Electrochemical behaviour of aqueous SO2 at polycrystalline gold electrodes in acidic media. A voltammetric and in-situ vibrational study. Part II. Oxidation of SO2 on bare and sulphur-modified electrodes

The electrochemical oxidation of SO2 on polycrystalline gold electrodes has been studied by means of cyclic voltammetry and in situ vibrational techni ques. On bare gold electrodes, SO2 is irreversibly oxidised on forward scan s at similar to0.6 V/RHE, featuring a diffusion-limited peak. Oxidation is inhibited by the formation of chemisorbed oxygen. A SO2 anodic current rise occurs on the reverse scan in parallel with the reduction of the metal oxi de layers. As shown by FT-IR, oxidation proceeds to yield a mixture of solu ble S(VI) species as stable reaction products. From vibrational spectra and results from the irreversible adsorption method, it follows that no strong ly adsorbed S-O-like residues are present onto the gold surface in the regi on 0.3-0.5 V/RHE. On sulphur-modified electrodes improved electrocatalysis is manifested by the shift of the diffusion-limited peak to lower potential s. The best performance is observed at a sulphur coverage of 0.5. At higher coverage, sulphur adlayers impart lower catalytic efficiency and eventuall y show strong poisoning properties. This behaviour is exhibited by sulphur adlayers generated either in situ by SO2 reduction or ex situ by sulphide a dsorption/oxidation in acidic or alkaline media. (C) 2000 Elsevier Science Ltd. All rights reserved.