ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS, vol.226, pp.953-963, 2012 (SCI-Expanded)
The underpotential deposition (UPD) of Copper on Au(111) in nonaqueous acetonitrile/perchlorate electrolyte has been investigated. The deposition mechanism is thereby strongly influenced by coadsorbed acetonitrile molecules and the stability of the solvation shell around the Cu(I) ions. The UPD mechanism obeys a two step mechanism even in presence of only none specifically adsorbing perchlorate ions. Thereby the first sub monolayer of copper is stabilized by coadsorbed acetonitrile molecules. However already 5% vol water content changes the structure within the double layer and consequently degrades the copper sub monolayer. At about 20% vol water content the Cu(I) ion/solvent complex is still stable. The reduction of Cu(I) ions from this complex is much faster compared to the reduction from the respective Cu(II) water complex.