The reactivity of platinum microelectrodes.

Despite the widespread application of ultramicroelectrodes (UMEs), the customary method of their electrochemical characterization via outer sphere redox probing has serious limitations. In this study we provide additional insights into this subject by measuring not only outer sphere redox couples, but also blank voltammetries and the reactivity towards various catalytic reactions of Pt UMEs. The data for the UMEs are compared to those for macroscale Pt electrodes that can be flame-annealed. Although the reactivity is similar for reactions that are rather insensitive to the surface structure (and/or composition), UMEs perform much worse for more surface sensitive catalytic reactions. This effect can be explained by the UMEs being contaminated much faster, though it remains to be established if the origin of this contamination lies in the preparation method or in the impurities in the (high-purity grade) chemicals used. Our study recommends that catalytic reactivity measurements on ultramicroelectrodes should always be accompanied by blank voltammetries and the results have to be interpreted extremely carefully.