Influence of thiourea on the nucleation of copper on polycrystalline platinum

Abstract

The influence of thiourea on the nucleation of copper from a 0.30 M CuSO4-1 M H2SO4 solution on polycrystalline platinum electrodes covered by a copper adlayer was investigated. In the case of diffusion controlled nucleation and growth the conditioning potential, that is, the potential of the electrode prior to the application of a large negative potential step, has a strong influence on the nucleation transients. This can result in either a promotion or an inhibition of the nucleation (which is characterized by a change in the nucleation rate constant and/or the site density) depending on the applied potential and the concentration of thiourea. In the region of mixed kinetics and for a fixed value of the conditioning potential (0.175 V vs Cu2+|Cu, that is, in the region of strongest inhibition), a new and rather unexpected effect was observed. Thus, after an induction period, which is proportional to the concentration of thiourea, the current increases sharply to a much higher value, but after reaching a maximum drops again to its original value. At present there is no ready explanation for this phenomenon, which has been called 'nucleation outbursts', but it deserves more investigation because the linearity between the induction time and the concentration of thiourea might have practical applications.