SERS spectroelectrochemical study of electrode processes at copper hexacyanoferrate modified electrode

Abstract

Electrochemical redox processes taking place at copper hexacyanoferrate (CuHCF) modified electrode have been investigated by near-infrared laser (785nm) induced surface-enhanced Raman spectroscopy (SERS). Raman bands observed within the spectral ranges of 2200–2000cm−1 and 500–100cm−1, as well as their dependence on electrode potential, have been analysed. The most characteristic Raman bands, related to triple CN bond vibrations and centered at 2187 and 2127cm−1 were assigned to the oxidised and the reduced forms of CuHCF, respectively. Time-resolved Raman spectroelectrochemical study shows that the electrochemical redox interconversions between these two forms proceed relatively slow, thus resembling the behaviour of structurally related cobalt hexacyanoferrate, and differing essentially from that of Prussian blue layer studied previously. It has been shown by the time-resolved Raman spectroelectrochemistry that the rate of some redox processes of solute species like the anodic oxidation of ascorbate or cathodic reduction of hydrogen peroxide at CuHCF modified electrode appears to be limited by the slow electrochemical redox transformations within the modifier layer itself rather than by the redox interactions of a modifier with the solute species.