Electrochemical behaviour of aqueous SO{sub}2 at polycrystalline gold electrodes in acidic media. A voltammetric and in-situ vibrational study. Part II. Oxidation of SO{sub}2 on bare and sulphur-modified electrodes

摘要

The electrochemical oxidation of SO{sub}2 on polycrystalline gold electrodes has been studied by means or cyclic voltammetry and in situ vibrational techniques. On bare gold electrodes SO{sub}2 is irreversibly oxidised on forward scans at ～0.6 V RHE featuring a diffusion-limited peak. Oxidation is inhibited by the formation of chemisorbed oxygen. A SO{sub}2 anodic current rise occurs on the reverse scan in parallel with the reduction of the metal oxide layers. As shown by FT-IR oxidation proceeds to yield a mixture of soluble S(VI) species as stable reaction products. From vibrational spectra and results from the irreversible adsorption method it follows that no strongly adsorbed S-O-like residues are present onto the gold surface in the region 0.3-0.5 V/RHE. On sulphur-modified electrodes improved electrocatalysis is manifested by the shift of the diffusion-limited peak to lower potentials. The best performance is observed at a sulphur coverage of 0.5. At higher coverage sulphur adlayers impart lower catalytic efficiency and eventually show strong poisoning properties. This behaviour is exhibited by sulphur adlayers generated either in situ by SO{sub}2 reduction or ex situ by sulphide adsorption oxidation in acidic or alkaline media.