Glycolate adsorption at gold and platinum electrodes: A theoretical and in situ spectroelectrochemical study

The adsorption of glycolate anions at sputtered gold thin-film electrodes was studied in perchloric acid solutions by cyclic voltammetry experiments combined with in situ Surface Enhanced Raman Scattering (SERS) and Surface Enhanced Infrared Reflection Absorption Spectroscopy under attenuated total reflection conditions (ATR-SEIRAS). Theoretical harmonic vibrational frequencies and band intensities obtained from B3LYP/LANL2DZ,6-31+G(d) calculations for glycolate species adsorbed on Au clusters with (1 1 1) orientation were used to interpret the experimental spectra. Vibrational data confirm the bidentate bonding of glycolate anions through the oxygen atoms of the carboxylate group, in a bridge configuration with the OCO plane perpendicular to the metal surface. The DFT calculations show no significant effect of the total charge of the metal cluster–adsorbate adduct on the vibrational frequencies of adsorbed glycolate species. The infrared experimental study is extended to platinum films electrochemically deposited onto sputtered gold thin-film electrodes showing the potential-dependent formation of adsorbed CO upon dissociative adsorption of glycolate anions. As in the case of gold, the reversible adsorption of glycolate anions takes place in a bidentate configuration as predicted by DFT calculations for glycolate adsorbed on Pt(1 1 1) clusters. At low glycolic acid concentration, the in situ ATR-SEIRA spectra evidence the formation of adsorbed oxalate as reaction intermediate.