Electrochemically induced structural modifications

As often underlined, one of the main targets of the electrochemical investigations on inorganic compounds is to ascertain their stability upon addition or removal of electrons. However, should the compounds undergo important molecular reorganizations as a consequence of such electron transfer processes, it is also important to ascertain the nature of such redox changes. 

In this light we will now consider some examples of electrochemically detectable molecular reorganisations induced by electron transfer processes, which can be chemically more appealing than the simple variations of bond distances/angles discussed up to now. 

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These results are quite interesting. The initial stages of Al deposition result in nanosized deposits. Indeed, from the STM studies we recently succeeded in making bulk deposits of nanosized Al with special bath compositions and special electrochemical techniques [10]. Moreover, the preliminary results on tip-induced nanostructuring show that nanosized modifications of electrodes by less noble elements are possible in ionic liquids, thus opening access to new structures that cannot be made in aqueous media. 

Although the electrochemical nature of the nano structuring process is convincingly demonstrated, the role of the externally applied electric field should be once more considered. Field-induced modifications of a surface on an atomic scale have been reported from various vacuum experiments [46-49]. The fields required for such manipulations are much larger than those applied here and usually necessitate very small distances between tip and surface, close to mechanical contact... 

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