Abstract
The behavior of trace interfacial water and its interaction with Li+ and Br- ions at Ag electrodes in the series of alcohols, methanol, ethanol, propanol, butanol and pentanol is studied using surface-enhanced Raman scattering (SERS). SERS spectra in the ν(O–H) region exhibit four bands from the interfacial water species which are a sensitive function of the nature of the solvent, the residual water concentration and the electrode potential. These bands are assigned to water species interacting with specifically adsorbed Br-, Li+ in the outer Helmholtz plane, “free’' water species in the interface, or hydroxide in LiOH microcrystallites precipitated onto the electrode surface. Interfacial water molecules cluster around Li+ and Br- ions. The spectral data suggest pronounced restructuring of the water in the interface in the vicinity of the potential of zero charge.
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