Development of sensor materials based on metal oxide semiconductors (MOS) for selective gas sensors is challenging for the tasks of air quality monitoring, early fire detection, gas leaks search, breath analysis, etc. An extensive range of sensor materials has been elaborated, but no consistent guidelines can be found for choosing a material composition targeting the selective detection of specific gases. Fundamental relations between material composition and sensing behavior have not been unambiguously established. In the present review, we summarize our recent works on the research of active sites and gas sensing behavior of n-type semiconductor metal oxides with different composition (simple oxides ZnO, In₂O₃, SnO₂, WO₃; mixed-metal oxides BaSnO₃, Bi₂WO₆), and functionalized by catalytic noble metals (Ru, Pd, Au). The materials were variously characterized. The composition, metal-oxygen bonding, microstructure, active sites, sensing behavior, and interaction routes with gases (CO, NH₃, SO₂, VOC, NO₂) were examined. The key role of active sites in determining the selectivity of sensor materials is substantiated. It was shown that the metal-oxygen bond energy of the MOS correlates with the surface acidity and the concentration of surface oxygen species and oxygen vacancies, which control the adsorption and redox conversion of analyte gas molecules. The effects of cations in mixed-metal oxides on the sensitivity and selectivity of BaSnO₃ and Bi₂WO₆ to SO₂ and VOCs, respectively, are rationalized. The determining role of catalytic noble metals in oxidation of reducing analyte gases and the impact of acid sites of MOS to gas adsorption are demonstrated.

Nanocrystalline perovskite-type BaSnO₃ was obtained via microwave-assisted hydrothermal route followed by annealing at variable temperature. The samples composition and microstructure were characterized. Particle size of 18–23 nm was unaffected by heat treatment at 275–700 °C. Materials DC-conduction was measured at variable temperature and oxygen concentration. Barium stannate exhibited n-type semiconductor behavior at 150–450 °C with activation energy being dependent on the materials annealing temperature. Predominant ionosorbed oxygen species types were estimated. They were shown to change from molecular to atomic species on increasing temperature. Comparative test of sensor response to various inorganic target gases was performed using nanocrystalline SnO₂-based sensors as reference ones. Despite one order of magnitude smaller surface area, BaSnO₃ displayed higher sensitivity to SO₂ in comparison with SnO₂. DRIFT spectroscopy revealed distinct interaction routes of the oxides surfaces with SO₂. Barium-promoted sulfate formation favoring target molecules oxidation was found responsible for the increased BaSnO₃ sensitivity to ppm-range concentrations of SO₂ in air.

Gallium(III) oxide is a promising functional wide-gap semiconductor for high temperature gas sensors of the resistive type. Doping of Ga₂O₃ with tin improves material conductivity and leads to the complicated influence on phase content, microstructure, adsorption sites, donor centers and, as a result, gas sensor properties. In this work, Ga₂O₃ and Ga₂O₃(Sn) samples with tin content of 0–13 at.% prepared by aqueous co-precipitation method were investigated by X-ray diffraction, nitrogen adsorption isotherms, X-ray photoelectron spectroscopy, infrared spectroscopy and probe molecule techniques. The introduction of tin leads to a decrease in the average crystallite size, increase in the temperature of β-Ga₂O₃ formation. The sensor responses of all Ga₂O₃(Sn) samples to CO and NH₃ have non-monotonous character depending on Sn content due to the following factors: the formation of donor centers and the change of free electron concentration, increase in reactive chemisorbed oxygen ions concentration, formation of metastable Ga₂O₃ phases and segregation of SnO₂ on the surface of Ga₂O₃(Sn) grains.

Tungsten oxide is a renowned material for resistive type gas sensors with high sensitivity to nitrogen oxides. Most studies have been focused on sensing applications of WO₃ for the detection of NO₂ and a sensing mechanism has been established. However, less is known about NO sensing routes. There is disagreement on whether NO is detected as an oxidizing or reducing gas, due to the ambivalent redox behavior of nitric oxide. In this work, nanocrystalline WO₃ with different particle size was synthesized by aqueous deposition of tungstic acid and heat treatment. A high sensitivity to NO₂ and NO and low cross-sensitivities to interfering gases were established by DC-resistance measurements of WO₃ sensors. Both nitrogen oxides were detected as the oxidizing gases. Sensor signals increased with the decrease of WO₃ particle size and had similar dependence on temperature and humidity. By means of in situ infrared (DRIFT) spectroscopy similar interaction routes of NO₂ and NO with the surface of tungsten oxide were unveiled. Analysis of the effect of reaction conditions on sensor signals and infrared spectra led to the conclusion that the interaction of WO₃ surface with NO was independent of gas-phase oxidation to NO₂.

Air humidity is one of the main factors affecting the characteristics of semiconductor gas sensors, especially at low measurement temperatures. In this work we analyzed the influence of relative humidity on sensor properties of the hybrid materials based on the nanocrystalline SnO₂ and In₂O₃ and Ru (II) heterocyclic complex and verified the possibility of using such materials for NO (0.25–4.0 ppm) and NO₂ (0.05–1.0 ppm) detection in high humidity conditions (relative humidity (RH) = 20%, 40%, 65%, 90%) at room temperature during periodic blue (λ_max = 470 nm) illumination. To reveal the reasons for the different influence of humidity on the sensors’ sensitivity when detecting NO and NO₂, electron paramagnetic resonance (EPR) spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) investigations were undertaken. It was established that the substitution of adsorbed oxygen by water molecules causes the decrease in sensor response to NO in humid air. The influence of humidity on the interaction of sensitive materials with NO₂ is determined by the following factors: the increase in charge carrier’s concentration, the decrease in the number of active sites capable of interacting with gases, and possible substitution of chemisorbed oxygen with NO₂⁻ groups.