LAUSR

Abstract We present a comprehensive study on the initial stages of silver electrodeposition on Pt (111), Au (111), and Au (100) single crystal surfaces in low-viscosity ionic liquids (ILs) containing dicyanamide anions: 1-butyl-1-methylpyrrolidinium dicyanamide [BMP][DCA] and 1-butyl-3-methylimidazolium dicyanamide [BMIm][DCA]. Electrochemical methods in combination with in situ scanning tunneling microscopy (STM) and ex situ atomic force microscopy (AFM) are employed to explore the Ag underpotential (upd) and overpotential (opd) deposition processes as well as the stability of the single crystal electrode surfaces in the absence of Ag+ ions. The substrate material is shown to significantly affect the mechanism of Ag deposit nucleation and growth in the ILs. While no Ag upd is detected on Pt (111), the formation of a Ag upd monolayer on a Au (111) electrode in both ILs is clearly visualized by in situ STM. The Ag adlayer formation on the Au electrodes in the underpotential regime facilitates Ag opd, which starts on Au (111) and Au (100) at much less negative potentials than on Pt (111). There is an excellent agreement between the electrochemical (voltammetry and chronoamperometry), AFM and STM data, demonstrating the nucleation and growth of individual Ag crystallites on Pt (111) according to the Volmer–Weber mechanism and the layer–by–layer growth of Ag deposit on Au (111) and Au (100). Only at high overpotentials, the Ag growth on the gold electrodes switches to the Stranski-Krastanov mode involving the appearance of 3D crystallites.