Journal of the American Chemical Society, Vol.137, No.43, 13752-13755, 2015
Recognizing Single Collisions of PtCl62- at Femtomolar Concentrations on Ultramicroelectrodes by Nucleating Electrocatalytic Clusters
We report the electrodeposition of electro-catalytic clusters of platinum from femtomolar platinate solutions. An inert carbon fiber ultramicroelectrode (UME) was held at a potential where proton reduction was unfavorable on carbon but favorable on platinum in a 1 M sulfuric acid solution. Upon addition of femtomolar amounts of hexachloroplatinic acid, which will also reduce to Pt-0 at the applied potential on the carbon fiber UME, cathodic blips were observed in the amperometric i-t response. These blips correspond to the reduction of protons to molecular hydrogen at the small platinum clusters followed by a rapid deactivation likely due to hydrogen bubble formation. On average, these current spikes occur when five platinum atoms have been formed on the electrode, as determined by a comparative analysis of experimental cathodic blips and calculated hexachloroplatinate molecule collision frequencies.