Electrochemical Promotion of Sulfur Dioxide Catalytic Oxidation

Abstract

The effect of electrochemical polarization on the catalytic oxidation in the molten system has been studied using a gold working electrode in the temperature range 400–460°C. A similar experiment has been performed with the industrial catalyst VK-58. The aim of the present investigation was to study a possible non‐Faradaic electrochemical promotion of the liquid‐phase catalytic reaction. It has been shown that there are two negative potential promotion areas with maximum effects at approximately −0.1 and −0.2 V, and one positive potential promotion area with the maximum effect between 0.1 and 0.3 V. There were no Faradaic reactions in the negative polarization region, and there was an anodic current which was less than 16% of the theoretical value for an exclusively Faradaic oxidation. Therefore the promotion effects at negative polarization are completely non‐Faradaic. All the promotion effects have been explained as mainly due to charging of the electric double layer at the gold electrode. The effect at −0.2 V also depends on the concentration and is more pronounced at higher concentrations. This has been ascribed to a destruction of the vanadium polymeric chains caused by the negative charge on the electrode. The Faradaic part of the promoting effect under positive polarization has been explained as the electrochemical pushing of the V(V) ↔ V(IV) equilibrium in the direction of V(V) formation. It has also been shown that when using the industrial VK-58 catalyst the activity can be increased up to four times by using the negative polarization effect with maximum at −0.2 V. © 2000 The Electrochemical Society. All rights reserved.