodes coated with a Al2O3 film after two ALD cycles displays a high discharge capacity of at 1C discharge current rate and a slightly decreased capacity at 15C in the voltage range between 2 and 4.5 V along with better cyclic performances; the reported values are among the best reported so far for sodium-ion batteries constructed using various P2-type cathodes.

    3. Molecular Engineering of Organic Dyes with a Hole-Extending Donor Tail for Efficient All-Solid-State Dye-Sensitized Solar Cells

      Jianfeng Lu, Dr. Yu-Cheng Chang, Hsu-Yang Cheng, Dr. Hui-Ping Wu, Prof. Yibing Cheng, Prof. Mingkui Wang and Prof. Eric Wei-Guang Diau

      Article first published online: 26 JUN 2015 | DOI: 10.1002/cssc.201500309

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      Dye hard: Hole-extending donor–acceptor–π–acceptor (D–A–π–A) organic dyes are designed and synthesized for all-solid-state dye-sensitized solar cells, and a power conversion efficiency of 5.5 % is achieved through co-sensitization with a new porphyrin dye, which extended the spectral response to 800 nm.

  4. Cover Pictures

    1. You have free access to this content
      An Organic Catalyst for Li–O2 Batteries: Dilithium Quinone-1,4-Dicarboxylate

      Jia Liu, Dr. Stéven Renault, Dr. Daniel Brandell, Dr. Torbjörn Gustafsson, Prof. Dr. Kristina Edström and Dr. Jiefang Zhu

      Article first published online: 26 JUN 2015 | DOI: 10.1002/cssc.201500761

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      The Inside Cover picture shows that a Li–O2 battery is expected to be used in electric vehicle applications due to its high theoretical specific energy. A typical Li–O2 battery contains a lithium-metal anode, a Li+-containing electrolyte, and a porous O2 cathode. A solid organic catalyst, dilithium quinone-1,4-dicarboxylate (Li2C8H2O6) is developed for the oxygen evolution reaction (OER) occurring in the Li–O2 battery. The electrocatalytic performance is evaluated by following the degradation of Li2O2 (depicted in the bottom right corner) during the charge process in a Li–O2 cell using in situ XRD and operando synchrotron radiation powder XRD measurements. The results indicate that the electrocatalytic activity of Li2C8H2O6 is similar to that of commercial Pt. The Li2O2 decomposition in a cell using Li2C8H2O6 as catalyst follows a pseudo-zero-order reaction, virtually without any side reactions. More details can be found in the Full paper by Liu et al. (DOI: 10.1002/cssc.201500381).

  5. Reviews

    1. Synthesis of Cyclic Carbonates from Epoxides and Carbon Dioxide by Using Organocatalysts

      Dr. Mirza Cokoja, Michael E. Wilhelm, Michael H. Anthofer, Prof. Dr. Dr. Wolfgang A. Herrmann and Prof. Dr. Fritz E. Kühn

      Article first published online: 26 JUN 2015 | DOI: 10.1002/cssc.201500161

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      Sustaining cycles: This review presents the state-of-the art strategies to convert carbon dioxide and epoxides into cyclic carbonates by using bifunctional organocatalysts with special regard to activity, carbon footprints, recycling, and the applicability of the highlighted systems on a large scale.

  6. Cover Pictures

    1. You have free access to this content
      Lithium Storage in Microstructures of Amorphous Mixed-Valence Vanadium Oxide as Anode Materials

      Di Zhao, Lirong Zheng, Ying Xiao, Xia Wang and Prof. Minhua Cao

      Article first published online: 26 JUN 2015 | DOI: 10.1002/cssc.201500811

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      The Back Cover picture shows the hydrangea-like amorphous mixed-valence VOx microspheres (a-VOx MSs), which were synthesized through a facile solvothermal method followed by controlled calcination. The a-VOx MSs show excellent lithium-storage performance in terms of high specific capacity, good rate capability, and long-term stability upon extended cycling. The excellent lithium storage performance can be attributed to the combined effect of the unique hydrangea-like structure, the mixed-valence, the amorphous nature, and the modification of the local V[BOND]O co-ordinations. More details can be found in the Full Paper by Zhao et al. (DOI: 10.1002/cssc.201500256).

    2. You have free access to this content
      Catalytic Oxidative Carbonylation of Amino Moieties to Ureas, Oxamides, 2-Oxazolidinones, and Benzoxazolones

      Dr. Raffaella Mancuso, Dr. Dnyaneshwar S. Raut, Dr. Nicola Della Ca', Dr. Francesco Fini, Prof. Dr. Carla Carfagna and Prof. Dr. Bartolo Gabriele

      Article first published online: 26 JUN 2015 | DOI: 10.1002/cssc.201500760

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      The Inside Back cover picture shows a recyclable catalytic method for the synthesis of ureas, oxamides, 2-oxazolidinones, and benzoxazolones by direct oxidative carbonylation of amines, β-amino alcohols, and 2-aminophenols. Reactions are carried out in an ionic liquid (IL) as the solvent ([Bmim][BF4]) at 100 °C and a pressure of 20 bar (4:1 mixture of CO–air) under non-explosive conditions and in the presence of catalytic amounts of PdI2 (0.2–1 mol %) in conjunction with KI (KI/PdI2 molar ratio: 10). The IL–catalyst system could be recycled several times without appreciable loss of activity whereas the products could be easily recovered from the reaction mixture by extraction with Et2O followed by crystallization. The ethereal solvent used for extraction could also be easily recovered and reused. More details can be found in the Full Paper by Mancuso et al. (DOI: 10.1002/cssc.201500343).

    3. You have free access to this content
      Mild and Robust Redox-Neutral Pd/C-Catalyzed Lignol β-O-4′ Bond Cleavage Through a Low-Energy-Barrier Pathway

      Maxim V. Galkin, Dr. Christian Dahlstrand and Dr. Joseph S. M. Samec

      Article first published online: 26 JUN 2015 | DOI: 10.1002/cssc.201500751

      Thumbnail image of graphical abstract

      The Cover picture shows a simple and efficient protocol for cleavage of the β-O-4’ bond in lignin model compounds catalyzed by Pd/C under redox-neutral conditions. The reactions are carried out at 80 °C in air using a green solvent system to yield the aryl ketones in near quantitative yields. Mild reaction conditions and absence of hydrogen allow a selective β-O-4’ bond cleavage without reduction of the aromatic rings. Mechanistic studies support a transfer hydrogenolysis pathway. More details on the reaction mechanism and on the advantages of the presented approach can be found in the Communication by Galkin et al. (DOI: 10.1002/cssc.201500117).

  7. Communications

    1. Thiazolylidene-Catalyzed Cleavage of Methyl Oleate-Derived α-Hydroxy Ketone to the Corresponding Free Aldehydes

      Elsa Deruer, Dr. Nicolas Duguet and Prof. Marc Lemaire

      Article first published online: 26 JUN 2015 | DOI: 10.1002/cssc.201500462

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      Thiazolylidene means business: The α-hydroxy ketone-derived from methyl oleate is cleaved under nonoxidative conditions to yield the corresponding aldehydes. The reaction proceeds through a retro-benzoin process catalyzed by a thiazolylidene species. The aldehydes produced are in equilibrium with their corresponding symmetric acyloins and can be recovered by distillation.

  8. Full Papers

    1. Heterojunction Synergies in Titania-Supported Gold Photocatalysts: Implications for Solar Hydrogen Production

      Dr. Vedran Jovic, Prof. Kevin E. Smith, Prof. Hicham Idriss and Dr. Geoffrey I. N. Waterhouse

      Article first published online: 24 JUN 2015 | DOI: 10.1002/cssc.201500126

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      Phase to phase: We probe the elusive anatase–rutile synergy that is critical to the high H2 production activity of Au/P25 TiO2 photocatalysts in alcohol/water mixtures under UV excitation. Our experimental data provide direct evidence that electrons photoexcited across the rutile band gap move to anatase lattice traps through interfacial heterojunctions, which thereby decreases electron–hole recombination rates and increases H2 evolution rates.

    2. AlF3 Surface-Coated Li[Li0.2Ni0.17Co0.07Mn0.56]O2 Nanoparticles with Superior Electrochemical Performance for Lithium-Ion Batteries

      Dr. Shuwei Sun, Dr. Yanfeng Yin, Dr. Ning Wan, Dr. Qing Wu, Dr. Xiaoping Zhang, Dr. Du Pan, Dr. Ying Bai and Dr. Xia Lu

      Article first published online: 24 JUN 2015 | DOI: 10.1002/cssc.201500143

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      Just a thin AlF3 layer: An AlF3 surface layer acts as a buffer to prevent the direct contact of the electrode with the electrolyte and, thus, enhances significantly the electrochemical performance and thermal stability. At the same time, it can largely suppress the undesirable growth of solid electrolyte interphase (SEI) film and, therefore, stabilizes the structure upon cycling.

    3. Screen-Printing of ZnO Nanostructures from Sol–Gel Solutions for Their Application in Dye-Sensitized Solar Cells

      Dr. Kuhu Sarkar, Erik V. Braden, Shannon A. Bonke, Prof. Dr. Udo Bach and Prof. Dr. Peter Müller-Buschbaum

      Article first published online: 24 JUN 2015 | DOI: 10.1002/cssc.201500450

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      Screen-printed ZnO nanostructures: Simple routes to produce dye-sensitized solar cells (DSSCs) by just printing the commonly used sol–gel system fail and more elaborated approaches are required. The synthesis of metal oxide nanostructures using the diblock copolymer-assisted sol–gel route can be successfully combined with standard printing methods to fabricate DSSCs, in which ZnO nanostructures emerge as a promising alternative to the usually applied TiO2.

    4. Processes forming Gas, Tar, and Coke in Cellulose Gasification from Gas-Phase Reactions of Levoglucosan as Intermediate

      Asuka Fukutome, Prof. Dr. Haruo Kawamoto and Prof. Dr. Shiro Saka

      Article first published online: 23 JUN 2015 | DOI: 10.1002/cssc.201500275

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      Towards coke-/tar-free gasification: Gaseous levoglucosan (LG) is gasified cleanly without the formation of any dehydration products (coke, furans, and aromatics). Coking occurs upon the cooling of LG to form the molten phase, in which intermolecular hydrogen bonding serves as an acid catalyst to promote dehydration.

    5. High-Performance Aqueous/Organic Dye-Sensitized Solar Cells Based on Sensitizers Containing Triethylene Oxide Methyl Ether

      Dr. Ryan Yeh-Yung Lin, Feng-Ling Wu, Chun-Ting Li, Pei-Yu Chen, Prof. Kuo-Chuan Ho and Prof. Jiann T. Lin

      Article first published online: 22 JUN 2015 | DOI: 10.1002/cssc.201500589

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      Spaced for efficiency: The wettability and lithium-ion trapping ability of phenothiazine sensitizers are intensified with the incorporation of the triethylene oxide methyl ether entity; this leads to highly efficient aqueous and organic dye-sensitized solar cells.

    6. Polystyrene-Templated Aerosol Synthesis of MoS2–Amorphous Carbon Composite with Open Macropores as Battery Electrode

      Seung Ho Choi and Prof. Yun Chan Kang

      Article first published online: 22 JUN 2015 | DOI: 10.1002/cssc.201500063

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      Void, not dense: Macroporous MoS2–amorphous carbon (MoS2–AC) composite microspheres with excellent Li- and Na-ion storage properties are prepared by means of one-pot spray pyrolysis. The macroporous composite microspheres have a high surface area in contact with liquid electrolyte and exhibits overall impressive Li- and Na-ion storage properties compared to dense composite microspheres.

    7. Catalytic Oxidative Carbonylation of Amino Moieties to Ureas, Oxamides, 2-Oxazolidinones, and Benzoxazolones

      Dr. Raffaella Mancuso, Dr. Dnyaneshwar S. Raut, Dr. Nicola Della Ca', Dr. Francesco Fini, Prof. Dr. Carla Carfagna and Prof. Dr. Bartolo Gabriele

      Article first published online: 18 JUN 2015 | DOI: 10.1002/cssc.201500343

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      Add value and recycle: We report the first general recyclable, catalytic oxidative carbonylation of amines, β-amino alcohols, and 2-aminophenols to ureas, oxamides, oxazolidinones, and benzoxazolones depending on carbonylation conditions. In all cases, the system catalyst/solvent (that is, an ionic liquid) could be easily recycled several times without appreciable loss of activity.

    8. Role of Exposed Surfaces on Zinc Oxide Nanostructures in the Catalytic Ethanol Transformation

      Marivi V. Morales, Dr. Esther Asedegbega-Nieto, Dr. Ana Iglesias-Juez, Prof. Inmaculada Rodríguez-Ramos and Prof. Antonio Guerrero-Ruiz

      Article first published online: 18 JUN 2015 | DOI: 10.1002/cssc.201500425

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      The missing zinc: Evidence is presented that indicates that structural differences in a series of ZnO samples can be correlated with their catalytic selectivity in the transformation of bioethanol into acetaldehyde. Detailed detection and characterization of the acid centers exposed at the ZnO surfaces leads us to associate these sites with the formation of ethylene in the case of catalysts with low surface areas.

    9. Acid-Functionalized Mesoporous Carbon: An Efficient Support for Ruthenium-Catalyzed γ-Valerolactone Production

      Dr. Alberto Villa, Dr. Marco Schiavoni, Dr. Carine E. Chan-Thaw, Dr. Pasquale F. Fulvio, Dr. Richard T. Mayes, Dr. Sheng Dai, Dr. Karren L. More, Dr. Gabriel M. Veith and Prof. Laura Prati

      Article first published online: 18 JUN 2015 | DOI: 10.1002/cssc.201500331

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      Which acid? Ordered mesoporous carbons are functionalized using P- and S-containing acid groups before the addition of Ru. The presence of S groups deactivates the Ru catalysts strongly, whereas the presence of P groups enhances the activity of the catalyst in levulinic acid hydrogenation and its durability.

    10. The Active Molybdenum Oxide Phase in the Methanol Oxidation to Formaldehyde (Formox Process): A DFT Study

      Marcos Rellán-Piñeiro and Prof. Núria López

      Article first published online: 17 JUN 2015 | DOI: 10.1002/cssc.201500315

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      Vacancies required: A density functional theory based study illustrates the reaction network for the conversion of methanol to formaldehyde with molybdenum oxide catalysts and indicates that catalyst activity is linked to the formation of oxygen vacancies at reasonable energy costs. Fe dopants in the Formox process facilitate the selective oxidation to formaldehyde by increasing the reversibility of the MoVI[BOND]MoIV redox pair.

    11. 3D Networked Tin Oxide/Graphene Aerogel with a Hierarchically Porous Architecture for High-Rate Performance Sodium-Ion Batteries

      Xiuqiang Xie, Shuangqiang Chen, Dr. Bing Sun, Prof. Dr. Chengyin Wang and Prof. Dr. Guoxiu Wang

      Article first published online: 16 JUN 2015 | DOI: 10.1002/cssc.201500149

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      Explore the pores: 3 D SnO2/graphene aerogels with a hierarchically porous structure are prepared by a facile self-assembly method, in which graphene nanosheets self-bridge to form 3D continuous networks with interconnected porous channels and SnO2 nanoparticles are homogeneously loaded on the graphene nanosheets. The integration of SnO2 nanoparticles leads to fast Na+ diffusion and electronic conductivity, giving rise to a promising high-rate performance as anode in sodium-ion batteries.

    12. Towards Stable Lithium–Sulfur Batteries with a Low Self-Discharge Rate: Ion Diffusion Modulation and Anode Protection

      Wen-Tao Xu, Hong-Jie Peng, Prof. Dr. Jia-Qi Huang, Chen-Zi Zhao, Xin-Bing Cheng and Prof. Dr. Qiang Zhang

      Article first published online: 16 JUN 2015 | DOI: 10.1002/cssc.201500428

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      All about me! The self-discharge rate of a stable lithium–sulfur cell can be controlled by anode protection from attack of polysulfides or through diffusion control of polysulfides by an ion-selective membrane.

  9. Reviews

    1. Safer Electrolytes for Lithium-Ion Batteries: State of the Art and Perspectives

      Julian Kalhoff, Dr. Gebrekidan Gebresilassie Eshetu, Dr. Dominic Bresser and Prof. Stefano Passerini

      Article first published online: 15 JUN 2015 | DOI: 10.1002/cssc.201500284

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      Safe and sound: The large-scale application of lithium-ion batteries is currently hindered by severe safety concerns when the cells are exposed to mechanical, thermal, or electrical abuse conditions. State-of-the-art electrolyte systems and potential alternatives are briefly surveyed, with a particular focus on their inherent safety characteristics.

  10. Highlights

    1. Silylations of Arenes with Hydrosilanes: From Transition-Metal-Catalyzed C[BOND]X Bond Cleavage to Environmentally Benign Transition-Metal-Free C[BOND]H Bond Activation

      Dr. Zheng Xu and Prof. Dr. Li-Wen Xu

      Article first published online: 12 JUN 2015 | DOI: 10.1002/cssc.201500467

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      Sustainable organosilicon chemistry: New catalytic methodologies for the silylation of aromatic compounds through C[BOND]X bond cleavage or C[BOND]H bond activation have been successfully developed in the past decades. Environmentally benign, transition-metal-free potassium tert-butoxide-catalyzed silylations of heterocycles are an important step forward in synthetic chemistry. enabling better atom economy in line with green chemistry principles.

  11. Communications

    1. Titanium(IV) in the Organic-Structure-Directing-Agent-Free Synthesis of Hydrophobic and Large-Pore Molecular Sieves as Redox Catalysts

      Dr. Jingui Wang, Prof. Dr. Toshiyuki Yokoi, Prof. Dr. Junko N. Kondo, Prof. Dr. Takashi Tatsumi and Prof. Dr. Yanli Zhao

      Article first published online: 12 JUN 2015 | DOI: 10.1002/cssc.201500443

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      Low cost comes true: Organic-structure-directing agents (OSDAs) are the most expensive ingredients among the initial raw materials used for the synthesis of molecular sieves. In this work, an OSDA-free process is developed to prepare large-pore BEA-type molecular sieves containing titanium(IV) as the framework element. The prepared molecular sieves show enhanced activity for the epoxidation of bulky alkenes.

  12. Full Papers

    1. A New Process for Maleic Anhydride Synthesis from a Renewable Building Block: The Gas-Phase Oxidehydration of Bio-1-butanol

      Dr. Giulia Pavarelli, Juliana Velasquez Ochoa, Dr. Aurora Caldarelli, Francesco Puzzo, Prof. Fabrizio Cavani and Dr. Jean-Luc Dubois

      Article first published online: 12 JUN 2015 | DOI: 10.1002/cssc.201500095

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      MA and PA together: Maleic anhydride (MA) can be produced by the one-pot oxidehydration of bio-1-butanol with a vanadyl pyrophosphate catalyst. The reaction mechanism includes the oxidation of butenes to crotonaldehyde and the oxidation of the latter to either furan or maleic acid, both of which are transformed to produce maleic anhydride. A non-negligible amount of phthalic anhydride (PA) is also formed.

    2. Layered Graphene–Hexagonal BN Nanocomposites: Experimentally Feasible Approach to Charge-Induced Switchable CO2 Capture

      Dr. Xin Tan, Dr. Liangzhi Kou and Prof. Sean C. Smith

      Article first published online: 12 JUN 2015 | DOI: 10.1002/cssc.201500026

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      Hybrid boron nitride and graphene nanosheets: An experimentally feasible strategy to charge up the wide-gap hexagonal boron nitride (h-BN) for charge-controlled switchable CO2 capture is presented. Extra electrons might be effectively transferred from the high-mobility graphene (G) layer utilized into h-BN layer on the surface of G such that CO2 capture/release can be simply controlled and reversed by switching on/off the charge states of the hybrid BN/G system.

    3. An Organic Catalyst for Li–O2 Batteries: Dilithium Quinone-1,4-Dicarboxylate

      Jia Liu, Dr. Stéven Renault, Dr. Daniel Brandell, Dr. Torbjörn Gustafsson, Prof. Dr. Kristina Edström and Dr. Jiefang Zhu

      Article first published online: 12 JUN 2015 | DOI: 10.1002/cssc.201500381

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      Under operation: Rechargeable Li–O2 battery have attracted considerable attention, due to its much higher theoretical specific energy. For its practical application, it is critical to develop an effective electrocatalyst especially for the OER process to achieve satisfactory energy efficiency, rate capability and cyclability. A new solid organic electrocatalyst, dilithium quinone-1,4-dicarboxylate (Li2C8H2O6) is expected to overcome the shortcomings of inorganic catalysts and is characterized using operando synchrotron radiation powder XRD.

  13. Communications

    1. Catalytic Production of Branched Small Alkanes from Biohydrocarbons

      Shin-ichi Oya, Daisuke Kanno, Dr. Hideo Watanabe, Dr. Masazumi Tamura, Dr. Yoshinao Nakagawa and Prof. Dr. Keiichi Tomishige

      Article first published online: 11 JUN 2015 | DOI: 10.1002/cssc.201500375

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      If you want to hang out, you′ve gotta branch out, alkanes: Selective dissociation of internal CH2[BOND]CH2 bonds located between branches in squalane proceeds over Ru/CeO2 without skeletal isomerization or aromatization, as compared to conventional methods using metal-acid bifunctional catalysts. The small alkanes produced are suitable components for biobased liquid fuels because of their branched structures.

    2. Low-Temperature Synthesis of Hierarchical Amorphous Basic Nickel Carbonate Particles for Water Oxidation Catalysis

      Yisu Yang, Dr. Fengli Liang, Mengran Li, Dr. Thomas E. Rufford, Dr. Wei Zhou and Prof. Dr. Zhonghua Zhu

      Article first published online: 11 JUN 2015 | DOI: 10.1002/cssc.201500182

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      …, that′s amor-phous: Hierarchical basic nickel carbonate particles are prepared at temperatures as low as 60 °C, using an evaporation-induced precipitation process. The products exhibited outstanding catalytic activities in the oxygen evolution reaction (OER), as compared to precious-metal-oxide catalysts such as RuO2 and IrO2. These results suggest the potential application of easily prepared hierarchical basic nickel carbonate particles as cheap and robust OER catalysts with high activity.

  14. Concepts

    1. The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations

      Joseph H. Montoya, Charlie Tsai, Dr. Aleksandra Vojvodic and Prof. Jens K. Nørskov

      Article first published online: 10 JUN 2015 | DOI: 10.1002/cssc.201500322

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      Towards renewable fertilizer: The synthesis of ammonia has played a key role in our society for its uses in fertilizer and other reactive nitrates. The traditional Haber–Bosch method of this synthesis requires extensive capital, making alternative technologies attractive. We outline an alternative route that might be achieved at ambient conditions. Using DFT, we demonstrate why an electrochemical process is severely limited by the energetics of metal catalysts.

  15. Full Papers

    1. Carbon Nanotubes as Support in the Platinum-Catalyzed Hydrolytic Dehydrogenation of Ammonia Borane

      Wenyao Chen, Dr. Xuezhi Duan, Dr. Gang Qian, Prof. De Chen and Prof. Xinggui Zhou

      Article first published online: 9 JUN 2015 | DOI: 10.1002/cssc.201500228

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      Just gimme defects please: The hydrolytic dehydrogenation of ammonia borane by platinum nanoparticles (NPs) is used to investigate the chemistry of carbon nanotube (CNT) supports. The use of defect-rich CNTs, as compared to pristine CNTs and CNTs rich in oxygen groups, not only enhances the binding energy of platinum, leading to the highest hydrogen generation rate, but also inhibits the adsorption of boron-containing species and stabilizes the platinum NPs to resist the agglomeration, leading to the highest durability.

  16. Communications

    1. Solvent-Free Synthesis of Zeolite Crystals Encapsulating Gold–Palladium Nanoparticles for the Selective Oxidation of Bioethanol

      Jian Zhang, Dr. Liang Wang, Dr. Longfeng Zhu, Qinming Wu, Chunyu Chen, Xiong Wang, Yanyan Ji, Dr. Xiangju Meng and Prof. Feng-Shou Xiao

      Article first published online: 3 JUN 2015 | DOI: 10.1002/cssc.201500261

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      Inner strength: The conversion of bioethanol into valuable products is an important topic in biomass conversion. Bimetallic gold–palladium nanoparticles encapsulated in zeolite crystals synthesized by a solvent-free strategy exhibit superior catalytic activity, unique selectivity, and high stability in aerobic oxidation of bioethanol. These features are important for future practical applications of the AuPd@S-1 catalyst.

  17. Reviews

    1. Hydrogen Storage Materials for Mobile and Stationary Applications: Current State of the Art

      Qiwen Lai, Dr. Mark Paskevicius, Dr. Drew A. Sheppard, Prof. Craig E. Buckley, Dr. Aaron W. Thornton, Dr. Matthew R. Hill, Dr. Qinfen Gu, Dr. Jianfeng Mao, Dr. Zhenguo Huang, Prof. Hua Kun Liu, Dr. Zaiping Guo, Amitava Banerjee, Dr. Sudip Chakraborty, Prof. Rajeev Ahuja and Prof. Kondo-Francois Aguey-Zinsou

      Article first published online: 1 JUN 2015 | DOI: 10.1002/cssc.201500231

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      Hydrogen Holy Grail: Light materials that enable the safe and compact storage of hydrogen remain the bottleneck of the hydrogen economy. This review presents a critical analysis of progress made over the last 20 years following the initial discovery of hydrogen reversibility in NaAlH4, which is a light, complex hydride.

  18. Full Papers

    1. Lithium Storage in Microstructures of Amorphous Mixed-Valence Vanadium Oxide as Anode Materials

      Di Zhao, Lirong Zheng, Ying Xiao, Xia Wang and Prof. Minhua Cao

      Article first published online: 28 MAY 2015 | DOI: 10.1002/cssc.201500256

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      Flower power: Hydrangea-like amorphous mixed-valence VOx microspheres (a-VOx MSs) are designed and synthesized through a facile solvothermal method followed by controlled calcination. The VOx microspheres show excellent lithium-storage performance in terms of high capacity, good rate capability, and long-term stability upon extended cycling. Moreover, the morphology and structure remain intact after testing over 200 cycles.

    2. Self-Assembled 3D Graphene-Based Aerogel with Co3O4 Nanoparticles as High-Performance Asymmetric Supercapacitor Electrode

      Dr. Lijing Xie, Dr. Fangyuan Su, Longfei Xie, Xiaoming Li, Zhuo Liu, Qingqiang Kong, Xiaohui Guo, Yaoyao Zhang, Liu Wan, Prof. Kaixi Li, Prof. Chunxiang Lv and Prof. Chengmeng Chen

      Article first published online: 26 MAY 2015 | DOI: 10.1002/cssc.201500355

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      Carbon of Blinding Light: An asymmetric supercapacitor is fabricated using a three-dimensional Co3O4–reduced graphene oxide aerogel as cathode, hierarchical porous carbon (HPC) as anode, and 6 M aqueous KOH solution as electrolyte. Three as-fabricated CR2032 coin-type asymmetric supercapacitors in series can drive a light-emitting-diode (LED) bulb brightly for 30 min after charging for only 30 s.

  19. Communications

    1. Hierarchically Structured Hole Transport Layers of Spiro-OMeTAD and Multiwalled Carbon Nanotubes for Perovskite Solar Cells

      Jiyong Lee, Dr. Mini Mol Menamparambath, Dr. Jae-Yeol Hwang and Prof. Seunghyun Baik

      Article first published online: 26 MAY 2015 | DOI: 10.1002/cssc.201403462

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      Respect the hierarchy! Multiwalled carbon nanotubes (MWNTs) are embedded in spiro-OMeTAD to improve electrical conductivity. Perovskite solar cells employing a hierarchical hole transport layer (HTL) structure, comprising pure spiro-OMeTAD and spiro-OMeTAD/MWNT layers, show better blocking of back-electron transfer while fully exploiting the enhanced conductivity of the spiro-OMeTAD/MWNT material. The power conversion efficiency of these perovskite solar cells is improved, to 15.1 %.

    2. The Effect of Different Phosphorus Chemical States on an Onion-like Carbon Surface for the Oxygen Reduction Reaction

      Xiaoyan Sun, Junyuan Xu, Yuxiao Ding, Dr. Bingsen Zhang, Zhenbao Feng and Prof. Dang Sheng Su

      Article first published online: 13 MAY 2015 | DOI: 10.1002/cssc.201500154

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      Peeling back the layers: The bonding state of phosphorus on nanocarbon has a significant effect on the catalytic activity of the oxygen reduction reaction. The formation of C[BOND]O[BOND]P bonds improves the activity, whereas C[BOND]P bonds have an adverse effect on stabilizing key intermediates during the reaction owing to the distorted graphitic structure.

  20. Full Papers

    1. Synthesis and Nanostructures of Metal Selenide Precursors for Cu(In,Ga)Se2 Thin-Film Solar Cells

      Ji-Hyun Cha, Se Jin Noh and Prof. Duk-Young Jung

      Article first published online: 8 MAY 2015 | DOI: 10.1002/cssc.201403464

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      GaGa over nanoparticles: Variation of the gallium concentration in Cu(In0.7Ga0.3)Se2 nanoparticles (CIGSe NPs is investigated by sonochemical synthesis in hydrazine/ethylene glycol solution. The CIGSe device prepared by the nanoink solution based process exhibits a conversion efficiency of 5.17 %.

    2. Heterojunction Solar Cells Based on Silicon and Composite Films of Graphene Oxide and Carbon Nanotubes

      LePing Yu, Dr. Daniel Tune, Dr. Cameron Shearer and Prof. Joseph Shapter

      Article first published online: 8 MAY 2015 | DOI: 10.1002/cssc.201500169

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      Composite electrode: Graphene oxide (GO) sheets are used as the surfactant to disperse single-walled carbon nanotubes (CNT) in water to prepare GO/CNT electrodes that are applied on silicon to form a heterojunction that can be used in solar cells.

    3. Thermoelectric Properties of Nanowires with a Graphitic Shell

      Jong Woon Lee, Dr. Eun Kyung Lee, Dr. Byung Sung Kim, Dr. Jae Hyun Lee, Hee Goo Kim, Hyeon Sik Jang, Dr. Sung Woo Hwang, Dr. Byoung Lyong Choi and Prof. Dr. Dongmok Whang

      Article first published online: 4 MAY 2015 | DOI: 10.1002/cssc.201403492

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      Cool under fire: The electrical and thermal properties of Si and SiO2 nanowires with a few-layer graphitic shell are explored; these structures exhibit enhanced electrical properties but no increase in thermal conductivity. Phonons are transported through the core nanowire, which has a large cross-sectional area relative to that of the graphitic shell, and the main current path is the graphitic shell owing to its good electrical conductivity.

    4. Improvement of Energy Capacity with Vitamin C Treated Dual-Layered Graphene–Sulfur Cathodes in Lithium–Sulfur Batteries

      Jin Won Kim, Joey D. Ocon, Dr. Ho-Sung Kim and Prof. Dr. Jaeyoung Lee

      Article first published online: 29 APR 2015 | DOI: 10.1002/cssc.201500111

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      Take your vitamins: a dual-layered cathode design based on a sulfur-nanoparticle–graphene composite as the sulfur active layer and vitamin C reduced graphene oxide as the polysulfide absorption layer with high energy and power densities is proposed (over 600 mAh g−1 for 100 cycles at 1C).

  21. Communications

    1. Mild and Robust Redox-Neutral Pd/C-Catalyzed Lignol β-O-4′ Bond Cleavage Through a Low-Energy-Barrier Pathway

      Maxim V. Galkin, Dr. Christian Dahlstrand and Dr. Joseph S. M. Samec

      Article first published online: 29 APR 2015 | DOI: 10.1002/cssc.201500117

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      Don′t, cleave me this way: A Pd/C catalyzed redox neutral C[BOND]O bond cleavage of 2-aryloxy-1-arylethanols has been developed. The reactions are carried out at mild conditions to yield the aryl ketones in near quantitative yields. Addition of catalytic amounts of a hydrogen source activates the catalyst sites, and allow to perform the reactions under mild conditions. Mechanistic studies support a transfer hydrogenolysis pathway.

  22. Full Papers

    1. Ceramic Lithium Ion Conductor to Solve the Anode Coking Problem of Practical Solid Oxide Fuel Cells

      Dr. Wei Wang, Feng Wang, Yubo Chen, Jifa Qu, Prof. Moses O. Tadé and Prof. Zongping Shao

      Article first published online: 29 APR 2015 | DOI: 10.1002/cssc.201500028

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      No coke without fire: The high Li+ conductivity of Li0.33La0.56TiO3 (LLTO) in the Ni/LLTO catalyst successfully compensates surface lithium loss caused by evaporation through bulk diffusion and leads to a much better coking resistance, which is beneficial for the long-term stability of solid oxide fuel cells.

    2. Carbon-Nanotubes-Supported Pd Nanoparticles for Alcohol Oxidations in Fuel Cells: Effect of Number of Nanotube Walls on Activity

      Jin Zhang, Dr. Shanfu Lu, Prof. Yan Xiang, Prof. Pei Kang Shen, Dr. Jian Liu and Prof. San Ping Jiang

      Article first published online: 21 APR 2015 | DOI: 10.1002/cssc.201500107

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      Three′s the magic number: Palladium nanoparticles (NPs) with controlled particle size are uniformly assembled on the surface of carbon nanotubes CNTs with varying numbers of walls. Pd NPs supported on triple-walled CNTs (TWNTs) have the highest mass activity and stability for methanol, ethanol and ethylene glycol oxidation reactions, as compared to Pd NPs supported on single-walled and multi-walled CNTs.

  23. Cover Pictures

    1. You have free access to this content
      Enhancing the Performance of a Robust Sol–Gel-Processed p-Type Delafossite CuFeO2 Photocathode for Solar Water Reduction

      Mathieu S. Prévot, Dr. Néstor Guijarro and Prof. Kevin Sivula

      Article first published online: 17 APR 2015 | DOI: 10.1002/cssc.201500314

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      The Back Cover picture shows a solution-processed thin film of semi-conducting CuFeO2 held in front of the sun. An impressive performance is reported using this material as a photocathode for the reduction of water molecules to hydrogen (as depicted in the bottom right corner) under solar radiation. In addition to being fully solution processable, the copper-based delafossite (crystal structure is shown in the top right corner) is a class of material known for being stable in aqueous environments. Moreover, it is only composed of earth-abundant materials, as suggested by the delafossite ore shown in the bottom right corner. Overall, these properties make p-type CuFeO2 a very attractive material in the quest for inexpensive, sustainable, and stable direct solar water splitting for the generation of carbon-free hydrogen. More details can be found in the Full Paper by Prévot et al. (DOI: 10.1002/cssc.201403146).

  24. Full Papers

    1. Niobium Doping Effects on TiO2 Mesoscopic Electron Transport Layer-Based Perovskite Solar Cells

      Dong Hoe Kim, Gill Sang Han, Won Mo Seong, Jin-Wook Lee, Byeong Jo Kim, Prof. Nam-Gyu Park, Prof. Kug Sun Hong, Dr. Sangwook Lee and Prof. Hyun Suk Jung

      Article first published online: 17 APR 2015 | DOI: 10.1002/cssc.201403478

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      Nb-doped TiO2 nanoparticles for perovskite solar cell: TiO2 nanoparticles doped with n-type Nb5+ have a diameter of 30 nm and a pure anatase phase; they are used for fabricating perovskite solar cells. Light doping increases the photovoltaic energy conversion efficiency by 10 % due to improved electron injection/transport properties of the nanoparticle-based electron transport layer.

    2. On the Role of Interfaces in Planar-Structured HC(NH2)2PbI3 Perovskite Solar Cells

      Dong-Jin Seol, Jin-Wook Lee and Nam-Gyu Park

      Article first published online: 16 APR 2015 | DOI: 10.1002/cssc.201403442

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      Focus on interfaces: A planar-junction perovskite solar cell composed of TiO2/formamidinium lead iodide(FAPbI3)/spiro-MeOTAD is fabricated, in which interfaces of FAPbI3 in contact with TiO2 and spiro-MeOTAD are modified to investigate the role of each interface. The TiO2/FAPbI3 interface is found to play an important role in determining short-circuit photocurrent, while the FAPbI3/spiro-MeOTAD interfacial role is involved in governing open-circuit voltage.

    3. Organic Dyes Incorporating the Dithieno[3,2-f:2′,3′-h]quinoxaline Moiety for Dye-Sensitized Solar Cells

      Jen-Shyang Ni, Wei-Siang Kao, Hao-Ju Chou and Prof. Jiann T. Lin

      Article first published online: 8 APR 2015 | DOI: 10.1002/cssc.201500193

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      More acceptance: New donor–acceptor′–acceptor-type sensitizers with a rigid dithieno[3,2-f:2′,3′-h]quinoxaline segment comprised of electron-rich and electron-deficient units in the conjugated spacer are proposed for dye-sensitized solar cells. Their structure gives rise to broad absorption spectra and high molar extinction coefficient, resulting in power conversion efficiencies higher than that of the N719 dye.

  25. Communications

    1. Hierarchical Vanadium Pentoxide Spheres as High-Performance Anode Materials for Sodium-Ion Batteries

      Dr. Dawei Su, Prof. Dr. Shixue Dou and Prof. Dr. Guoxiu Wang

      Article first published online: 30 MAR 2015 | DOI: 10.1002/cssc.201500139

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      In higher spheres: Hierarchical V2O5 spheres are synthesized and demonstrate a preferred (110) orientation, exposing more open interlayers of its crystal structure. When tested in sodium-ion batteries, the as-prepared V2O5 spheres achieve high discharge capacity, superior high rate capability, and excellent cyclability. The promising electrochemical performance is ascribed to the unique hierarchical spherical architecture and preferred exposure of the (110) crystal planes.

  26. Full Papers

    1. Very Important Paper

      Incorporation of a Metal Oxide Interlayer using a Virus-Templated Assembly for Synthesis of Graphene-Electrode-Based Organic Photovoltaics

      Dr. Yong Man Lee, Wanjung Kim, Dr. Young Hun Kim, Jung Kyu Kim, Ji-ryang Jang, Prof. Woo-Seok Choe, Prof. Jong Hyeok Park and Prof. Pil J. Yoo

      Article first published online: 25 MAR 2015 | DOI: 10.1002/cssc.201403487

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      Virus scan: The synthesis and incorporation of a WO3 interlayer into graphene-electrode-based organic photovoltaic (OPV) devices is developed by using an engineered biotemplate of M13 viruses. Owing to uniform deposition of the WO3 layer and maintenance of the electrical properties of the graphene electrode, a remarkable increase in the photoconversion efficiency (>20 %) relative to that of conventional OPVs can be obtained.

    2. Nanotubular Heterostructure of Tin Dioxide/Titanium Dioxide as a Binder-Free Anode in Lithium-Ion Batteries

      Myungjun Kim, Joobong Lee, Seonhee Lee, Seongrok Seo, Dr. Changdeuck Bae and Prof. Hyunjung Shin

      Article first published online: 20 MAR 2015 | DOI: 10.1002/cssc.201500005

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      Solid foundations: Arrays of TiO2, SnO2, heterotubular TiO2/SnO2, and TiO2/SnO2/TiO2 as binder-free anodes in lithium-ion batteries are successfully synthesized by using template-assisted atomic-layer deposition (ALD), which enables not only precise structural control, but also suppression of a large volume change in SnO2.

  27. Reviews

    1. Boundary Engineering for the Thermoelectric Performance of Bulk Alloys Based on Bismuth Telluride

      Hyeona Mun, Prof. Soon-Mok Choi, Prof. Kyu Hyoung Lee and Prof. Sung Wng Kim

      Article first published online: 17 MAR 2015 | DOI: 10.1002/cssc.201403485

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      Boundary engineering for thermoelectrics: For a further enhancement of the thermoelectric figure of merit, boundary engineering is demonstrated as one of the most effective ways to enhance the thermoelectric performance of conventional thermoelectric materials such as Bi2Te3, PbTe, and SiGe alloys. We review the boundary engineering strategy into two parts; 1) grain boundary engineering and 2) phase boundary engineering using Bi2Te3-based bulk alloys.

  28. Full Papers

    1. β-Functionalized Push–Pull Porphyrin Sensitizers in Dye-Sensitized Solar Cells: Effect of π-Conjugated Spacers

      Dr. Masatoshi Ishida, Daesub Hwang, Dr. Zhan Zhang, Yung Ji Choi, Juwon Oh, Dr. Vincent M. Lynch, Dr. Dong Young Kim, Prof. Dr. Jonanthan L. Sessler and Prof. Dr. Dongho Kim

      Article first published online: 6 MAR 2015 | DOI: 10.1002/cssc.201500085

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      Pushing through it: A series of new β-functionalized push–pull-structured porphyrin dyes are synthesized. Together, these dyes allow the effect of the π-conjugated spacer on the performance of dye-sensitized solar cells (DSSCs) to be assessed. The highest conversion efficiency in the present study (8.2 %) is achieved by using a doubly β-butadiene-linked porphyrin as the sensitizer with a cobalt-based redox shuttle as the mediator.

    2. Surfactant Effects on the Morphology and Pseudocapacitive Behavior of V2O5⋅H2O

      Aniu Qian, Kai Zhuo, Myung Sik Shin, Woo Won Chun, Bit Na Choi and Prof. Chan-Hwa Chung

      Article first published online: 25 FEB 2015 | DOI: 10.1002/cssc.201403477

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      Morphing into it: The effect of diverse surfactants on the morphology of V2O5H2O powders is studied. The pseudocapacitive behavior of V2O5H2O powders mediated by polyethylene glycol 6000exhibit a high capacitance at a scan rate of 5 mV s−1. Moreover, the V2O5H2O electrode mediated by Pluronic P-123 delivers a high capacitance with excellent stability after 200 cycles.

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