An SFG and DFG investigation of polycrystalline Au, Au-Cu and Au-Ag-Cu electrodes in contact with aqueous solutions containing KCN

In this paper, the behaviour of polycrystalline Au, Au-Cu (Cu 25%) and Au-Ag-Cu (Ag 10%, Cu 15%) electrodes in contact with neutral aqueous solutions of KCN has been studied as a function of potential by means of in situ sum frequency generation (SFG) and difference frequency generation (DFG) spectroscopies. The potential-dependent spectra have been analysed quantitatively with a model for the second-order non-linear susceptibility accounting for vibrational and electronic effects. The potential-dependence of the CN- stretching band position and of the free-electron contribution to the real part of the non-resonant component of the second-order susceptibility have been accounted for. Spectroelectrochemical results were complemented by cyclic voltammetric measurements. The chief stress in this work has been placed on systematising and quantifying the interaction between the vibrational and electronic structures of the electrodic interfaces studied. The effects of adsorbates on the electronic structure of the adsorbing electrode, as a function of electrode alloy composition and applied potential are particularly critical for the understanding of Au-alloy electrochemistry in the presence of cyanide and cyanocomplexes. The systematic comparison of SFG and DFG spectra measured under the same electrochemical conditions for Au, Au-Cu and Au-Ag-Cu electrodes discloses a rich phenomenology related to the electronic structure of the interface