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.
Within the last few years topological insulators (TIs) have attracted a lot of interest due to their unique electronic structure with spin-polarized topological surface states (TSSs), which may pave the way for these materials to have a great potential in multiple applications. However, to enable consideration of TIs as building blocks for novel devices, stability of TSSs towards oxidation should be tested. Among the family of TIs with tetradymite structure, Sb 2 Te 3 is of p-type and appears to be the least explored material since its TSS is unoccupied in the ground state, a property that allows the use of optical excitations to generate spin currents relevant for spintronics. Here, we report relatively fast surface oxidation of Sb 2 Te 3 under ambient conditions. We show that the clean surface reacts rapidly with molecular oxygen and slowly with water, and that humidity plays an important role at the stage of the oxide-layer growth. In humid air, we show that Sb 2 Te 3 oxidizes in a time scale of minutes to hours, and much faster than other tetradymite TIs. The high surface reactivity revealed by our experiments is of critical importance and must be taken into account for the production and exploitation of novel TI-based devices using Sb 2 Te 3 as working material. Our results provide a fundamental and comprehensive understanding of the universal trend underlying the chemical reactivity of TIs.2
Nanocomposites SnO2/SiO2 with a silicon content of [Si]/([Sn] + [Si]) = 3/86 mol.% were obtained by the hydrothermal method. The composition and microstructure of the samples were characterized by EDX, XRD, HRTEM and single-point Brunauer-Emmet-Teller (BET) methods. The surface sites were investigated using thermal analysis, FTIR and XPS. It is shown that the insertion of silicon dioxide up to the value of [Si]/([Sn] + [Si]) = 19 mol.% stabilizes the growth of SnO2 nanoparticles during high-temperature annealing, which makes it possible to obtain sensor materials operating stably at different temperature conditions. The sensor properties of SnO2 and SnO2/SiO2 nanocomposites were studied by in situ conductivity measurements in the presence of 10–200 ppm CO in dry and humid air in the temperature range of 150–400 °C. It was found that SnO2/SiO2 nanocomposites are more sensitive to CO in humid air as compared to pure SnO2, and the sample with silicon content [Si]/([Sn] + [Si] = 13 mol.% is resistant to changes in relative air humidity (RH = 4%–65%) in the whole temperature range, which makes it a promising sensor material for detecting CO in real conditions. The results are discussed in terms of the changes in the composition of surface-active groups, which alters the reactivity of the obtained materials.
Variable air humidity affects the characteristics of semiconductor metal oxides, which complicates the reliable and reproducible determination of CO content in ambient air by resistive gas sensors. In this work, we determined the sensor properties of electrospun ZnO and ZnO/Pd nanofibers in the detection of CO in dry and humid air, and investigated the sensing mechanism. The microstructure of the samples, palladium content, and oxidation state, type, and concentration of surface groups were characterized using complementary techniques: X-ray fluorescent spectroscopy, XRD, high-resolution transmission electron microscopy (HRTEM), high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), energy-dispersive X-ray (EDX) mapping, XPS, and FTIR spectroscopy. The sensor properties of ZnO and ZnO/Pd nanofibers were studied at 100–450 °C in the concentration range of 5–15 ppm CO in dry (RH25 = 0%) and humid (RH25 = 60%) air. It was found that under humid conditions, ZnO completely loses its sensitivity to CO, while ZnO/Pd retains a high sensor response. On the basis of in situ diffuse reflectance IR Fourier transform spectroscopy (DRIFTS) results, it was concluded that high sensor response of ZnO/Pd nanofibers in dry and humid air was due to the electronic sensitization effect, which was not influenced by humidity change.
To obtain a nanocrystalline SnO2 matrix and mono- and bimetallic nanocomposites SnO2/Pd, SnO2/Pt, and SnO2/PtPd, a flame spray pyrolysis with subsequent impregnation was used. The materials were characterized using X-ray diffraction (XRD), a single-point BET method, transmission electron microscopy (TEM), and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) with energy dispersive X-ray (EDX) mapping. The electronic state of the metals in mono- and bimetallic clusters was determined using X-ray photoelectron spectroscopy (XPS). The active surface sites were investigated using the Fourier Transform infrared spectroscopy (FTIR) and thermo-programmed reduction with hydrogen (TPR-H2) methods. The sensor response of blank SnO2 and nanocomposites had a carbon monoxide (CO) level of 6.7 ppm and was determined in the temperature range 60–300 °C in dry (Relative Humidity (RH) = 0%) and humid (RH = 20%) air. The sensor properties of the mono- and bimetallic nanocomposites were analyzed on the basis of information on the electronic state, the distribution of modifiers in SnO2 matrix, and active surface centers. For SnO2/PtPd, the combined effect of the modifiers on the electrophysical properties of SnO2 explained the inversion of sensor response from n- to p-types observed in dry conditions.
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