Synergistic Effect of Surface Acidity and PtOx Catalyst on the Sensitivity of Nanosized Metal–Oxide Semiconductors to Benzene

Benzene is a potentially carcinogenic volatile organic compound (VOC) and its vapor must be strictly monitored in air. Metal-oxide semiconductors (MOS) functionalized by catalytic noble metals are promising materials for sensing VOC, but basic understanding of the relationships of materials composition and sensors behavior should be improved. In this work, the sensitivity to benzene was comparatively studied for nanocrystalline n-type MOS (ZnO, In2O3, SnO2, TiO2, and WO3) in pristine form and modified by catalytic PtOx nanoparticles. Active sites of materials were analyzed by X-ray photoelectron spectroscopy (XPS) and temperature-programmed techniques using probe molecules. The sensing mechanism was studied by in situ diffuse-reflectance infrared (DRIFT) spectroscopy. Distinct trends were observed in the sensitivity to benzene for pristine MOS and nanocomposites MOS/PtOx. The higher sensitivity of pristine SnO2, TiO2, and WO3 was observed. This was attributed to higher total concentrations of oxidation sites and acid sites favoring target molecules' adsorption and redox conversion at the surface of MOS. The sensitivity of PtOx-modified sensors increased with the surface acidity of MOS and were superior for WO3/PtOx. It was deduced that this was due to stabilization of reduced Pt sites which catalyze deep oxidation of benzene molecules to carbonyl species.