Kinetics of Metal Deposition via Surface-limited Redox Replacement Reaction

In this work, we examined the kinetics of metal deposition via surface-limited redox replacement reaction (SLRR). The model system was Pt submonolayer deposition on Au(111) via redox replacement of Pb and Cu underpotentially deposited (UPD) monolayers (MLs) on Au(111). The deposition kinetics were studied through the formalism of the comprehensive analytical model developed to fit open circuit potential (OCP) transients from our deposition experiments. Reaction half time, reaction order, and reaction rate constant were extracted and discussed within the frame of their application to the design and control of deposition experiments. Through the scope of the analytical model, different aspects of SLRR (i.e., the nature of the UPD metal monolayer participating in the redox reaction, the transport limitation, and the role of the anions/electrolyte) were investigated in terms of their effects on the reaction kinetics.