Titanium dioxide doped with vanadium as effective catalyst for selective oxidation of diphenyl sulfide to diphenyl sulfonate

Marcelina Radko,Sylwia Górecka,Katarzyna Pamin,Dominik Wierzbicki,Lucjan Chmielarz,Stefan Witkowski,Andrzej Kowalczyk,Ewa Bidzińska

doi:10.1007/s10973-018-7119-9

Abstract

Diphenyl sulfide was oxidized to sulfoxide and sulfone over V-doped TiO2 using a 30% solution of H2O2. The TiO2 samples with different intended content of vanadium (0.02, 0.05, 0.1 and 0.18 mass%) were prepared by incipient wetness impregnation. Physicochemical properties of the V-doped TiO2 were characterized by chemical analysis (ICP-OES), X-ray diffraction (XRD/in situ HT-XRD), UV–Vis diffuse reflectance spectrometry (UV–Vis DRS), N2-sorption measurements, electron paramagnetic resonance and cyclic voltammetry. Both vanadium oxide loading and calcination temperature influenced the structure of the V-TiO2 samples. Vanadium species deposited on TiO2 decreased temperatures required for anatase to rutile phase transformation. The V-TiO2 samples were found to be efficient catalysts for oxidation of sulfides to sulfones. The sample with the lowest vanadium content (0.02VTiO2) presented among the studied catalysts the best catalytic properties with respect to high conversion of diphenyl sulfide to diphenyl sulfonate. An increase in vanadium loading resulted in decrease in catalytic activity of the samples. Also non-modified TiO2 presented significantly lower catalytic activity in comparison with 0.02VTiO2. This interesting effect was related to the formation of highly dispersed vanadium species catalytically active in Ph2S oxidation in the case of the samples with lower V-content. An increase in vanadium loading results in the formation of more aggregated V-species inactive, or less active, in the process of diphenyl sulfide oxidation.

Highlights

The samples of vanadium-doped TiO2 were tested as catalysts for oxidation of diphenyl sulfide (Ph2S) to diphenyl sulfoxide (Ph2SO) and sulfone (Ph2SO2) using hydrogen peroxide as an oxidation agent
It should be noted that intensities of the reflections characteristic of rutile increased, while intensities of the reflections characteristic of anatase decreased after deposition of vanadium on the TiO2 support
Similar results were recently reported by Shao et al [29], who suggested that this interesting effect is related to many factors, duration and temperature of calcination, synthesis method and type of dopant metal used

Summary

Introduction

The sample with the lowest vanadium content (0.02VTiO2) presented among the studied catalysts the best catalytic properties with respect to high conversion of diphenyl sulfide to diphenyl sulfonate. This interesting effect was related to the formation of highly dispersed vanadium species catalytically active in Ph2S oxidation in the case of the samples with lower V-content. An increase in vanadium loading results in the formation of more aggregated V-species inactive, or less active, in the process of diphenyl sulfide oxidation.

Results

Conclusion