Electrochemistry metal modifications

Microelectrodes, due to their unique properties, such as small size, non-planar diffusion, small capacitance, and small current, have provided a major breakthrough in electrochemistry. Taking advantage of the superior properties of diamond, the diamond microelectrode is a promising new device for several applications in electrochemistry. Furthermore, modification of the diamond microelectrode with appropriate metal nanoparticles increases the quality of the measurements, in the terms of sensitivity, stability, and selectivity. 

Kohei Uosaki received his B.Eng. and M.Eng. degrees from Osaka University and his Ph.D. in Physical Chemistry from flinders University of South Australia. He vas a Research Chemist at Mitsubishi Petrochemical Co. Ltd. from 1971 to 1978 and a Research Officer at Inorganic Chemistry Laboratory, Oxford University, U.K. bet veen 1978 and 1980 before joining Hokkaido University in 1980 as Assistant Professor in the Department of Chemistry. He vas promoted to Associate Professor in 1981 and Professor in 1990. He is also a Principal Investigator of International Center for Materials Nanoarchitectonics (MANA) Satellite, National Institute for Materials Science (NIMS) since 2008. His scientific interests include photoelectrochemistry of semiconductor electrodes, surface electrochemistry of single crystalline metal electrodes, electrocatalysis, modification of solid surfaces by molecular layers, and non-linear optical spectroscopy at interfaces. 

This chapter will carefully differentiate situations in which coordination of metal ions assists in the achievement of specific electrochemical aims from experiments designed to study the electrochemistry of coordination compounds. (For information on the latter topic, see, particularly, Chapters 8.1-8.3). Two major areas have been selected for consideration one almost classical, namely the electrodeposition of metals, the other of more recent origin, namely the modification of electrode surfaces. 

Protoporphyrin-IX, structural modifications 87H(26)1947. Sandwich-compounds of metals with porphyrins 90MI42. Spectroscopy, electrochemistry, and applications of porphyrins, monograph 87MI18. 

Professor in 1981 and Professor in 1990. He is also a Principal Investigator of International Center for Materials Nanoarchitectonics (MANA) Satellite, National Institute for Materials Science (NIMS) since 2008. His scientific interests include photoelectrochemistry of semiconductor electrodes, surface electrochemistry of single crystalline metal electrodes, electrocatalysis, modification of solid surfaces by molecular layers, and non-linear optical spectroscopy at interfaces. 

Electrochemistry can be used to affect oxidation catalysis on metals and metallic oxides [13] in a very pronounced and reversible manner. The observed promotional phenomena are due to an electrochemically driven and controlled backspillover of ionic species on the catalyst surface. These species, which in some cases cannot form via gas phase adsorption, alter the catalyst work function and affect the binding strengths of chemisorbed reactants and intermediates in a pronounced and theoretically predictable manner. This electrochemically controlled variation in the binding strength of adsorbates causes the observed pronounced modification in catalytic activity and selectivity. The ability of solid electrolytes to act as reversible promoter donors to influence oxidation catalysis is of considerable theoretical and, potentially, practical interest. 

The modification of platinum surfaces by foreign metal atoms promotes the oxidation of methanol either in UHV conditions or in the electrochemical environment. This promotion model has been mainly discussed in electrochemistry using the third body model [37], the ligand effect [38], or the bifunctional effect [9,39,40], A theoretical review on the inclusion of metal reaction promoters was undertaken by Anderson et al. [41] and later discussed in [42],... 

Electrochemical promotion (EP) denotes electrically controlled modification of heterogeneous catalytic activity and/or selectivity. This recently discovered phenomenon has made a strong impact on modem electrochemistry/ catalysis/ and surface science. Although it manifests itself also using aqueous electrolytes/ the phenomenon has mainly been investigated in gas-phase reactions over metal and metal oxide catalysts. In the latter case, the catalyst, which is an electron conductor, is deposited in the form of a porous thin film on a solid electrolyte support, which is an ion conductor at the temperature of the catalytic reaction. Application of an electric potential on the catalyst/support interface or, which is equivalent, passing an electric current between catalyst and support, causes a concomitant change also in the properties of the adjacent catalyst/gas interface, where the catalytic reaction takes place. This results in an alteration of the catalytic behaviour, controllable with the applied potential or current. 

In electrochemistry an electrode is an electronic conductor in contact with an ionic conductor. The electronic conductor can be a metal, or a semiconductor, or a mixed electronic and ionic conductor. The ionic conductor is usually an electrolyte solution however, solid electrolytes and ionic melts can be used as well. The term electrode is also used in a technical sense, meaning the electronic conductor only. If not specified otherwise, this meaning of the term electrode is the subject of the present chapter. In the simplest case the electrode is a metallic conductor immersed in an electrolyte solution. At the surface of the electrode, dissolved electroactive ions change their charges by exchanging one or more electrons with the conductor. In this electrochemical reaction both the reduced and oxidized ions remain in solution, while the conductor is chemically inert and serves only as a source and sink of electrons. The technical term electrode usually also includes all mechanical parts supporting the conductor (e.g., a rotating disk electrode or a static mercury drop electrode). Furthermore, it includes all chemical and physical modifications of the conductor, or its surface (e.g., a mercury film electrode, an enzyme electrode, and a carbon paste electrode). However, this term does not cover the electrolyte solution and the ionic part of a double layer at the electrode/solution interface. Ion-selective electrodes, which are used in potentiometry, will not be considered in this chapter. Theoretical and practical aspects of electrodes are covered in various books and reviews [1-9]. 

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