ChemPhysChem

Cover image for Vol. 13 Issue 12

Special Issue: Electrochemisty and Energy

August 27, 2012

Volume 13, Issue 12

Pages 2805–3060

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Essay
    9. Communication
    10. Articles
    1. You have free access to this content
      Cover Picture: Contrast in Electron-Transfer Mediation between Graphene Oxide and Reduced Graphene Oxide (ChemPhysChem 12/2012) (page 2805)

      Dr. Wiphada Hongthani, Dr. Avinash J. Patil, Prof. Stephen Mann and Dr. David J. Fermín

      Article first published online: 17 AUG 2012 | DOI: 10.1002/cphc.201290056

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      The cover picture shows a sub-monolayer of ssDNA-stabilised reduced graphene oxide assembled by electrostatic adsorption. The reduced graphene sheets are capable of mediating electron transfer from redox species in solution to electrode surfaces modified by an insulating self-assembled monolayer. This behaviour contrasts with the insulating properties of the graphene oxide precursor. Voltammetric and impedance responses provide information on density of state and electrochemical reactivity of these carbon-based nanostructures. Details can be found in the article by D. J. Fermín et al. on p. 2956 ff.

    2. You have free access to this content
      Inside Cover: Electrochemistry in Reverse Biased Dye Solar Cells and Dye/Electrolyte Degradation Mechanisms (ChemPhysChem 12/2012) (page 2806)

      Simone Mastroianni, Dr. Angelo Lembo, Prof. Thomas M. Brown, Dr. Andrea Reale and Prof. Aldo Di Carlo

      Article first published online: 17 AUG 2012 | DOI: 10.1002/cphc.201290057

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      Mismatched dye solar cells in modules can be forced to operate in reverse bias (RB). As shown on p. 2964 ff. by T. M. Brown et al., 0.4 V in RB with time has little effect on cell efficiency whereas harsher but real tests leads to increasing overpotentials at electrodes causing H2 evolution, dye degradation and breakdown.

  2. Editorial

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Essay
    9. Communication
    10. Articles
    1. You have free access to this content
      Photoelectrochemical Energy Conversion (pages 2807–2808)

      Prof. Hans-Joachim Lewerenz

      Article first published online: 23 MAR 2012 | DOI: 10.1002/cphc.201200199

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Essay
    9. Communication
    10. Articles
    1. Graphical Abstract: ChemPhysChem 12/2012 (pages 2811–2817)

      Article first published online: 17 AUG 2012 | DOI: 10.1002/cphc.201290058

  4. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Essay
    9. Communication
    10. Articles
    1. Changes in Direction (page 2823)

      Article first published online: 17 AUG 2012 | DOI: 10.1002/cphc.201200631

  5. Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Essay
    9. Communication
    10. Articles
    1. The Electrochemistry of Nanostructured Titanium Dioxide Electrodes (pages 2824–2875)

      Dr. Thomas Berger, Dr. Damián Monllor-Satoca, Milena Jankulovska, Dr. Teresa Lana-Villarreal and Dr. Roberto Gómez

      Article first published online: 29 JUN 2012 | DOI: 10.1002/cphc.201200073

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      Ubiquitous titania electrodes: The electrochemistry of nanostructured titanium dioxide electrodes is reviewed with a focus on the fundamental aspects that determine their behavior both in the dark and under illumination (see picture). Some applications in the fields of environmental remediation (heterogeneous photocatalysis), and energy saving (electrochromism), generation (artificial photosynthesis) and accumulation (Li-ion batteries) are also dealt with.

  6. Minireviews

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Essay
    9. Communication
    10. Articles
    1. Ultrafast Photoinduced Electron Transfer at Electrodes: The General Case of a Heterogeneous Electron-Transfer Reaction (pages 2877–2881)

      Prof. Dr. Lars Gundlach and Prof. Dr. Frank Willig

      Article first published online: 24 APR 2012 | DOI: 10.1002/cphc.201200151

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      Electron-transfer reaction dynamics at electrodes (see picture) have a long history of both theoretical modeling and experimental efforts to test such theories with contributions by many researchers. This Minireview reports on the most recent fundamental experimental data which have solved some of the long-standing issues and opened up the field to further experimental and theoretical progress.

    2. Interfacial Dynamics and Solar Fuel Formation in Dye-Sensitized Photoelectrosynthesis Cells (pages 2882–2890)

      Dr. Wenjing Song, Dr. Zuofeng Chen, Dr. Christopher R. K. Glasson, Dr. Kenneth Hanson, Hanlin Luo, Michael R. Norris, Dennis L. Ashford, Dr. Javier J. Concepcion, Dr. M. Kyle Brennaman and Dr. Thomas J. Meyer

      Article first published online: 19 JUN 2012 | DOI: 10.1002/cphc.201200100

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      Catch the sun: Dye-sensitized photoelectrosynthesis cells (DSPECs) represent a promising approach to solar fuels with solar-energy storage in chemical bonds. The targets are water splitting and carbon dioxide reduction by water to CO, other oxygenates, or hydrocarbons (see picture). A systematic basis for DSPECs comprises a modular approach with light absorption/excited-state electron injection, and catalyst activation assembled in integrated structures.

  7. Essay

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Essay
    9. Communication
    10. Articles
    1. Obituary: Dieter M. Kolb (1942–2011) (page 2891)

      Prof. Dr. Gerhard Ertl and Prof. Dr. Hans-Joachim Lewerenz

      Article first published online: 29 MAR 2012 | DOI: 10.1002/cphc.201200109

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  8. Communication

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Essay
    9. Communication
    10. Articles
    1. Stable Sensitization of ZnO by Improved Anchoring of Indoline Dyes (pages 2893–2897)

      Jane Falgenhauer, Christoph Richter, Dr. Hidetoshi Miura and Prof. Dr. Derck Schlettwein

      Article first published online: 6 JUN 2012 | DOI: 10.1002/cphc.201200085

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      Indoline dyes with additional anchor groups are studied as sensitizers for ZnO in view of potential applications in photovoltaics. Improved performance is observed, as well as a better adsorption of the dye on ZnO—even in the presence of competing coadsorbates—which leads to an increased stability of the dye-sensitized solar cells.

  9. Articles

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireviews
    8. Essay
    9. Communication
    10. Articles
    1. Epitaxial III–V Films and Surfaces for Photoelectrocatalysis (pages 2899–2909)

      Dr. Henning Döscher, Oliver Supplie, Matthias M. May, Philipp Sippel, Christian Heine, Dr. Andrés G. Muñoz, Dr. Rainer Eichberger, Prof. Hans-Joachim Lewerenz and Prof. Thomas Hannappel

      Article first published online: 13 AUG 2012 | DOI: 10.1002/cphc.201200390

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      Built for two: InP(100)-based half-cells show significant solar-to-hydrogen efficiencies, but require a bias due to insufficient voltage. Tandem absorber structures may provide both adequate potential and efficient utilization of the solar spectrum. The picture shows contour lines of calculated limiting conversion efficiencies for ideal monolithic tandem solar cells.

    2. Dynamic Response of Thin-Film Semiconductors to AC Voltage Perturbations (pages 2910–2918)

      Dr. Fabio La Mantia, Dr. Jelena Stojadinović, Prof. Dr. Monica Santamaria and Prof. Dr. Francesco Di Quarto

      Article first published online: 8 MAY 2012 | DOI: 10.1002/cphc.201200226

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      The other side counts: The charge accumulated on the metal/semiconductor (M/SC) junction interfaced with electrolyte (El) gives rise to an induced bound charge density, σ, which influences the ac response of the semiconductor in solution (see picture).

    3. Electrochemical Single-Molecule AFM of the Redox Metalloenzyme Copper Nitrite Reductase in Action (pages 2919–2924)

      Dr. Xian Hao, Prof. Dr. Jingdong Zhang, Prof. Dr. Hans E. M. Christensen, Prof. Dr. Hongda Wang and Prof. Dr. Jens Ulstrup

      Article first published online: 13 JUN 2012 | DOI: 10.1002/cphc.201200220

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      Bo(u)nd to act: We study the electrochemical behavior of the redox metalloenzyme copper nitrite reductase immobilized on a Au(111)-electrode surface modified by a self-assembled cysteamine molecular monolayer using a combination of cyclic voltammetry and electrochemically-controlled atomic force microscopy. The enzyme shows no voltammetric signals in the absence of nitrite substrate, whereas a strong reductive electrocatalytic signal appears in the presence of nitrite.

    4. Physical and Electrochemical Analysis of an Indoor–Outdoor Ageing Test of Large-Area Dye Solar Cell Devices (pages 2925–2936)

      Simone Mastroianni, Alessandro Lanuti, Dr. Stefano Penna, Dr. Andrea Reale, Prof. Thomas M. Brown, Prof. Aldo Di Carlo and Prof. Franco Decker

      Article first published online: 13 AUG 2012 | DOI: 10.1002/cphc.201200110

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      The time of their life: The long-term lifetime of large-area dye solar cell devices was tested under outdoor conditions and indoors with continuous light soaking. Different degradation rates were found in outdoor samples with horizontally and vertically oriented cells, and in cells working at open-circuit voltage and maximum power point (see picture). Correlation between electrolyte triiodide depletion and degradation phenomena is analyzed.

    5. Iron Resonant Photoemission Spectroscopy on Anodized Hematite Points to Electron Hole Doping during Anodization (pages 2937–2944)

      Dr. Artur Braun, Qianli Chen, Dorota Flak, Dr. Giuseppino Fortunato, Dr. Krisztina Gajda-Schrantz, Prof. Dr. Michael Grätzel, Prof. Dr. Thomas Graule, Dr. Jinghua Guo, Dr. Tzu-Wen Huang, Dr. Zhi Liu, Anastasiya V. Popelo, Dr. Kevin Sivula, Dr. Hiroki Wadati, Pradeep P. Wyss, Liang Zhang and Prof. Dr. Junfa Zhu

      Article first published online: 5 JUN 2012 | DOI: 10.1002/cphc.201200074

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      Changing potential: Anodization of α-Fe2O3 (hematite) electrodes in alkaline electrolyte under constant potential conditions the electrode surface in a way that the properties of the material are altered, as determined by cyclic voltammetry, X-ray photoelectron spectroscopy, and near-edge X-ray absorption fine structure spectroscopy (see picture).

    6. Photocatalytic Generation of Syngas Using Combustion-Synthesized Silver Bismuth Tungstate (pages 2945–2955)

      Dr. Norma R. de Tacconi, Dr. Hari Krishna Timmaji, Dr. Wilaiwan Chanmanee, Dr. Muhammad N. Huda, Pranab Sarker, Dr. Csaba Janáky and Prof. Krishnan Rajeshwar

      Article first published online: 16 MAR 2012 | DOI: 10.1002/cphc.201200046

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      Silver bismuth tungstate nanoparticles are prepared by solution combustion synthesis, modified with a Pt co-catalyst, and finally used for the photogeneration of syngas (CO+H2). Formic acid is used to produce CO2 in situ and subsequently reduce it to CO. The photocatalytic activity of these nanoparticles is superior to that of nanoparticles prepared by solid-state synthesis.

    7. Contrast in Electron-Transfer Mediation between Graphene Oxide and Reduced Graphene Oxide (pages 2956–2963)

      Dr. Wiphada Hongthani, Dr. Avinash J. Patil, Prof. Stephen Mann and Dr. David J. Fermín

      Article first published online: 2 AUG 2012 | DOI: 10.1002/cphc.201200407

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      Electron-launching nanopads: Chemically reduced graphene oxide mediates the electron-transfer responses across insulating molecular layers at electrode surfaces. The significant contrast in electrochemical reactivity (see picture) with graphene-oxide sheets provides information on changes of the density of states brought about by the chemical reduction step.

    8. Electrochemistry in Reverse Biased Dye Solar Cells and Dye/Electrolyte Degradation Mechanisms (pages 2964–2975)

      Simone Mastroianni, Dr. Angelo Lembo, Prof. Thomas M. Brown, Dr. Andrea Reale and Prof. Aldo Di Carlo

      Article first published online: 26 JUN 2012 | DOI: 10.1002/cphc.201200229

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      Hydrogen evolution in reverse biased cell: Subjecting a dye solar cell to prolonged reverse bias causes degradation of its charge transfer mechanisms, ascribed to partial irreversible oxidations of the dye molecules, and significant decrease of the diffusion limited current. As a result, the potential across the reverse biased cell increases in time, causing gas, identified as hydrogen, to evolve at the counter electrode, leading to cell failure.

    9. Avoiding Diffusion Limitations in Cobalt(III/II)-Tris(2,2′-Bipyridine)-Based Dye-Sensitized Solar Cells by Tuning the Mesoporous TiO2 Film Properties (pages 2976–2981)

      Dr. Hoi Nok Tsao, Pascal Comte, Dr. Chenyi Yi and Prof. Michael Grätzel

      Article first published online: 31 JUL 2012 | DOI: 10.1002/cphc.201200435

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      At the limit: It is illustrated how diffusion limitations of cobalt redox couples in dye-sensitized solar cells (see picture) can be eliminated by tuning the porosity, particle and pore sizes of the mesoporous TiO2 layers through simple TiCl4 post-treatment. Thus, thicker TiO2 films required for higher photocurrent densities can be used without encountering mass transport limitations, leading to power conversion efficiencies of 10 %.

    10. Strongly Reduced Si Surface Recombination by Charge Injection during Etching in Diluted HF/HNO3 (pages 2982–2988)

      Stefanie M. Greil, Dr. Andreas Schöpke and Dr. Jörg Rappich

      Article first published online: 3 JUL 2012 | DOI: 10.1002/cphc.201200269

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      The bends: The surface recombination of light-induced charge carriers during the etching of Si is investigated by means of photoluminescence measurements (see picture). The surface recombination velocity is strongly reduced during the first stages of etching, pointing to a interface well passivated by the etching process.

    11. High-Amplitude versus Low-Amplitude Current Oscillations during the Anodic Oxidation of p-Type Silicon in Fluoride Containing Electrolytes (pages 2989–2996)

      Konrad Schönleber and Prof. Dr. Katharina Krischer

      Article first published online: 28 JUN 2012 | DOI: 10.1002/cphc.201200230

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      High and low: In the oscillatory electrooxidation of p-type Si, two types of current oscillations with high (red) and low (black and blue) amplitudes (see picture), exist, which follow different mechanisms. This observation clarifies apparently contradictory observations reported in the literature.

    12. Quantized Electron-Transfer Pathways at Nanoparticle–Redox Centre Hybrids (pages 2997–3007)

      Dr. Laura Cabo-Fernández, Dr. Dan F. Bradley, Dr. Simon Romani, Prof. Simon J. Higgins and Prof. David J. Schiffrin

      Article first published online: 21 JUN 2012 | DOI: 10.1002/cphc.201200142

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      Differential pulse voltammetry and cyclic voltammetry measurements show that it is possible to distinguish quantized double-layer charging events of the core from electron transfer to ferrocene (Fc) groups attached to a nanoparticle surface in Fc–monolayer-protected clusters (Fc-MPCs). The voltammetric features depend on the number of redox centres incorporated in the cluster and an electrostatic switching mechanism can be observed at the nanoscale.

    13. Trap States in TiO2 Films Made of Nanowires, Nanotubes or Nanoparticles: An Electrochemical Study (pages 3008–3017)

      Milena Jankulovska, Dr. Thomas Berger, Prof. Dr. Stanislaus S. Wong, Dr. Roberto Gómez and Dr. Teresa Lana-Villarreal

      Article first published online: 27 JUN 2012 | DOI: 10.1002/cphc.201200072

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      Voltammetric signals related to grain boundary traps can be unequivocally identified when working with TiO2 nanostructured electrodes of different morphologies. Various ways of controlling these traps—and thus the electrochemical behavior of TiO2—are discussed.

    14. Visible-Light Photooxidation of Water to Oxygen at Hybrid TiO2–Polyheptazine Photoanodes with Photodeposited Co-Pi (CoOx) Cocatalyst (pages 3018–3024)

      Michal Bledowski, Lidong Wang, Ayyappan Ramakrishnan, Angélique Bétard, Dr. Oleksiy V. Khavryuchenko and Prof. Radim Beranek

      Article first published online: 5 APR 2012 | DOI: 10.1002/cphc.201200071

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      A visible difference: TiO2–polyheptazine (TiO2–PH) hybrid photoanodes loaded with photodeposited cobalt oxide-based oxygen-evolving cocatalyst (Co-Pi) exhibit visible-light-driven photooxidation of water to oxygen at moderate bias potentials (see picture).

    15. Photoanodes Based on Nanostructured WO3 for Water Splitting (pages 3025–3034)

      Dr. Alessandra Tacca, Dr. Laura Meda, Dr. Gianluigi Marra, Dr. Alberto Savoini, Dr. Stefano Caramori, Dr. Vito Cristino, Prof. Carlo Alberto Bignozzi, Dr. Victoria Gonzalez Pedro, Dr. Pablo P. Boix, Dr. Sixto Gimenez and Prof. Juan Bisquert

      Article first published online: 24 APR 2012 | DOI: 10.1002/cphc.201200069

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      Light capture: Anodically grown WO3 electrodes show interesting properties displaying both a partial visible absorption and good charge-transport abilities. They exhibit typical crystalline oxide nanostructures and they reach 70 % of photon-to-current conversion in 1 M H2SO4 at 1.5 V versus SCE under illumination (see picture).

    16. Thermodynamic Aspects of the Synthesis of Thin-Film Materials for Solar Cells (pages 3035–3046)

      Dr. Jonathan J. Scragg, Dr. Phillip J. Dale, Diego Colombara and Prof. Laurence M. Peter

      Article first published online: 24 APR 2012 | DOI: 10.1002/cphc.201200067

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      The solar-cell materials Cu2ZnSnSe4 and Cu(In,Ga)Se2 (CZTS and CIGS) are taken as a case study to show how thermal stability at surfaces and interfaces can be predicted and rationalized. The authors describe how the annealing conditions can be controlled to maximize the stability—and therefore the quality—of the material.

    17. Benzene Oxidation at Diamond Electrodes: Comparison of Microcrystalline and Nanocrystalline Diamonds (pages 3047–3052)

      Prof. Yu. V. Pleskov, Dr. M. D. Krotova, Dr. V. V. Elkin, Dr. V. P. Varnin, I. G. Teremetskaya, Dr. A. V. Saveliev and Dr. V. G. Ralchenko

      Article first published online: 16 MAR 2012 | DOI: 10.1002/cphc.201101059

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      It is all about adsorptivity: During benzene oxidation at a boron-doped diamond electrode, adsorption of a reaction intermediate occurs, which partially blocks the electrode surface and lowers the anodic current (see picture, blue curve). However, using a nanocrystalline diamond electrode, benzene is oxidized concurrently with oxygen evolution, and a (quinoid) intermediate is adsorbed at the electrode.

    18. Solar Hydrogen Generation with Wide-Band-Gap Semiconductors: GaP(100) Photoelectrodes and Surface Modification (pages 3053–3060)

      Dr. Bernhard Kaiser, Dominic Fertig, Jürgen Ziegler, Joachim Klett, Dr. Sascha Hoch and Prof. Dr. Wolfram Jaegermann

      Article first published online: 14 AUG 2012 | DOI: 10.1002/cphc.201200432

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      The photoelectrochemical conversion of sunlight into chemical fuels such as hydrogen requires careful interface engineering of semiconductor materials to achieve high conversion efficiencies. Recent results on the optimization of p-GaP semiconductor electrodes for solar hydrogen generation are summarized.

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