Raman spectroelectrochemical study of electrode processes at Neutral red- and poly(Neutral red) modified electrodes

The redox dye Neutral red (NR), adsorbed and electropolymerized at a roughened gold electrode, has been studied by Raman spectroscopy at lambda(ex) of 676.4 nm in an electrochemical cell. Spectral bands have been assigned based on density functional theory (DFT) calculations. The number and position of the bands, as well as their intensity depend on electrode potential, allowing one to discern different redox forms of NR or its polymer. The observed changes in band positions and intensities have been analyzed. Electrooxidation of hydroquinone and ascorbic acid at a gold electrode modified with adsorbed or electropolymerized layer of NR has been studied with in situ Raman spectroelectrochemical technique. During electrooxidation of solution species, NR layer contains both oxidized and reduced forms of this modifier. It has been shown that the relative content of a reduced form of NR at electrode surface increases with increasing concentration of any of oxidizable species used. It has been concluded that anodic oxidation of ascorbic acid or hydroquinone at NR or polyNR modified electrode proceeds within the modifier layer rather than at a modifier/electrolyte interface. In this respect, electrooxidation follows a redox mechanism. (C) 2009 Elsevier B.V. All rights reserved.