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In this paper we describe an unusual electrochemical phenomenon, namely cathodic corrosion of platinum. We show that all existing models of cathodic corrosion are inconsistent with our experimental observations. Therefore, we present a new model of cathodic corrosion, which is based on the assumption that metal anions are formed at the electrode surface during the corrosion process. These anionic species function as precursors for the formation of the final product of cathodic corrosion–metal nanoparticles.

We demonstrate how cathodic corrosion in concentrated aqueous solutions enables one to prepare nanoparticles of various metals and metal alloys. Using various characterization methods we show that the composition of nanoparticles remains that of the starting material, and the resulting size distribution remains rather narrow. For the case of platinum we show how the size and possibly even the shape of the nanoparticles can be easily controlled by the parameters of corrosion. Finally, we discuss the advantages of using the nanoparticles prepared by cathodic corrosion for applications in (electro-)catalysis.