Ferrocene-terminated alkanethiol self-assembled monolayers: An electrochemical and in situ surface-enhanced infra-red absorption spectroscopy study

•The substrate surface structure affects strongly the properties of FcC11 SAMs.•Incorporation of NO3− and (H)SO4(2)− upon FcC11 oxidation is revealed by SEIRAS.•The coadsorption of interfacial water with FcC11 was quantified.•Spectroscopic approach is suggested for the estimate of Epztc of Fc-terminated SAMs.•Structure changes in the FcC11-adalyer upon oxidation are distinguished. The effect of anions on the redox behavior and structure of 11-ferrocenyl-1-undecanethiol (FcC11) monolayers (SAM) on Au(111) single crystal and Au(111-25nm) thin film electrodes was investigated in 0.1M solutions of HPF6, HClO4, HBF4, HNO3, and H2SO4 by cyclic voltammetry (CV) and in situ surface-enhanced infrared reflection-absorption spectroscopy (SEIRAS). We demonstrate that the FcC11 redox peaks shift toward positive potentials and broaden with increasing hydrophilicity of the anions. In situ surface-enhanced IR-spectroscopy (SEIRAS) provided direct access for the incorporation of anions into the oxidized adlayer. The coadsorption of anions is accompanied by the penetration of water molecules. The latter effect is particularly pronounced in aqueous HNO3 and H2SO4 electrolytes. The adlayer permeability increases with increasing hydrophilicity of the anions. We also found that even the neutral (reduced) FcC11 SAM is permeable for water molecules. Based on the property of interfacial water to reorient upon charge inversion, we propose a spectroscopic approach for estimating the potential of zero total charge of the FcC11-modified Au(111) electrodes in aqueous electrolytes.