Catalytic and photocatalytic oxidation of diphenyl sulphide to diphenyl sulfoxide over titanium dioxide doped with vanadium, zinc, and tin

Abstract

Samples of TiO₂ (P25) doped with zinc, tin, and vanadium, thermally treated at 550 °C for 6 h, were tested as catalysts and photocatalysts for the oxidation of diphenyl sulphide to diphenyl sulfoxide and sulfone, using hydrogen peroxide as an oxidation agent. Thermal treatment of pure TiO₂ and its vanadium-doped forms resulted in a decrease of anatase and an increase of rutile content. The opposite effect was observed for TiO₂ doped with zinc or tin, where thermal treatment resulted in the rutile to anatase phase transition. The role of V, Zn, and Sn admixtures as TiO₂ phase-composition controllers was postulated. The catalytic and photocatalytic activity was found to be influenced more by the rutile and anatase contents of the samples than the presence of admixtures. The rutile-containing samples, TiO₂ and V-TiO₂, presented much better activity in the catalytic oxidation of diphenyl sulphide compared with the catalysts that only contained the anatase phase, Sn-TiO₂ and Zn-TiO₂. The reaction efficiency was significantly improved under UV radiation. In this case, the best photocatalytic activity was found for calcined TiO₂, containing both anatase and rutile components. An increase in rutile content, observed in the vanadium-doped TiO₂, decreased the efficiency of the photocatalytic diphenyl sulphide oxidation. Thus, the presence of both anatase and rutile phases, with their favourable contributions, typical for P25, is necessary for the effective oxidation of Ph₂S to Ph₂SO. Moreover, it was shown that for the second oxidation stage, Ph₂SO to Ph₂SO₂, the presence of the rutile phase is very important.