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 (λmax = 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.
Formaldehyde (HCHO) is an important indicator of indoor air quality and one of the markers for detecting lung cancer. Both medical and air quality applications require the detection of formaldehyde in the sub-ppm range. Nanocomposites SnO2/TiO2 are promising candidates for HCHO detection, both in dark conditions and under UV illumination. Nanocomposites TiO2@SnO2 were synthesized by ALD method using nanocrystalline SnO2 powder as a substrate for TiO2 layer growth. The microstructure and composition of the samples were characterized by ICP-MS, TEM, XRD and Raman spectroscopy methods. The active surface sites were investigated using FTIR and TPR-H2 methods. The mechanism of formaldehyde oxidation on the surface of semiconductor oxides was studied by in situ DRIFTS method. The sensor properties of nanocrystalline SnO2 and TiO2@SnO2 nanocomposites toward formaldehyde (0.06–0.6 ppm) were studied by in situ electrical conductivity measurements in dark conditions and under periodic UV illumination at 50–300 °C. Nanocomposites TiO2@SnO2 exhibit a higher sensor signal than SnO2 and a decrease in the optimal measurement temperature by 50 °C. This result is explained based on the model considering the formation of n-n heterocontact at the SnO2/TiO2 interface. UV illumination leads to a decrease in sensor response compared with that obtained in dark conditions because of the photodesorption of oxygen involved in the oxidation of formaldehyde.
In this work, the hybrids based on nanocrystalline SnO2 or In2O3 semiconductor matrixes and heterocyclic Ru(II) complex are studied as materials for gas sensors operating at room temperature under photoactivation with visible light. Nanocrystalline semiconductor oxides are obtained by chemical precipitation with subsequent thermal annealing and characterized by XRD, SEM and single-point BET methods. The heterocyclic Ru(II) complex is synthesized for the first time and investigated by 1H NMR, 13C NMR APT, MALDI-MS analysis, and UV-Vis spectroscopy. The HOMO and LUMO energies of the Ru(II) complex are calculated from cyclic voltammetry data. The hybrid materials are characterized by TGA-MS analysis and EDX mapping. The optical properties of hybrids are studied by UV-Vis spectroscopy in the diffuse reflection mode. The investigation of spectral dependencies of photoconductivity of hybrid samples demonstrates that the role of organic dye consists in shifting the photosensitivity range towards longer wavelengths. Sensor measurements demonstrate that hybrid materials are able to detect NO2 in the concentration range of 0.25–2 ppm without the use of thermal heating under periodic illumination with even low-energy long-wavelength (red) light.
The development of safety sensors is an urgent necessity for the successful use of hydrogen in real conditions, which may differ, in particular, by the oxygen content in the surrounding atmosphere. Palladium-modified zinc oxide shows the high sensitivity when detecting hydrogen in air; however, studies of the sensor properties and the operation mechanism of the ZnO/Pd sensor when reducing gases are detected in an oxygen deficient or inert atmosphere have not been effectuated. In this work, we synthesized the ZnO and ZnO/Pd nanofibers by electrospinning and for the first time determined their sensor properties in the detection of CO, NH3 and H2 in different oxygen backgrounds. The microstructure and composition of nanofibers were characterized by electron microscopy, X-ray diffraction, X-ray fluorescent spectroscopy, and X-ray photoelectron spectroscopy. The interaction with the gas phase was investigated in situ by diffuse reflectance IR Fourier transform spectroscopy (DRIFTS). The sensor properties of ZnO and ZnO/Pd nanofibers were studied at 100–450 °C towards CO, NH3 and H2 in the N2/O2 gas mixtures containing 0.0005–20% O2. When detecting CO, a decrease in the oxygen concentration from 20 to 0.0005% in the gas phase does not lead to a significant change in the sensor response. At the same time, when detecting NH3 and especially H2, a decrease in oxygen concentration down to 0.0005% results in the dramatic increase in the sensor response of ZnO/Pd nanofibers. This result is discussed in terms of palladium hydride formation, modulation of the potential barrier at the ZnO/Pd interface, as well as changes in the concentration of donor defects and charge carriers in the ZnO matrix. Synthesized electrospun ZnO/Pd nanofibers are extremely promising materials for sensors for detecting hydrogen in an oxygen free atmosphere.
In this work we analyze the effectiveness of decoration of nanocrystalline SnO2/TiO2 composites with gold nanoparticles (Au NPs) and platinum nanoparticles (Pt NPs) in enhancing gas sensor properties in low-temperature HCHO detection. Nanocrystalline SnO2/TiO2 composites were synthesized by a chemical precipitation method with following modification with Pt and Au NPs by the impregnation method. The nanocomposites were characterized by TEM, XRD, Raman and FTIR spectroscopy, DRIFTS, XPS, TPR-H2 methods. In HCHO detection, the modification of SnO2 with TiO2 leads to a shift in the optimal temperature from 150 to 100 °C. Further modification of SnO2/TiO2 nanocomposites with Au NPs increases the sensor signal at T = 100 °C, while modification with Pt NPs gives rise to the appearance of sensor responses at T = 25 °C and 50 °C. At 200 °C nanocomposites exhibited high selectivity toward formaldehyde within the sub-ppm concentration range among different VOCs. The influence of Pt and Au NPs on surface reactivity of SnO2/TiO2 composite and enhancement of the sensor response toward HCHO was studied by DRIFT spectroscopy and explained by the chemical and electronic sensitization mechanisms.