Influence of mesoporous and platinum-modified titanium dioxide preparation methods on photocatalytic activity in liquid and gas phase

• Published in: Applied catalysis. B, Environmental Environmental, 2007-11, Vol.77 (1-2), p.35-45
• Main Authors: Kozlova, Ekaterina A., Vorontsov, Alexander V.
• Format: Article
• Language: English
• Subjects: acetone; Adsorption; Catalysis; Catalysts; Chemical warfare agent; Decontamination; Oxidation; Phosphonate; Photocatalysis; Photooxidation; Platinum; Q1; Sarin; Soman; Spectroscopy; Sulfates; surface area; Temperature; Template synthesis; TiO2; titanium dioxide
• ISSN: 0926-3373; 1873-3883
• DOI: 10.1016/j.apcatb.2007.07.001

Mesoporous titanium dioxide photocatalysts have been synthesized by template method using widely used precursors and templates with the purpose of choosing the best method for liquid and gas phase photocatalytic oxidation. Titanyl sulphate (TS) and tetrabutyl titanate (TBT) were precursors and cetyl trimethylammonium bromide (CTAB) and dodecylamine (DDA) were templates. Hydrothermal treatment temperature was optimized for the best obtained photocatalyst. The catalysts were characterized by N2 adsorption–desorption measurements, XRD and UV–vis diffuse reflectance spectroscopy. Samples obtained from TBT contained significant amounts of brookite. Activity was measured in liquid phase for dimethyl methylphosphonate (DMMP) and in gas phase for acetone complete oxidation. The highest activity in liquid phase was observed for catalyst prepared from TS and DDA and aged at 160°C. Activity was higher than that of TiO2 Degussa P25 in the low concentration range. The highest activity in gas phase was observed for catalyst prepared from TBT and CTAB. Activity of mesoporous catalysts correlates with their surface area and pore volume for gas phase reaction, whereas in the case of liquid phase DMMP oxidation, there is no sufficient correlation. The effect of DMMP initial concentration on initial oxidation rate is well fitted by Langmuir–Hinshelwood competitive adsorption model. Mesoporous catalysts possess higher adsorption constant but lower reaction rate constant than TiO2 P25. Platinum was deposited by impregnation and soft chemical reduction (SCR) or photodeposition methods (PD). Catalysts obtained by PD were 50% more active than by SCR and 4.5-fold more active than TiO2 P25 in aqueous phase. The reasons for extraordinarily high activity of this mesoporous catalyst are discussed.