Surface Raman scattering of the butanol isomers on emersed Ag and Au electrodes

Surface Raman scattering in the ν(C-H) region of 1-butanol, 2-butanol, and isobutyl alcohol on emersed rough and smooth Ag and Au electrodes is reported and is compared to the corresponding in-situ surface-enhanced Raman scattering results. Identical spectral behavior is observed for the rough and smooth emersed electrodes compared to the in-situ electrodes, suggesting that the solvent structure and orientation at the electrode is retained upon emersion. The behavior of the ν(Au-Br) band and the ν(O-H) band from interfacial water solvating ions suggests that the electrolyte structure is also retained upon emersion. The stability of the emersed layer is extremely dependent on solvent evaporation, atmospheric purity, and electrode contamination. A new spectroelectrochemical cell that allows routine collection of spectra from emersed smooth and rough electrodes is also described.