Study of adsorption of citrate on Pt by CV and EQCM

Citrates are frequently used as additives in the electrodeposition of metals such as manganese in order to improve deposit characteristics and process efficiency. Nevertheless, few studies have been reported on the mechanism of citrate adsorption. This paper presents the results of a study of citrate adsorption onto platinum from solutions of various citrate concentrations in 0.1 M HClO4. Simultaneous observations with an electrochemical quartz crystal microbalance (EQCM) and cyclic voltammetry (CV) indicate that with increasing concentrations, up to 10−2 M, the fractional surface coverage by citrate rises to 13% in the region of hydrogen UPD, and the anodic formation of PtO is inhibited and reduced by as much as 43%. Combination of EQCM with cathodic linear-sweep voltammetry shows the interactions of citrate with platinum oxidation and hydrogen UPD. Thus, this approach reveals changes in additive adsorption with potential and indicates in particular the influence of the additive on the adsorption and desorption of hydrogen as a step in understanding metal deposition.