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Nanopatterned and Nanoparticle-Modified Electrodes

  • Erscheinungsdatum: 13.03.2017
  • Verlag: Wiley-VCH
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Nanopatterned and Nanoparticle-Modified Electrodes

Volume XVII in the 'Advances in Electrochemical Science and Engineering' series, this monograph covers progress in this rapidly developing field with a particular emphasis on important applications, including spectroscopy, medicinal chemistry and analytical chemistry. As such it covers nanopatterned and nanoparticle-modified electrodes for analytical detection, surface spectroscopy, electrocatalysis and a fundamental understanding of the relation between the electrode structure and its function. Written by a group of international experts, this is a valuable resource for researchers working in such fields as electrochemistry, materials science, spectroscopy, analytical and medicinal chemistry. Richard C. Alkire is Professor Emeritus of Chemical & Biomolecular Engineering Charles and Dorothy Prizer Chair at the University of Illinois, Urbana, USA. He obtained his degrees at Lafayette College and University of California at Berkeley. He has received numerous prizes, including Vittorio de Nora Award and Lifetime National Associate award from National Academy. Philip N. Bartlett is Head of the Electrochemistry Section, Deputy Head of Chemistry for Strategy, and Associate Dean for Enterprise in the Faculty of Natural and Environmental Sciences at the University of Southampton. He received his PhD from Imperial College London and was a Lecturer at the University of Warwick and a Professor for Physical Chemistry at the University of Bath, before moving to his current position. His research interests include bioelectrochemistry, nanostructured materials, and chemical sensors. Jacek Lipkowski is Professor at the Department of Chemistry and Biochemistry at the University of Guelph, Canada. His research interests focus on surface analysis and interfacial electrochemistry. He has authored over 120 publications and is a member of several societies, including a Fellow of the International Society of Electrochemistry.


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Nanopatterned and Nanoparticle-Modified Electrodes

Chapter 1
Surface Electrochemistry with Pt Single-Crystal Electrodes

Victor Climent and Juan M. Feliu
1.1 Introduction

The sensitivity of electrochemical processes to the crystallographic structure of the electrode surface is now a well-established fact demonstrated for numerous reactions. Except for outer sphere processes, the majority of electrochemical reactions involve the formation of adsorbed intermediates. In fact, the concepts underneath the electrocatalytic phenomena are intimately linked to the existence of strong interactions of reacting species and the electrode surface [1]. In this case, adsorption energies are very sensitive to the geometries of the adsorption sites, strongly affecting the energetic pathway from reactants to products and, in consequence, the rate of the reaction.

In addition, the properties of the interphase are affected by the crystallographic structure of the electrode. Considering that the electron transfer has to take place in the narrow region that separates the metal from the solution, it is easy to understand that the interfacial properties will also have strong effect on the rate of most reactions. Anion-specific adsorption, distribution of charges at the interphase, and even interaction of water with the metal surface are aspects of the interphase that need to be considered in order to get the complete picture about the influence of the structure on the electrochemical reactivity.

In this sense, the approach of interfacial electrochemistry has been proved as very convenient (and inexpensive) to study the interaction of molecules and ions with metal surfaces. An iconic moment in the development of electrochemistry as a surface-sensitive approach is the introduction of the flame annealing methodology by the French scientist Jean Clavilier [2, 3]. Earlier attempts to obtain a surface-sensitive electrochemical response with well-defined metal surfaces resulted in dissimilar and contradictory results [4-8]. The flame annealing technique not only offered a much simpler method in comparison with the more complex approaches based on ultrahigh-vacuum (UHV) preparation of the surface but also offered the opportunity to perform the experiments in many different laboratories across the world, soon proving the reproducibility of the results. Immediately after the introduction of this methodology, some controversy arose because it revealed aspects of the electrochemical behavior of platinum not previously reported (the so-called unusual adsorption states) [9-11]. This initial controversy was soon resolved, and now the correct electrochemistry of platinum single crystals is well established and understood [11, 12].

The knowledge gained about the electrochemical reactivity of platinum from the studies using well-defined electrode surfaces has resulted in very useful understanding of the behavior of more complex electrode structures, such as polycrystalline materials and nanoparticles.

Figure 1.1 2D representation of the process of cutting a crystal through a plane, resulting on a stepped surface.
1.2 Concepts of Surface Crystallography

An atomically flat surface is generated by cutting a single crystal in a desired orientation with respect to the crystallographic axis of the crystal. The ideal surface that is obtained by such process can be understood as the result of removing all the atoms whose center lies on one side of the cutting plane and keeping all the atoms lying on the other side. Because the cutting plane does not necessarily pass through the center of all of the atoms, the resulting surface is not perfectly flat, and, in the more general case, the atomic centers of the atoms will define a regular distribution of terraces separated with steps which may also contain some corners or kinks. This process is illustrated in Figure 1.1 for t

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