ChemPhysChem

Cover image for Vol. 11 Issue 13

Special Issue: Electrochemistry

September 10, 2010

Volume 11, Issue 13

Pages 2653–3023

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Reviews
    8. Minireviews
    9. Communications
    10. Articles
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    1. Cover Picture: Cellobiose Dehydrogenase: A Versatile Catalyst for Electrochemical Applications (ChemPhysChem 13/2010) (page 2653)

      Dr. Roland Ludwig, Wolfgang Harreither, Federico Tasca and Prof. Lo Gorton

      Article first published online: 6 SEP 2010 | DOI: 10.1002/cphc.201090063

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      The picture shows electron-transfer pathways between a sugar substrate (aldose) oxidized by cellobiose dehydrogenase (CDH) and an electrode. CDH is a two-domain oxidoreductase with a larger FAD-containing (FAD: flavin adenine dinucleotide, shown in yellow) dehydrogenase domain connected through a linker region to a smaller heme-b-containing (shown in red) cytochrome domain. Two electrons are initially donated by the substrate (aldose) to the catalytic domain. The electrons are then transferred to the electrode either in the direct electron transfer (DET) mode via the heme or in the mediated electron transfer (MET) mode through the help of small redox mediator molecules (light blue). On p. 2674, L. Gorton et al. review the biochemical and bioelectrochemical chacteristics of CDH as well as those biosensors and biofuel-cell anodes based on CDH and the possible use of this enzyme in bioelectrosynthesis.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Reviews
    8. Minireviews
    9. Communications
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    1. Inside Cover: Some More Observations on the Unique Electrochemical Properties of Electrode–Monolayer–Nanoparticle Constructs (ChemPhysChem 13/2010) (page 2654)

      Jonathan Dyne, Yu-Shan Lin, Leo M. H. Lai, Joshua Z. Ginges, Dr. Erwann Luais, Dr. Joshua R. Peterson, Ian Y. Goon, Prof. Rose Amal and Prof. J. Justin Gooding

      Article first published online: 6 SEP 2010 | DOI: 10.1002/cphc.201090064

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      A nanoparticle attached to SAM-modified electrodes provides unexpected conducting pathways for electron transfer between redox species in solution and the underlying electrode, as described by J. J. Gooding et al. on p. 2807.

  3. Editorial

    1. Top of page
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    4. Editorial
    5. Graphical Abstract
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    8. Minireviews
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      Editorial: Modern Electrochemistry: Interdisciplinary Research at the Forefront of Science (pages 2655–2656)

      Prof. Dr. Dieter M. Kolb, Prof. Dr. Christian Amatore and Prof. Dr. Richard G. Compton

      Article first published online: 20 AUG 2010 | DOI: 10.1002/cphc.201000616

  4. Graphical Abstract

    1. Top of page
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    4. Editorial
    5. Graphical Abstract
    6. News
    7. Reviews
    8. Minireviews
    9. Communications
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    1. Graphical Abstract: ChemPhysChem 13/2010 (pages 2658–2667)

      Article first published online: 6 SEP 2010 | DOI: 10.1002/cphc.201090065

  5. News

    1. Top of page
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    4. Editorial
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    7. Reviews
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  6. Reviews

    1. Top of page
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    4. Editorial
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    6. News
    7. Reviews
    8. Minireviews
    9. Communications
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    1. Cellobiose Dehydrogenase: A Versatile Catalyst for Electrochemical Applications (pages 2674–2697)

      Dr. Roland Ludwig, Wolfgang Harreither, Federico Tasca and Prof. Lo Gorton

      Article first published online: 26 JUL 2010 | DOI: 10.1002/cphc.201000216

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      An enzyme with contacts: Cellobiose dehydrogenase (CDH) is an extracellular flavocytochrome consisting of flavodehydrogenase (DHCDH) and cytochrome (CYTCDH) domains with the ability to communicate with an electrode by direct (DET) or mediated electron transfer (MET; see picture). Bioelectrochemical techniques used to elucidate basic mechanistic and kinetic properties of CDH and pioneer potential applications in biosensors, biofuel cells and bioelectrosynthesis are presented.

    2. Doped TiO2 and TiO2 Nanotubes: Synthesis and Applications (pages 2698–2713)

      Yoon-Chae Nah, Indhumati Paramasivam and Patrik Schmuki

      Article first published online: 20 JUL 2010 | DOI: 10.1002/cphc.201000276

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      Nanotubular arrays: The fabrication, properties, and selected applications of doped TiO2 materials are reviewed, with an emphasis on self-organized nanotube layers formed by anodization (see picture). Various types of dopants, doping methods, and applications of modified TiO2 nanotubes are discussed.

  7. Minireviews

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    1. What Happens Inside a Fuel Cell? Developing an Experimental Functional Map of Fuel Cell Performance (pages 2714–2731)

      Dr. Daniel J. L. Brett, Prof. Anthony R. Kucernak, Dr. Patricia Aguiar, Stephen C. Atkins, Prof. Nigel P. Brandon, Dr. Ralph Clague, Prof. Lesley F. Cohen, Dr. Gareth Hinds, Dr. Christos Kalyvas, Dr. Gregory J. Offer, Dr. Bradley Ladewig, Dr. Robert Maher, Dr. Andrew Marquis, Dr. Paul Shearing, Dr. Nikos Vasileiadis and Dr. Velisa Vesovic

      Article first published online: 20 AUG 2010 | DOI: 10.1002/cphc.201000487

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      What's going on inside? Fuel cells are complex devices that rely on many coupled physical and chemical processes to operate. Understanding how a fuel cell works and appreciating how these processes interact is key to realising advanced designs and discovery of new materials. Novel diagnostic techniques are being used to examine the internal workings of fuel cells over a wide range of distance scales (see picture).

    2. Platinum and Non-Platinum Nanomaterials for the Molecular Oxygen Reduction Reaction (pages 2732–2744)

      Prof. Dr. Nicolas Alonso-Vante

      Article first published online: 1 APR 2010 | DOI: 10.1002/cphc.200900817

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      Tailoring catalytic centers: Several chemical approaches to the tailoring of nanodivided catalysts for the molecular oxygen reduction reaction (ORR) are presented. The main focus is given to the physical and chemical structures of platinum-based and non-platinum-based cathode materials. Substrate effects and details of the electrochemical ORR pathway are also discussed.

    3. Electrochemically Assisted Fabrication of Metal Atomic Wires and Molecular Junctions by MCBJ and STM-BJ Methods (pages 2745–2755)

      Dr. Jing-Hua Tian, Yang Yang, Dr. Xiao-Shun Zhou, Dr. Bernd Schöllhorn, Dr. Emmanuel Maisonhaute, Zhao-Bin Chen, Fang-Zu Yang, Prof. Yong Chen, Prof. Christian Amatore, Prof. Bing-Wei Mao and Prof. Zhong-Qun Tian

      Article first published online: 24 AUG 2010 | DOI: 10.1002/cphc.201000284

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      Atomic wires and molecular junctions are fundamental units in nanoelectronics. Recent approaches to the fabrication and characterization of these unique metallic and molecular structures are presented (see picture). An interesting strategy consists in combining electrochemical techniques with the mechanically controllable break junction (EC-MCBJ) or the STM break junction (EC-STMBJ) methods.

    4. Electrochemical Probes for Detection and Analysis of Exocytosis and Vesicles (pages 2756–2763)

      Lisa Mellander, Dr. Ann-Sofie Cans and Prof. Andrew G. Ewing

      Article first published online: 24 AUG 2010 | DOI: 10.1002/cphc.201000258

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      Unraveling exocytosis: Recent developments in electrochemical methods to detect exocytosis across a single cell and to measure the transmitter content of single vesicles removed from cells are reviewed (see picture).

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      The Electrode/Ionic Liquid Interface: Electric Double Layer and Metal Electrodeposition (pages 2764–2778)

      Yu-Zhuan Su, Yong-Chun Fu, Yi-Min Wei, Dr. Jia-Wei Yan and Prof. Bing-Wei Mao

      Article first published online: 18 AUG 2010 | DOI: 10.1002/cphc.201000278

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      On the boundary: The intrinsic strong interactions in ionic liquids substantially influence the structure and processes at electrode/ionic liquid interfaces. By employing in situ scanning probe techniques and spectroscopy (see picture), structural information about electrode/ionic liquid interfaces is obtained with high spatial resolution at the molecular level.

    6. Theoretical Investigations of the Oxygen Reduction Reaction on Pt(111) (pages 2779–2794)

      Dr. John A. Keith, Prof. Dr. Gregory Jerkiewicz and Dr. habil. Timo Jacob

      Article first published online: 19 AUG 2010 | DOI: 10.1002/cphc.201000286

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      Modeling an elusive system: A current review on the mechanism of the oxygen reduction reaction (ORR) on Pt(111) (see figure) is presented. Beginning with an abridged introduction to fundamental computational chemistry methods, the authors investigate the multiple-pathway ORR and the influences of solvation, thermal energy (e.g. entropy), and electrode potential on each step.

  8. Communications

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    1. Effect of Degree of Glycosylation on Charge of Glucose Oxidase and Redox Hydrogel Catalytic Efficiency (pages 2795–2797)

      Dr. Olivier Courjean , Dr. Victoria Flexer , Antonin Prévoteau , Dr. Emmanuel Suraniti  and Dr. Nicolas Mano

      Article first published online: 30 APR 2010 | DOI: 10.1002/cphc.201000178

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      Good interactions: The surface charge of an enzyme (see figure, negative charge in red), rather than its size, is the main parameter that governs a good interaction between a polycationic redox polymer and a polyanionic enzyme, resulting in higher catalytic current densities.

    2. Determination of the Activation Volume for CO Oxidation on Platinum by Pressure Modulation (pages 2798–2801)

      Dr. Han-Chun Wang and Prof. Dr. Helmut Baltruschat

      Article first published online: 14 JUL 2010 | DOI: 10.1002/cphc.201000253

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      Highly charged! A pressure-modulation technique is applied to determine the activation volume for CO oxidation on platinum. The negative value obtained suggests the formation of the positively charged transition state [H+⋅⋅⋅O⋅⋅⋅CO] (see figure; grey: Pt; red: O; black: C; blue: H) for which the volume is largely reduced with respect to that of the reactants.

    3. Simplified Cost-Effective Preparation of High-Performance Ag–Pt Nanowire Motors (pages 2802–2805)

      Dr. Sirilak Sattayasamitsathit, Wei Gao, Dr. Percy Calvo-Marzal, Dr. Kalayil Manian Manesh and Prof. Joseph Wang

      Article first published online: 26 JUL 2010 | DOI: 10.1002/cphc.201000348

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      Nanomotors: A simplified cost-effective template approach for preparing efficient gold-free bimetal Ag–Pt nanowire motors, where the silver segment is obtained by a partial removal of the silver sacrificial layer is described (see figure). The unusual behavior, reflecting the ‘active’ role of the Ag segment and the asymmetry of the catalytic surface provides the ultrafast motion of these nanomotors.

  9. Articles

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    1. Some More Observations on the Unique Electrochemical Properties of Electrode–Monolayer–Nanoparticle Constructs (pages 2807–2813)

      Jonathan Dyne, Yu-Shan Lin, Leo M. H. Lai, Joshua Z. Ginges, Dr. Erwann Luais, Dr. Joshua R. Peterson, Ian Y. Goon, Prof. Rose Amal and Prof. J. Justin Gooding

      Article first published online: 28 JUL 2010 | DOI: 10.1002/cphc.201000250

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      Switching on” the electrochemistry of ruthenium due to the immobilization of gold nanoparticles on a passivating self-assembled monolayer (SAM) is investigated (see figure). Gap-mode Raman studies reveal the location of the nanoparticles on top of the SAM and further electrochemical observations are presented on the impacts of nanoparticle diameter and surface charge.

    2. Efficient Platinum-Free Counter Electrodes for Dye-Sensitized Solar Cell Applications (pages 2814–2819)

      Dr. Shahzada Ahmad, Dr. Jun-Ho Yum, Prof. Hans-Jürgen Butt, Dr. Mohammad K. Nazeeruddin and Prof. Michael Grätzel

      Article first published online: 25 AUG 2010 | DOI: 10.1002/cphc.201000612

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      Reducing the costs: Highly efficient platinum-free dye-sensitized solar cells are fabricated using poly(3,4-propylenedioxythiophene) as the counter electrode (see picture). These cells work effectively, also under diffuse-light conditions.

    3. A Changed Electrode Reaction Mechanism between the Nano- and Macroscales (pages 2820–2824)

      Fallyn W. Campbell, Stephen R. Belding and Prof. Richard G. Compton

      Article first published online: 15 JAN 2010 | DOI: 10.1002/cphc.200900863

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      Electrode kinetic data for the electro-reduction of 4-nitrophenol in aqueous solution are compared for bulk silver macro-electrodes and arrays of silver nanoparticles. The electrode kinetics and mechanism change qualitatively and quantitatively. The figure shows experimental voltammograms recorded at an array of silver nanoparticles of radius r=15 nm.

    4. Oxygen Reduction Reaction at Three-Phase Interfaces (pages 2825–2833)

      Dr. Ram Subbaraman, Dr. Dusan Strmcnik, Dr. Arvydas P. Paulikas, Dr. Vojislav R. Stamenkovic and Dr. Nenad M. Markovic

      Article first published online: 20 JUL 2010 | DOI: 10.1002/cphc.201000190

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      Not non-adsorbing: The kinetics of the oxygen reduction reaction are studied at metal–supporting electrolyte–Nafion three-phase interfaces (see picture). It is shown that Nafion is not a non-adsorbing electrolyte and that the sulfonate groups present in its structure are specifically adsorbed on a wide range of surfaces.

    5. Toxicity Response of Electroactive Microbial Biofilms—A Decisive Feature for Potential Biosensor and Power Source Applications (pages 2834–2837)

      Sunil Patil, Dr. Falk Harnisch and Prof. Dr. Uwe Schröder

      Article first published online: 6 JUL 2010 | DOI: 10.1002/cphc.201000218

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      Robust and active: The effect of biocides on wastewater-derived electroactive microbial biofilms is described. The robustness of these biofilms and their bioelectrocatalytic performance in comparison to suspended microbial planktonic cells is demonstrated (see picture).

    6. Reactivity of Gold Nanobelts with Unique {110} Facets (pages 2838–2843)

      Dr. Ying Chen, Dr. Srdjan Milenkovic and Prof. Dr. Achim Walter Hassel

      Article first published online: 23 AUG 2010 | DOI: 10.1002/cphc.201000322

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      Buckle up: Gold nanobelts with the less common {110} crystalline surface (see picture) are prepared by a combination of directional solid-state decomposition of an Fe[BOND]Au eutectoid followed by a phase-selective dissolution process. The fabrication procedure of Au nanobelts is straightforward and suitable for mass production. They could be used for electrochemical or biosensing applications, or in nanodevices.

    7. 1.7 nm Platinum Nanoparticles: Synthesis with Glucose Starch, Characterization and Catalysis (pages 2844–2853)

      Christian Engelbrekt, Karsten Holm Sørensen, Teis Lübcke, Dr. Jingdong Zhang, Dr. Qingfeng Li, Chao Pan, Prof. Niels J. Bjerrum and Prof. Jens Ulstrup

      Article first published online: 16 AUG 2010 | DOI: 10.1002/cphc.201000380

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      Nanosweets: The synthesis of monodisperse platinum nanoparticles (PtNPs) by a green recipe is described (see picture). Glucose serves as a reducing agent and starch as a stabilization agent to protect the freshly formed PtNP cores in buffered aqueous solutions. The PtNPs show high catalytic activity for the reduction of dioxygen and hydrogen peroxide as well as for the oxidation of dihydrogen.

    8. Electrochemical Synthesis of Core–Shell Catalysts for Electrocatalytic Applications (pages 2854–2861)

      Christian Kulp, Dr. Xingxing Chen, Andrea Puschhof, Stefanie Schwamborn, Dr. Christoph Somsen, Prof. Dr. Wolfgang Schuhmann and Prof. Dr. Michael Bron 

      Article first published online: 20 APR 2010 | DOI: 10.1002/cphc.200900881

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      Covering the core: Platinum shells are deposited around carbon-supported gold nanoparticles on a glassy carbon (GC) working electrode (WE) by pulsed electrodeposition from solutions containing Pt ions to prepare core–shell electrocatalysts (see schematic; RE=reference electrode, CE=counter electrode) that can be used for oxygen reduction. Selective Pt deposition on the Au/C catalyst is observed.

    9. Triple Phase Boundary Photovoltammetry: Resolving Rhodamine B Reactivity in 4-(3-Phenylpropyl)-Pyridine Microdroplets (pages 2862–2870)

      Andrew M. Collins, Xiaohang Zhang, Jonathan J. Scragg, Prof. Gary J. Blanchard and Dr. Frank Marken

      Article first published online: 16 APR 2010 | DOI: 10.1002/cphc.200000094

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      Photoelectrochemical processes for rhodamine B in a 4-(3-phenylpropyl)-pyridine microphase immobilized on graphite and immersed in aqueous buffer solution (see picture) are demonstrated.

    10. Perfluoroalkyl Phosphonic and Phosphinic Acids as Proton Conductors for Anhydrous Proton-Exchange Membranes (pages 2871–2878)

      Mahesha B. Herath, Prof. Stephen E. Creager, Dr. Alex Kitaygorodskiy and Dr. Darryl D. DesMarteau

      Article first published online: 2 JUL 2010 | DOI: 10.1002/cphc.201000184

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      Proton-transport mechanisms: A conclusive explanation for the basic proton-transport mechanisms under anhydrous conditions in perfluorinated phosphonic, phosphinic, sulfonic, and carboxylic acid systems is offered (see figure). Proton hopping or structure diffusion is proposed for the perfluorinated phosphonic and phosphonic acids, whereas a vehicle mechanism is proposed for the perfluorinated sulfonic acid and carboxylic acids systems.

    11. On the Reactivity of Sulfosalts in Cyanide Aqueous Media: Structural, Bonding and Electronic Aspects (pages 2879–2886)

      Angel M. Meléndez, Dr. Rubén Arroyo and Prof. Dr. Ignacio González

      Article first published online: 2 AUG 2010 | DOI: 10.1002/cphc.201000187

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      Solid action: A study of physical properties in correlation with the chemistry and structure of the Ag3AsS3–Ag3SbS3 series is obtained by a combination of spectroscopic and electrochemical measurements to investigate their electrochemical reactivity in cyanide media (see figure). The difficulty to anodically dissolve the proustite–pyrargyrite series is related to the presence of AsS3 and SbS3 pyramidal substructures.

    12. Controlled Orientation of DNA in a Binary SAM as a Key for the Successful Determination of DNA Hybridization by Means of Electrochemical Impedance Spectroscopy (pages 2887–2895)

      Magdalena Gębala and Prof. Wolfgang Schuhmann

      Article first published online: 2 AUG 2010 | DOI: 10.1002/cphc.201000210

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      The composition of the monolayer, the ionic strength, the surface coverage with single-stranded DNA (ssDNA), and the electrode pretreatment are prerequisites for reliably detecting DNA hybridization using electrochemical impedance spectroscopy. Co-assembly of mercaptopropionic acid is proposed as a means to control the electrode/electrolyte interface (see figure).

    13. Study of Carbon Monoxide Oxidation on Mesoporous Platinum (pages 2896–2905)

      Thomas F. Esterle, Prof. Andrea E. Russell and Prof. Philip N. Bartlett

      Article first published online: 24 JUN 2010 | DOI: 10.1002/cphc.201000212

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      CO stripping voltammetry on mesoporous Pt differs from that on polycrystalline Pt, both in the position of the peaks and the presence of an additional prewave. These differences arise due to the convex shape of the Pt surface within the pores. Inside the pores, certain Pt sites are not accessible to CO (see picture). Smaller O species may however adsorb on these sites (i.e. OH) giving rise to additional features on the CO stripping voltammetry.

    14. Preparation and Electrochemical Behavior of PtRu(111) Alloy Single-Crystal Surfaces (pages 2906–2911)

      Dr. Ahmed M. El-Aziz, Dr. Rüdiger Hoyer and Dr. Ludwig A. Kibler

      Article first published online: 21 JUL 2010 | DOI: 10.1002/cphc.201000261

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      Janus-surface: PtRu(111) can behave similar to Pt(111) or Ru(0001) depending on the preparation conditions (see picture). Geometric and electronic effects lead to altered electrochemical properties that can be interesting for electrocatalytic reactions.

    15. Voltammetric Manifestation of the Ultraslow Dynamics at the Interface between Water and an Ionic Liquid (pages 2912–2918)

      Prof. Takashi Kakiuchi, Prof. Yukinori Yasui, Prof. Yuki Kitazumi and Prof. Naoya Nishi

      Article first published online: 16 AUG 2010 | DOI: 10.1002/cphc.201000314

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      The ultraslow relaxation of the electrical double layer on the ionic-liquid (IL) side of the interface between water and trioctylmethylammonium bis(nonafluorobutanesulfonyl)amide is not voltammetrically visible for the ion transfer if no significant specific interactions are present between the transferring ions and the IL ions. A self-inhibition mechanism is proposed to explain these unusual features (see picture).

    16. Fundamental Aspects of Electrodeposition for the Realization of Plasmonic Nanostructures (pages 2919–2930)

      Dr. Andrés G. Muñoz, Dr. Katarzyna Skorupska and Prof. Hans-Joachim Lewerenz

      Article first published online: 18 AUG 2010 | DOI: 10.1002/cphc.201000363

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      Electrodeposition is used for the preparation of nanoparticles and nanostructures that allow, in principle, surface plasmon excitation. The (photo)electrodeposition process of Rh and Au nanoparticles (see picture) as well as of heterodimeric enzymes onto silicon surfaces is investigated and the resulting structures are discussed with regard to applications in photoelectroctalysis and biosensing.

    17. Prediction of Local pH Variations during Amperometric Monitoring of Vesicular Exocytotic Events at Chromaffin Cells (pages 2931–2941)

      Dr. Christian Amatore, Dr. Stéphane Arbault, Dr. Yann Bouret, Dr. Manon Guille and Dr. Frédéric Lemaître

      Article first published online: 9 APR 2010 | DOI: 10.1002/cphc.201000102

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      Amperometric detection of exocytosis: During the electrochemical detection of exocytotic release at a carbon microelectrode surface, a significant amount of protons is generated. Considering a cell membrane–electrode cleft in which protons are formed (see picture), the evolution of the mean pH in this zone is simulated from a physicochemical point of view.

    18. In situ X-ray Absorption Analysis of ∼1.8 nm Dendrimer-Encapsulated Pt Nanoparticles during Electrochemical CO Oxidation (pages 2942–2950)

      Michael G. Weir, V. Sue Myers, Prof. Anatoly I. Frenkel and Prof. Richard M. Crooks

      Article first published online: 16 AUG 2010 | DOI: 10.1002/cphc.201000452

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      Zap ′em! In situ structural characterization (see picture) of ∼1.8 nm Pt nanoparticles during an electrochemical reaction demonstrates the stability of this material under catalytic conditions. This nanoparticle size is compatible with first-principles theory, so the results reported represent an important step toward direct comparison of theory and experiment.

    19. Metallization of Ultra-Thin, Non-Thiol SAMs with Flat-Lying Molecular Units: Pd on 1, 4-Dicyanobenzene (pages 2951–2956)

      Felix Eberle, Martin Metzler, Prof. Dr. Dieter M. Kolb, Marc Saitner, Prof. Dr. Patrick Wagner and Prof. Dr. Hans-Gerd Boyen

      Article first published online: 16 AUG 2010 | DOI: 10.1002/cphc.201000309

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      Metallization of ultrathin organic layers: High-resolution STM-studies of 1,4-dicyanobenzene, representing a new class of self-assembled monolayer (SAM) molecules, reveal propeller-like assemblies, each of which consists of three molecules, all lying flat on the gold surface (see figure). This arrangement still allows electrochemical metal deposition on top of the molecules despite the close vicinity to the Au surface.

    20. Charge Transport in Redox Polyelectrolyte Multilayer Films: The Dramatic Effects of Outmost Layer and Solution Ionic Strength (pages 2957–2968)

      Dr. Mario Tagliazucchi and Prof. Dr. Ernesto J. Calvo

      Article first published online: 13 JUL 2010 | DOI: 10.1002/cphc.201000172

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      Last but not least: The nature of the last assembled polyelectrolyte in a redox-active multilayer film (see picture) has a great impact on the charge-transport kinetics. At low ionic strength, the electron-hopping diffusion coefficient for a polyanion-capped film is significantly smaller than that for a polycation-capped one, but the effect is offset at increasing salt concentrations.

    21. Evaluation of the Chemical Reactions from Two Electrogenerated Species in Picoliter Volumes by Scanning Electrochemical Microscopy (pages 2969–2978)

      Qian Wang, Joaquín Rodríguez-López and Prof. Dr. Allen J. Bard

      Article first published online: 4 AUG 2010 | DOI: 10.1002/cphc.201000183

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      A “picoliter beaker” can be created by micro-positioning two ultramicroelectrode probes using the scanning electrochemical microscope (SECM). The probes can electrogenerate in situ species that react inside of it. The authors evaluate the use of the feedback mode of SECM to study these reactions (see picture).

    22. Dioxygen Reduction by Cobalt(II) Octaethylporphyrin at Liquid|Liquid Interfaces (pages 2979–2984)

      Dr. Raheleh Partovi-Nia, Prof. Bin Su, Manuel A. Méndez, Benoit Habermeyer, Dr. Claude P. Gros, Prof. Jean-Michel Barbe, Prof. Zdenek Samec and Prof. Hubert H. Girault

      Article first published online: 6 JUL 2010 | DOI: 10.1002/cphc.201000200

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      Molecular electrocatalysis: The oxygen reduction reaction catalyzed by cobalt(II) (2,3,7,8,12,13,17,18-octaethylporphyrin) [Co(OEP)] can be driven at soft interfaces formed between water and 1,2-dichloroethane (DCE) (see picture). Thus, in the presence of Co(OEP) in DCE and an aqueous acidic solution, oxygen is reduced. This reduction reaction is facilitated when ferrocene is present in excess in the organic phase.

    23. Probing Redox Reactions of Immobilized Cytochrome c Using Evanescent Wave Cavity Ring-Down Spectroscopy in a Thin-Layer Electrochemical Cell (pages 2985–2991)

      Dr. Hayley V. Powell, Dr. Mathias Schnippering, Michelle Cheung, Prof. Julie V. Macpherson, Dr. Stuart R. Mackenzie, Dr. Vasilios G. Stavros and Prof. Patrick R. Unwin

      Article first published online: 28 JUL 2010 | DOI: 10.1002/cphc.201000213

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      Electron transfer in real time: Evanescent wave cavity ring-down spectroscopy (EW-CRDS) is used to monitor the reduction, by [FeEDTA]2−, of an adsorbed layer of oxidized cytochrome c immobilized on fused silica (see picture). The difference in the absorption spectra of the reduced and oxidized forms allows direct monitoring of the electron transfer (ET) in real time.

    24. Epitaxial Growth of Gold on H[BOND]Si(111): The Determining Role of Hydrogen Evolution (pages 2992–3001)

      Patricia Prodhomme, Samantha Warren, Robert Cortès, Hugo Feitosa Jurca, Fouad Maroun and Philippe Allongue

      Article first published online: 19 AUG 2010 | DOI: 10.1002/cphc.201000236

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      Growing ultraflat gold layers on Si? An electrochemical model is proposed to describe the epitaxial electrodeposition of Au on Si(111) at a very negative potential (see picture). The model outlines the determining role of the hydrogen evolution reaction, which promotes a uniform nucleation of multilayer Au(111) nuclei and then induces a preferential lateral growth of the gold islands.

    25. Spatially Resolved ATR-FTIRS Study of the Formation of Macroscopic Domains and Microislands during CO Electrooxidation on Pt (pages 3002–3010)

      Philipp R. Bauer, Dr. Antoine Bonnefont and Prof. Katharina Krischer

      Article first published online: 16 AUG 2010 | DOI: 10.1002/cphc.201000301

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      Self-organized patterns on two widely different spatial length scales form during continuous electrochemical oxidation of CO on Pt. High-coverage CO domains are observed with spatially resolved FTIR spectroscopy (left). When the CO coverage within these domains is below saturation coverage, they subdivide into densely packed microislands, as can be seen from the marginal red-shift of the CO vibrational band (right).

    26. Fabrication of Nanoelectrodes and Metal Clusters by Electrodeposition (pages 3011–3017)

      Jeyavel Velmurugan and Michael V. Mirkin

      Article first published online: 19 JUL 2010 | DOI: 10.1002/cphc.201000321

      Thumbnail image of graphical abstract

      Electrodeposition at nanoelectrodes: Nanometer-sized metal electrodes are prepared by electrodeposition of Hg or Pt on polished or recessed nanoelectrodes. The deposition of Hg is monitored chronoamperometrically to produce flat disk-type electrodes (see figure), which are characterized by voltammetry and scanning electrochemical microscopy.

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      Preview: ChemPhysChem 14/2010 (page 3023)

      Article first published online: 6 SEP 2010 | DOI: 10.1002/cphc.201090067

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