Effect of Cs+ ions on the electrochemical nanogravimetric response of platinum electrode in acid media

Platinum electrodes have been investigated in sulfuric acid solutions in the presence and absence of Cs+ ions by electrochemical quartz crystal nanobalance (EQCN). An unusual potential dependence of the quartz crystal frequency response has been observed in the presence of Cs+ ions. The frequency decrease is more pronounced in the region of the underpotential deposition of hydrogen, and the frequency decrease in the double layer region diminishes as the concentration ratio of Cs+ and ions increases. After immersion in Cs2SO4 solutions the frequency change was higher than that expected taking into account the density and viscosity. The effects observed can be explained by the specific adsorption of Cs+ ions on the Pt surface, which competes with the hydrogen adsorption. At more positive potentials than the potential of zero charge (pzc) a desorption of the Cs+ ions starts. In this potential region both Cs+ and HSO4- ions are adsorbed at the platinum surface. In the double layer region the mass change caused by the desorption of Cs+ ions and the starting adsorption of sulfate ions compensates each other. (C) 2010 Elsevier B.V. All rights reserved.