Photocatalytic degradation of unsymmetrical dimethylhydrazine on TiO2/SBA-15 under 185/254 nm vacuum-ultraviolet

Abstract

In this work, TiO₂/SBA-15 was synthesized via an in situ hydrothermal method and was used for vacuum-ultraviolet (VUV) photocatalytic degradation of unsymmetrical dimethylhydrazine (UDMH) for the first time. Compared with photocatalysis under UV irradiation, VUV photocatalysis exhibited higher photodegradation efficiency due to the synergetic effect of direct photolysis, indirect photooxidation and photocatalytic oxidation. The synthesized TiO₂/SBA-15 catalysts exhibited ordered mesoporous structure and anatase phase TiO₂. Titanium content, initial pH and substrate concentration impacted degradation efficiency of UDMH in the VUV photocatalysis process. Among the prepared catalysts, TiO₂/SBA-15 with the molar ratio of Ti/Si = 1 : 3 (TS-2) showed the best photocatalytic activity under VUV light, with the rate constant of 0.02511 min⁻¹, which is 1.91 times that with VUV/P25. The superior photocatalytic activity of TS-2 is mainly related to the good balance between the specific surface area and TiO₂ contents. The photodegradation efficiency decreases with the increase in the initial UDMH concentration and the maximum degradation rate was obtained at pH 9.0. In the VUV/TS-2 process, ˙OH played a more important role in the degradation of UDMH than ˙O₂⁻ and the degradation pathways contained bond breaking, amidation, isomerisation and oxidation reactions. The TS-2 also showed good reusability with the rate constant maintained at above 90% after five cycles and exhibited satisfactory degradation efficiency in tap water.