Determination of C<Subscript>1</Subscript>-C<Subscript>3</Subscript> carboxylic acids in air using a sensor

The adsorption of C₁-C₃ carboxylic acids on modified films of different natures and polarities is studied in exposuring piezoelectric sensors to acid vapors. The method of film fabrication and the ratio of components in the mixed films are optimized; the sensitivity and selectivity of films are calculated; piezoelectric sensors are proposed for the separate determination of acids in air; and equations for calculating their concentrations are derived.     

Metal oxide semiconductor sensors for determination of reactive gas impurities in air

Characteristics of metal oxide semiconductor sensors intended for measuring O₃, NO _x , Cl₂, C1O₂, and HCl microconcentrations were discussed. Specific features of detection of these microimpurities with semiconductor sensors were determined. The size of signal generated by sensors with WO₃-, ZnO-, and In₂O₃-based sensing layers was examined in relation to the O₃, NO _x , Cl₂, C1O₂, and HCl concentration. The sensitivities exhibited by the semiconductor sensors with respect to target impurities make them suitable for measuring their maximum permissible concentrations in sanitary zones and for monitoring background ozone level in atmosphere. Examples of application of gas analyzers based on semiconductor sensors in determination of gas impurities in the open atmosphere were given.     

Separate determination of C1-C3 aliphatic nitrohydrocarbons in air with the use of an electronic nose

An electronic nose system based on piezoresonance sensors was proposed for the analysis of C₁-C₃ nitrohydrocarbons in air. The responses of the multisensor system to the action of aliphatic hydrocarbon vapors were studied over a wide concentration range (5.0 × 10^?3?7.5 × 10^?2 g/m³).     

Determination of low chlorine concentrations in air using semiconductor chemical sensors

Comparative studies of electophysical gas-sensitive properties of semiconductor metal oxides (NiO, WO₃, and In₂O₃) in detecting trace concentrations of chlorine in air at 250–300°C were performed. WO₃ and In₂O₃ film sensors were found to have the best sensitivity, selectivity, and stability. However, WO₃ films are characterized by a longer relaxation time (3 min) compared to In₂O₃ films, for which it is no longer than 30 s. The kinetic and steady-state relative conductivity values of In₂O₃ films as functions of the chlorine concentration in air fall on the same curve in the range 0.01–0.7 ppm. This suggests that the concentration of chlorine in air can be determined from the initial rates of the variation of the relative conductivity of films, which significantly decreases the time of analysis (from 40 to 5 s at a sensor working temperature of 300°C). Changes in air humidity in the range from 40 to 80% have no effect on the initial rates of the variation of the relative conductivity of In₂O₃ films under kinetic conditions. The mechanism of the variation of In₂O₃ film conductivity in detecting chlorine in air was discussed.     

Catalytic oxidation of unsymmetrical dimethylhydrazine on Pt/SiO<Subscript>2</Subscript>

Specific features of oxidation of unsymmetrical dimethylhydrazine on a Pt-containing catalyst were studied. The temperature dependence of the unsymmetrical dimethylhydrazine conversion was determined, and the main intermediate and final reaction products were identified. Platinum behaves in the process as a multifunctional catalyst participating in dehydrogenation, hydrogenolysis, and oxidation. A new method was suggested for detecting unsymmetrical dimethylhydrazine in air. It consists in catalytic conversion of unsymmetrical dimethylhydrazine and detection of the nitrogen dioxide formed with semiconductor gas sensors. The method was successfully used for detecting unsymmetrical dimethylhydrazine in air at concentrations in the range 0.1–10 mg m^–3.     

Development and Calibration of a Portable Air Sampler

This paper describes the development and calibration of a portable air sampler for detecting chemical vapors. The air sampler is equipped with a preconcentrator, a battery operated mini-pump, a three-way valve, capacitive sensors housed in a sensing chamber, and a data acquisition and control circuit board. The preconcentrator is used to adsorb trace level chemicals and to thermally desorb them into the sensing chamber. The air sampler was calibrated using known concentrations of ethylbenzene vapor generated by an Environics gas mixing system. The air sampler was also tested using low concentration toluene and ethanol vapors generated by diffusion based vapor generation device. The concentration factor of the preconcentrator was experimentally determined.     

Sensitivity of semiconductor metal oxides (SnO2, WO3, ZnO) to hydrogen sulfide in dry and humid gas media

The sensitivity of semiconductor sensors based on tin (SnO₂), tungsten (WO₃), and zinc (ZnO) oxides and SnO₂ with catalytic admixtures of La₂O₃ and CuO to hydrogen sulfide is studied at H₂S concentration 50 ppm in dry air in the temperature range 100–600°C. Concentration dependences for oxides are studied in the temperature range 350–450°C and H₂S concentration range 0.5–100 ppm at the humidity of gas media 0–80 rel. %. It is shown that, under the specified conditions, the resistance and of sensors to H₂S in air weakly depends on humidity. It was found that sensors based on SnO₂ with an admixture of 3% La₂O₃ working at 350°C are the best for the registration of H₂S by the set of performance and operation characteristics. A presumable mechanism of H₂S interaction with oxide surfaces is considered, according to which each H₂S molecule releases seven electrons to the conductivity zone of the oxide and molecules of metal oxides in the surface layer are, possibly, partially replaced by sulfide molecules.     

Tin Acetylacetonate as a Precursor for Producing Gas-Sensing SnO<Subscript>2</Subscript> Thin Films

To expand the range of precursors used in the sol–gel technology for applying nanostructured SnO₂ thin films promising as components of semiconductor chemical gas sensors, the efficiency of using tin acetylacetonate solutions with various precursor concentrations was demonstrated. It was determined that finely divided SnO₂ with a crystallite size of 3–4 nm (cassiterite) can be obtained by hydrolysis by atmospheric moisture in the course of solvent evaporation at room temperature. Using tin acetylacetonate solutions with various precursor concentrations for applying SnO₂ thin films by dip coating to the surface of rough ceramic Al₂O₃-based substrates with platinum interdigital electrodes and a microheater resulted in significant differences in microstructure, continuity, thickness, and porosity of the produced coatings. In a lower-concentration (0.13 mol/L) tin acetylacetonate solution, a multilayer dense continuous SnO₂ coating was applied, whereas in a higher-concentration (0.25 mol/L) solution, the formed layer comprised aggregated nanoparticles 30–60 nm in size and had much more defects and higher porosity. The sensitivity of the obtained thin-film nanostructures to the most practically important gaseous analytes: CO, H₂, CH₄, CO₂, and NO₂. The produced two-dimensional nanomaterials were shown to be promising for detecting carbon monoxide at 200–300°C in dry air.     

Structure of SmCl3, DyCl3, and HoCl3 molecules based on the data of synchronous electron diffraction and mass-spectrometric experiment

Saturated vapors of SmCl₃, DyCl₃, and HoCl₃ have been studied in the framework of a synchronous electron diffraction and mass-spectrometric experiment at temperatures 1205 K, 1160 K, and 1148 K, respectively. In vapors of all compounds, along with monomer molecular forms, an insignificant (up to 2 mol.%) amount of dimers was detected. Parameters of the effective configuration of monomer molecules were determined. For molecules SmCl₃, DyCl₃, and HoCl₃ values of internuclear distances r _g(Ln-Cl) were 2.511(5) Å, 2.453(5) Å, and 2.444(5) Å, values of valence angles ∠_g(Cl-Ln-Cl) were 115.6(11)°, 116.8(10)°, and 116.6(10)°, respectively. It is shown that parameters of the r _g-structure are not incompatible with the notion of a planar equilibrium geometrical configuration of molecules SmCl₃, DyCl₃, and HoCl₃. Main tendencies in the change of structural and vibration characteristics in the series of lanthanide trichlorides are considered.     

Detection of organophosphorus compounds with semiconductor gas sensors using adsorption preconcentration

Effective concentrators for organophosphorus compounds, highly sensitive semiconductor sensors, and a prototype of a detector for specific determination of low concentrations of organophosphorus compounds in air were developed. It is preferable to use as concentrating sorbents silicates with low density of surface hydroxy groups, ensuring high degree of recovery of the target compound by thermal desorption without its decomposition. SnO₂ modified with RuO₂ is the most sensitive sensor material.     

Proton‐Conductive 3D LnIII Metal–Organic Frameworks for Formic Acid Impedance Sensing

Metal‐organic frameworks (MOFs) as new classes of proton‐conducting materials have been highlighted in recent years. Nevertheless, the exploration of proton‐conducting MOFs as formic acid sensors is extremely lacking. Herein, we prepared two highly stable 3D isostructural lanthanide(III) MOFs, {(M(μ₃‐HPhIDC)(μ₂‐C₂O₄)_0.5(H₂O))?2 H₂O}_n (M=Tb ( ZZU‐1 ); Eu ( ZZU‐2 )) (H₃PhIDC=2‐phenyl‐1H‐imidazole‐4,5‐dicarboxylic acid), in which the coordinated and uncoordinated water molecules and uncoordinated imidazole N atoms play decisive roles for the high‐performance proton conduction and recognition ability for formic acid. Both ZZU‐1 and ZZU‐2 show temperature‐ and humidity‐dependent proton‐conducting characteristics with high conductivities of 8.95×10^?4 and 4.63×10^?4 S cm^‐1 at 98 % RH and 100 °C, respectively. Importantly, the impedance values of the two MOF‐based sensors decrease upon exposure to formic acid vapor generated from formic aqueous solutions at 25 °C with good reproducibility. By comparing the changes of impedance values, we can indirectly determine the concentration of HCOOH in aqueous solution. The results showed that the lowest detectable concentrations of formic acid aqueous solutions are 1.2×10^?2 mol L^?1 by ZZU‐1 and 2.0×10^?2 mol L^?1 by ZZU‐2 . Furthermore, the two sensors can distinguish formic acid vapor from interfering vapors including MeOH, N‐hexane, benzene, toluene, EtOH, acetone, acetic acid and butane. Our research provides a new platform of proton‐conductive MOFs‐based sensors for detecting formic acid.     

Mechanism of the Reaction of 1,1-Dimethylhydrazine with Copper(II) and Palladium(II) Chloride Complexes Containing Poly-(N-2-Alcoxycarbonylethyl)-Ethyleneimine

The mechanism of the sorption of 1,1-dimethylhydrazine vapors with metal chloride complexes of poly-(N-2-R-oxycarbonylethyl)-ethyleneimines (R = –n-C₄H₉, –n-C₁₀H₂₁) was studied by Fourier transform IR spectroscopy (FTIR) and piezoelectric resonance. The structure of the products was determined. This allowed for the optimization of the chemical composition and structure of poly-(N-2-R-oxycarbonylethyl)-ethyleneimine-based complexes in their use as sensitive coatings of piezoelectric sensors for determining 1,1-dimethylhydrazine vapors in air.     

Semiconductor Sensors for Studying the Heterogeneous Destruction of Ozone at Low Concentrations

Prospects for the use of semiconductor resistive sensors in studies of the heterogeneous destruction of ozone at low concentrations (5–400 μg/m³) were shown. The influence of various factors (sensor temperature, gas flow rate, ozone concentration) on the results of ozone concentration measurements with sensors of various types was studied. Methods for forming a sensitive layer of In₂O₃(3% Fe₂O₃) sensors with specified parameters of calibration curves were proposed. The optimum conditions for the operation of sensors in a flow mode were formulated. The results of the study of heterogeneous destruction of ozone on microfiber polymer and natural disperse (sand, coals) materials obtained by the developed method were presented.     

Gas-Sensing Properties of Doped In2O3 Films as Sensors for NO2 in Air

A number of sensing systems based on indium oxide doped with various metal oxides (In₂O₃ · WO₃, In₂O₃ · ZnO, In₂O₃ · RuO₂, In₂O₃ · Gd₂O₃, and In₂O₃ · Sm₂O₃) in amounts of no more than 3–5 mol % and also Au · In₂O₃ films were studied as sensors for detecting NO₂ in air. The working temperature of sensors was 250°C (except for In₂O₃ · RuO₂, for which T = 150–190°C). In₂O₃ · WO₃-based sensors reach a high sensitivity especially at a concentration of NO₂ in air higher than 10 ppm (the relative sensor conductivity changes by 2.5 orders of magnitude). However, a shortcoming of this system is an increased response time (7–9 min) as compared to the other studied systems, for which the response time does not exceed 15–20 s. In₂O₃ · Gd₂O₃ and In₂O₃ · Sm₂O₃ films exhibit the best sensing properties in sensitivity, selectivity, and stability. Various NO₂ species adsorbed on the surface of dispersed indium oxide were detected by Fourier-transform IR spectroscopy. The mechanism of changing the conductivity of In₂O₃ · Gd₂O₃ films upon detecting NO₂ in air is discussed.     

Gas-sensitive properties of thin nickel oxide films

The results of a study of the gas-sensitive properties of nickel oxide layers with respect to n-hexane, acetone, ethanol, benzene, o-xylene, toluene and ammonia are presented. NiO layers 100 ± 5 nm thick were obtained by chemical vapor deposition in the systems (EtCp)₂Ni–О₂–Ar and (EtCp)₂Ni–О₃–О₂–Ar. The electrical resistance of the layers changes in the presence of hexane, ethanol, benzene, and ammonia vapors. The electrical resistance of the obtained layers changed in the presence of vapors of hexane, ethanol, benzene and ammonia. Response and recovery time of the sensing element of the gas sensors did not exceed 6 s in the temperature range 500–600 K.     

Potassium polytitanate gas-sensor study by impedance spectroscopy

Nanocrystalline potassium polytitanates K₂O·nTiO₂·mH₂O represent a new type of semiconducting compounds which are characterized by a high specific surface that makes them promising for use in gas sensors. In this work, we have studied potassium polytitanate mesoporous nanoparticle agglomerates placed over a SiO₂/Si substrate equipped with multiple coplanar electrodes to measure the electrical response to various organic vapors, 1000 ppm of concentration, mixed with air by impedance spectrometry in range of the 10⁻²–10⁶ Hz. The recorded impedance data for each sensor segment are associated with RC components of an equivalent circuit which are applied to selectively recognize the test vapors exploiting a “multisensor array” approach.     

Hydrogen content in proton-conducting perovskites CaZr1 − x Sc x O3 − x /2 (x = 0.0–0.2)

The hydrogen content in CaZr_{1 ? x} Sc _x O_{3 ? x/2} (x = 0.00–0.20) and BaZr_0.9Y_0.1O_3-α (for comparison) was studied by powder nuclear microanalysis. The samples were saturated with heavy water (D₂O) vapors at 350 and 400°C in air. The chemical expansion of the CaZr_0.95Sc_0.05O_3-α and BaZr_0.95Y_0.05O_3-α samples at 700°C was measured at different water vapor pressures. A model was suggested to explain the lowered hydrogen content in oxides based on CaZrO₃.     

Transition metals Fe3+, Ni2+ modified titanium dioxide (TiO2) film sensors fabricated by CPT method to sense some toxic environmental pollutant gases

The present investigation deals synthesis of undoped TiO₂, Ni²⁺ doped TiO₂, and Fe³⁺ doped TiO₂ nanoparticles by low-cost co-precipitation (CPT) method. The thick film sensors of all the fabricated modified TiO₂ nanoparticles were designed by a screen printing strategy. The prepared thick film sensors were characterized by various sophisticated techniques. The structural parameters of undoped TiO₂ and modified TiO₂ film sensors were characterized by X-Ray Diffraction (XRD) which confirmed anatase phase of TiO₂ lattice. The surface morphological properties of all the prepared materials were confirmed by means of scanning electron microscope (SEM). The energy dispersive spectroscopy (EDS) confirms the elemental composition of all the prepared materials. High-Resolution Transmission Electron Microscopy (HR-TEM) was utilized to investigate the crystal lattice of fabricated TiO₂ material. The HR-TEM results revealed the anatase phase crystal morphology of prepared material. The prepared TiO₂ materials were also characterized by means of X-Ray photoelectron spectroscopy (XPS) to confirm the surface doping, specific biding energies, chemical states and elemental composition of modified TiO₂ materials. The Brunauer–Emmett–Teller (BET) study was carried to investigate the specific surface area of all the prepared sensors. The Fe³⁺ doped TiO₂ sensor found with enhanced surface area (83.10 ​m²/g) in comparison to Ni²⁺ doped TiO₂ and bare TiO₂ (67.34 ​m²/g). All the prepared materials were investigated for gas sensing characteristics. The NO₂, SO₂, and CO₂ gases were investigated for all the prepared sensors. The reusability test confirms that the Fe³⁺ doped TiO₂ is reproducible and stable sensor for long time repeated sensing of SO₂ and NO₂ vapors. Importantly, Fe³⁺ doped TiO₂ sensor showed rapid response and recovery towards SO₂ and NO₂ vapors.     

Organic vapour sensing using localized surface plasmon resonance spectrum of metallic nanoparticles self assemble monolayer

The response of localized surface plasmon resonance (LSPR) spectra of gold and silver nanoparticles, and gold nanoshells to organic vapors was investigated. The surface area of nanomaterials was sufficiently high for quantitative adsorption of volatile organic compounds (VOCs). Surface adsorption and condensation of VOCs caused the environmental refractive index to increase from n = 1.00 in pure air to as high as n = 1.29 in near saturated toluene vapor. The extinction and wavelength shift of the LSPR spectra were very sensitive to changes in the surface refractive index of the nanoparticles. Responses of the LSPR band were measured with a real-time UV-vis spectrometer equipped with a CCD array detector. The response of silver nanoparticles to organic vapors was most sensitive in changes in extinction, while gold nanoshells exhibited red-shifts in wavelength (∼250 nm/RIU) when exposed to organic vapors. The LSPR spectral shifts primarily were determined by the volatility and refractive indices of the organic species. The T₉₀ response time of the VOC-LSPR spectrum was less than 3 s and the response was completely reversible and reproducible.     

Direct analysis of ultra-trace semiconductor gas by inductively coupled plasma mass spectrometry coupled with gas to particle conversion-gas exchange technique

An inductively coupled plasma mass spectrometry (ICPMS) coupled with gas to particle conversion-gas exchange technique was applied to the direct analysis of ultra-trace semiconductor gas in ambient air. The ultra-trace semiconductor gases such as arsine (AsH₃) and phosphine (PH₃) were converted to particles by reaction with ozone (O₃) and ammonia (NH₃) gases within a gas to particle conversion device (GPD). The converted particles were directly introduced and measured by ICPMS through a gas exchange device (GED), which could penetrate the particles as well as exchange to Ar from either non-reacted gases such as an air or remaining gases of O₃ and NH₃. The particle size distribution of converted particles was measured by scanning mobility particle sizer (SMPS) and the results supported the elucidation of particle agglomeration between the particle converted from semiconductor gas and the particle of ammonium nitrate (NH₄NO₃) which was produced as major particle in GPD. Stable time-resolved signals from AsH₃ and PH₃ in air were obtained by GPD-GED-ICPMS with continuous gas introduction; however, the slightly larger fluctuation, which could be due to the ionization fluctuation of particles in ICP, was observed compared to that of metal carbonyl gas in Ar introduced directly into ICPMS. The linear regression lines were obtained and the limits of detection (LODs) of 1.5 pL L⁻¹ and 2.4 nL L⁻¹ for AsH₃ and PH₃, respectively, were estimated. Since these LODs revealed sufficiently lower values than the measurement concentrations required from semiconductor industry such as 0.5 nL L⁻¹ and 30 nL L⁻¹ for AsH₃ and PH₃, respectively, the GPD-GED-ICPMS could be useful for direct and high sensitive analysis of ultra-trace semiconductor gas in air.