The growth of the second underpotentially deposited silver layer on Pt(100)

The electrodeposition of Ag on Pt(100)-(1 × 1) in perchlorate electrolyte was studied by means of time-resolved in situ scanning tunnelling microscopy (STM) and cyclic voltammetry. One monolayer of Ag is deposited underpotentially (upd) ca. 500 mV positive of the Ag⁺/Ag equilibrium potential. Several millivolts positive of the equilibrium potential, a second well defined upd layer forms. Its growth was observed to proceed via island formation and coalescence. This process occurs in two separate stages that manifest themselves in voltammetric peaks as well as in the STM images.