Anastasia Grebenkina

Nanocrystalline TiO₂ is a perspective semiconductor gas-sensing material due to its long-term stability of performance, but it is limited in application because of high electrical resistance. In this paper, a gas-sensing nanocomposite material with p-p heterojunction is introduced based on p-conducting Cr-doped TiO₂ in combination with p-conducting Cr₂O₃. Materials were synthesized via a single-step flame spray pyrolysis (FSP) technique and comprehensively studied by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) specific surface area analysis, transition electron microscopy (TEM), energy dispersive X-ray (EDX) spectroscopy, X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and Raman spectroscopy. Gas sensor performance in direct current (DC) mode was studied toward a number of gasses (H₂, CO, CH₄, NO₂, H₂S, NH₃) as well as volatile organic compounds (VOCs) (acetone, methanol, and formaldehyde) in dry and humid conditions. The long-term stability of the obtained materials’ gas sensor performance was evaluated alongside with an ex situ study of structural evolution. High sensitivity toward oxygenated VOCs and a lower detection limit below ppm level with a limited influence of humidity were shown. The long-term gas sensor performance stability of the obtained materials and its connection to the defect structure of doped TiO₂ is demonstrated.

In this work, we primarily aimed to study the Nb(V) doping effect on the surface activity and optical and electrical properties of nanocrystalline TiO₂ obtained through flame-spray pyrolysis. Materials were characterized using X-ray diffraction, Raman spectroscopy and IR, UV and visible spectroscopy. The mechanism of surface reaction with acetone was studied using in situ DRIFTs. It was found that the TiO₂-Nb-4 material demonstrated a higher conversion of acetone at a temperature of 300 °C than pure TiO₂, which was due to the presence of more active forms of chemisorbed oxygen, as well as higher Lewis acidity of the surface. Conduction activation energies (E_act) were calculated for thin films based on TiO₂-Nb materials. The results of the MB photobleaching experiment showed a non-monotonic change in the photocatalytic properties of materials with an increase in Nb(V) content, which was caused by a combination of factors, such as specific surface area, phase composition, concentration of charge carriers as well as their recombination due to lattice point defects.