Impedancemetric gas sensor based on Pt and WO3 co-loaded TiO2 and ZrO2 as total NOx sensing materials

Pt-loaded metal oxides [WO₃/ZrO₂, MO_x/TiO₂ (MO_x = WO₃, MoO₃, V₂O₅), WO₃ and TiO₂] equipped with interdigital Au electrodes have been tested as a NO_x (NO and NO₂) gas sensor at 500 °C. The impedance value at 4 Hz was used as a sensing signal. Among the samples tested, Pt-WO₃/TiO₂ showed the highest sensor response magnitude to NO. The sensor was found to respond consistently and rapidly to change in concentration of NO and NO₂ in the oxygen rich and moist gas mixture at 500 °C. The 90% response and 90% recovery times were as short as less than 5–10 s. The impedance at 4 Hz of the present device was found to vary almost linearly with the logarithm of NO_x (NO or NO₂) concentration from 10 to 570 ppm. Pt-WO₃/TiO₂ showed responses to NO and NO₂ of the same algebraic sign and nearly the same magnitude, while Pt/WO₃ and WO₃/TiO₂ showed higher response to NO than NO₂. The impedance at 4 Hz in the presence of NO for Pt-WO₃/TiO₂ was almost equal at any O₂ concentration examined (1–99%), while in the case of Pt/WO₃ and WO₃/TiO₂ the impedance increased with the oxygen concentration. The features of Pt-WO₃/TiO₂ are favorable as a NO_x sensor that can monitor and control the NO_x concentration in automotive exhaust. The effect of WO₃ loading of Pt-WO₃/ZrO₂-based sensor is studied to discuss the role of surface W-OH sites on the NO_x sensing.     

Electrical characterization of porous BaTiO3 using impedance spectroscopy in humid condition

The humidity response characteristics of La doped BaTiO₃ with different sintered densities and room temperature electrical conductivities were investigated using complex impedance measurement. The samples with low density and high resistivity showed the large and nearly linear sensitivity to the change of humidity. The impedance spectra of samples, when exposed to high humidity, can exhibit microstructure-related features, even though they do not give rise to a noticeable characteristic change when exposed to low humidity. The observed impedance patterns were dependent upon the density, and hence the oxidation kinetics of BaTiO₃.     

Doping behavior of CdO in BaTiO3-based PTCR ceramics

Impurities have great influence on the PTCR effect in BaTiO₃ ceramics, especially a donor and an acceptor. When Cd replaces Ba as equivalent impurity, neither donor nor acceptor does it act as. However, it was found that doping with either solid CdO or vapor one resulted in the enhancement of the PTCR effect of BaTiO₃-based semiconducting ceramics. The mechanism of the enhancement of the PTCR effect is also discussed.     

Highly sensitive and fast responding CO sensor using SnO2 nanosheets

A highly sensitive and fast responding CO sensor was fabricated from a sheet-like SnO₂. The SnO sheets were prepared by a room temperature reaction between SnCl₂, hydrazine and NaOH, and they were subsequently oxidized into SnO₂ sheets at high temperature (600 °C). The morphology and size of the SnO₂ sheets could be controlled during the formation of SnO, which influence the sensor response (R_a/R_g) and response time to a great extent. The sensor response of SnO nanosheets to 10 ppm CO was enhanced up to 2.34, and the 90% sensor response time could be reduced to 6 s, which are significantly higher and shorter than those of SnO₂ powders (1.57 and 88 s), respectively. The realization of both a high sensitivity and rapid response were explained in terms of rapid gas diffusion onto the entire sensing surface due to the less-agglomerated and very thin structure of SnO₂ nanosheets and the catalytic effect of Pt.     

NOx sensing properties of In2O3 nanoparticles prepared by metal organic chemical vapor deposition

In₂O₃ nanoparticles were deposited by low-temperature metal organic chemical vapor deposition. The response of 10-nm thick In₂O₃ particle containing layers to NO_x and O₂ gases is investigated. The lowest detectable NO_x concentration is 200 ppb and the sensor performance is strongly dependent on the gas partial pressure as well as on the operating temperature. The sensor response towards 200 ppm of NO_x is found to be above 10⁴. Furthermore, the cross-sensitivity against O₂ is very low, demonstrating that the In₂O₃ nanoparticles are very suitable for the selective NO_x detection.     

High-performance solid-electrolyte SOx sensor using MgO-stabilized zirconia tube and Li2SO4---CaSO4---SiO2 auxiliary phase

Solid-electrolyte-based electrochemical SO_x sensors fabricated with MgO-stabilized zirconia and Li₂SO₄---CaSO₄---SiO₂ (4:4:2 in molar ratio) exhibit fairly good sensing characteristics for 2–200 ppm SO₂ in air at 600–750 °C, with the e.m.f. responses following the Nernst equation for the two-electron reduction of SO₂. The 90% response and 90% recovery times to 20 ppm SO₂ are 10 s and 7 min at 650 °C, and 10 s and 3 min at 700 °C, respectively. It is further found that the sensor exhibits excellent selectivity to SO_x in the coexistence of CO₂ and NO_x, and good long-term stability. The sensor is simple in structure, easy to prepare, and quite tough chemically and mechanically. These features should ensure practical use for this SO_x sensor.     

Microstructure, electrical and ethanol-sensing properties of perovskite-type SmFe0.7Co0.3O3

Ultrafine SmFe_0.7Co_0.3O₃ powder, prepared by a sol–gel method, shows a single-phase orthogonal perovskite structure. The influence of annealing temperature upon its crystal cell volume, microstructure, electrical and ethanol-sensing properties was investigated in detail. When the annealing temperature increases from 600 to 950 °C, the unit cell volume of the SmFe_0.7Co_0.3O₃ sample reduces, and its average grain size increases. When the annealing temperature increases from 600 to 850 °C, the optimal working temperature and response to ethanol of the SmFe_0.7Co_0.3O₃ sensor increase, and the response–recovery time shortens. But when the annealing temperature further increases from 850 to 950 °C, there are decreases of the optimal working temperature and sensor response, and the response–recovery time is prolonged. The results indicate that, as for sensor response, its optimal annealing temperature is about 850 °C, and the sensor based on SmFe_0.7Co_0.3O₃ annealed at 850 °C shows the highest response S = 80.8 to 300 ppm ethanol gas, and it has the best response–recovery and selectivity characteristics. When the ethanol concentration is as low as 500 ppm, the curve of its optimal response versus concentration is nearly linear. Meanwhile, the influence mechanisms of annealing temperature upon the conductance, the optimal working temperature and sensor response for SmFe_0.7Co_0.3O₃ were studied.     

High aspect ratio In2O3 nanowires: Synthesis, mechanism and NO2 gas-sensing properties

Flexural In₂O₃ nanowires with high aspect ratios were synthesized via a hydrothermal–annealing route. The as-synthesized In₂O₃ nanowires had diameters of 30–50 nm and length up to several microns. Various reaction parameters, such as the kind of reagents, the time of hydrothermal treatment, annealing time and annealing temperature, were investigated by a series of control experiments. The as-synthesized In₂O₃ nanowires showed excellent gas-sensing properties to NO₂ in terms of sensor response and selectivity.     

Potentiometric CO2 gas sensor with lithium phosphorous oxynitride electrolyte

Potentiometric cell, Au/LiCoO₂ 5 m/o Co₃O₄/Li_2.88PO_3.73N_0.14/Li₂CO₃/Au, has been fabricated and investigated for monitoring CO₂ gas. A LiCoO₂–Co₃O₄ mixture was used as the solid-state reference electrode instead of a reference gas. The idea is to keep the lithium activity constant on the reference side using thermodynamic equilibrium at a given temperature. The thermodynamic stability of the reference electrode was studied from the phase stability diagram of Li–Co–C–O system. The Gibb’s free energy of formation of LiCoO₂ was estimated at 500°C from the measured value of the cell emf. The sensors showed good reversibility and fast response toward changing CO₂ concentrations from 200 to 3000 ppm. The emf values were found to follow a logarithmic Nernstian behavior in the 400–500°C temperature range. CH₄ gas did not show any interference effect. Humidity and CO gas decreased the emf values of the sensor slightly. NO and NO₂ gases affect this sensor significantly at low temperatures. However, increased operating temperature seems to reduce the interference.     

H2 sensors using Fe2O3-based thin film

This paper describes the fabrication procedure as well as the sensing properties of new hydrogen sensors using Fe₂O₃-based thin film. The film is deposited by the r.f. sputtering technique; its composition is Fe₂O₃, TiO₂(5 mol%) and MgO(0–12 mol%). The conductance change of the film is examined in various test gases. The sensitivity to hydrogen gas is enhanced by treating the film in vacuum at 550 °C for 4 h and then in air at 700 °C for 2 h. The sputtered film is identified to be polycrystalline -Fe₂O₃ based on X-ray diffraction patterns. However, the surface layer is considered to be changed to Fe₃O₄ after heating in vacuum and then to γ-Fe₂O₃ after heating in air. The film is thus a multilayer one with a thin γ-Fe₂O₃ layer on a -Fe₂O₃ layer. The sensing mechanism is discussed based on measurements of the physical properties of the film, such as the temperature dependence of the sensor conductance, X-ray diffraction pattern, surface morphology, RBS (Rutherford back-scattering) spectrum and optical absorption spectrum.     

Selective NH3 gas sensor based on Langmuir-Blodgett polypyrrole film

Polypyrrole thin films have been deposited onto a glass substrate by the Langmuir-Blodgett technique to fabricate a selective ammonia (NH₃) gas sensor. The d.c. electrical resistance of the sensing elements is found to exhibit a specific increase upon exposure to different gases such as NH₃, CO, CH₄, H₂ in N₂ and pure O₂. The polypyrrole thin-film detector shows a considerable increase of resistance when exposed to NH₃ in N₂, and negligible response when exposed to comparable concentrations of interfering gases such as CO, CH₄, H₂ in N₂ and pure O₂. The calibration curve for NH₃ in N₂ at room temperature is measured in the concentration range from 0.01 to 1%. The relative change of the electrical resistance is about 10% for the lower detectable limit of 100 ppm of NH₃ in N₂. The sensitivity of the Langmuir-Blodgett polypyrrole towards ammonia is considerably higher than that of the electrochemical polypyrrole. The fast rise time and the high sensitivity of the detector are reported as a function of number of the polypyrrole layers. Long-term aging tests of the selective NH₃ gas sensor are performed.     

Production of singlet oxygen by Ru(dpp(SO3)2)3 incorporated in polyacrylamide PEBBLES

Polyacrylamide (PAA) and amine-functionalized PAA (AFPAA) nanoparticles with disulfonated 4,7-diphenyl-1,10-phenantroline ruthenium (Ru(dpp(SO₃)₂)₃) have been prepared. The nanoparticles produced have a hydrodynamic radius of 20–25 nm.

The amount of singlet oxygen (¹O₂) produced by Ru(dpp(SO₃)₂)₃ as been measured using anthracene-9,10-dipropionic acid (ADPA). A kinetic model for the disappearance of ADPA, by steady state irradiation of Ru(dpp(SO₃)₂)₃ at 465 nm, has been developed taking also into account a consumption not mediated by ¹O₂. This direct consumption of ADPA is evaluated by irradiating in the presence of NaN₃ and is about 30% of the total. All the experimental results are very well described by the model developed, both for free Ru(dpp(SO₃)₂)₃ and with this dye incorporated in the nanoparticles.

It is found that the polyacrylamide matrix does not quench the ¹O₂ produced, allowing it to reach the external solution of the nanoparticles and react with ADPA. When the matrix possesses amine groups, AFPAA, the amount of ¹O₂ that reacts with ADPA is slightly reduced, 60%, but most of the ¹O₂ produced can still leave the particles and react with external molecules. The particles produced may therefore be used as sources of ¹O₂ in photodynamic therapy (PTD) of cancers. The fact that those nanoparticles do not quench significantly the ¹O₂ makes possible the future development of ¹O₂ sensors based on PAA nanoparticles with the appropriate sensor molecule enclosed.     

Effect of surface modification on NO2 sensing properties of SnO2 varistor-type sensors

NO₂ sensing properties of SnO₂-based varistor-type sensors have been investigated in the temperature range of 400-650°C and in the NO₂ concentration range of 15–30 ppm. Pure SnO₂ exhibited a weak nonlinear I–V characteristic in air, but clear nonlinearity in NO₂ at 450°C. The breakdown voltage of SnO₂ shifted to a high electric field upon exposure to NO₂ and the magnitude of the shift was well correlated with NO₂ concentration. Thus, SnO₂ exhibited some sensitivity to NO₂ as a varistor-type sensor. When SnO₂ particles coated with a SiO₂ thin film were used as a raw material for fabricating a varistor, the breakdown voltage in air was approximately the double that of pure SnO₂ and the sensitivity to 15 ppm NO₂ was enhanced slightly. However, the sensitivity to 30 ppm NO₂ decreased. The Cr₂O₃-loading on SnO₂ also led to an increase in the breakdown voltage in air, but the Cr₂O₃ addition was not effective for promoting the NO₂ sensitivity under the present experimental conditions.     

Material properties and the influence of metallic catalysts at the surface of highly dense SnO2 films

We present an approach to optimize the specific response to gases by using specially prepared nanosized platinum on highly dense sputtered polycrystalline SnO₂. Structural and morphological analyses of the SnO₂ and platinum thin films were performed. Gas measurements were carried out with single chip thin-film SnO₂ sensor arrays on silicon substrates. Pt nanoclusters covering the sensitive layer significantly affect the O₃, CO and NO₂ sensitivities and the corresponding dynamic response.     

Electrochemical measurement of SO3-SO2 in process gas streams

The two major industrial sources of sulphur dioxide emissions are electrical generation and non-ferrous smelting. While flue-gas scrubbing and acid-plant technology are well established, continuous methods for the determination of SO₂ in these process streams are based on expensive conventional UV or IR spectroscopic instrumentation in which the gases must be conditioned prior to analysis. Additionally, there appears to be no reliable continuous low-maintenance method of analysis for SO₃ in gases. Solid-state sensors for the continuous real-time measurement of concentrations of SO₃ and SO₂ in process gas streams offer the possibility of monitoring the efficiency of flue-gas scrubbing, determining the concentrations of SO₃ in corrosion-susceptible ducting or in acid-plant conversion towers and guarding against excessive releases of SO₃ from acid-plant tail gas. The measurement of SO₂ and SO₃ in gases by solid-state electrochemistry is reviewed. The electrochemical cells are described, and wherever possible, the temperature and concentration ranges of the various solid-state devices reported in the literature are given. We conclude with a summary of the further requirements for a successful inexpensive commercial solid-state sensor for SO₃ and SO₂ measurement in process gas streams.     

Pyroelectric and dielectric properties of sol–gel derived barium–strontium–titanate (Ba0.64Sr0.36TiO3) thin films

The barium–strontium–titanate (BST, Ba_0.64Sr_0.36TiO₃) thin films have been prepared by the sol–gel method on a platinum-coated silicon substrate. The resulting thin films show very good dielectric and pyroelectric properties. The dielectric constant and dissipation factor for Ba_0.64Sr_0.36TiO₃ thin film at a frequency of 200 Hz were 592 and 0.028, respectively. The dependence of the capacitance as a function of the voltage shows a strongly non-linear character, and two peaks characterizing spontaneous polarization switching can be clearly seen in this curve, indicating that the films have a ferroelectric nature. The capacitance changed from 495 to 1108 pF with the applied voltage in the −5 to +5 V range at a frequency of 100 kHz. The peak pyroelectric coefficient at 30 °C is 1080 μC/m² K. The pyroelectric coefficient at room temperature (25 °C) is 1860 μC/m² K, and the figure-of-merit of this film is 37.4 μC/m³ K. The high pyroelectric coefficients and the greater figures-of-merit of Ba_0.64Sr_0.36TiO₃ thin films make it possible to be used for thermal infrared detection and imaging.     

Room temperature synthesis of γ-Fe2O3 by sonochemical route and its response towards butane

Nanocrystalline gamma iron oxide (γ-Fe₂O₃) has been synthesized at room temperature through sonication-assisted precipitation technique. The key in obtaining γ-Fe₂O₃ at room temperature lies in exploiting high-power ultrasound (600 W). The gas-sensing properties to n-butane of pure γ-Fe₂O₃ were investigated by studying the electrical properties of the sensor elements fabricated from the synthesized powder. The maximum response (90%) of the sensor to 1000 ppm n-butane at 300 °C can be explained on the basis of catalytic activity of the nanocrystallites. The response and recovery time of the sensor to 1000 ppm n-butane were less than 12 s and 120 s, respectively.     

Titania NOx sensors for exhaust monitoring

Oxide semiconductors have been examined to develop NO_x sensors for exhaust monitoring. Titania doped with trivalent elements, such as Al³⁺, Sc³⁺, Ga³⁺ or In³⁺, has a good sensitivity and selectivity to NO between 450 and 550 °C, and shows rapid response. A sensor probe for monitoring exhaust NO_x has been fabricated. Many kinds of interference gases, such as C₃H₆, CO and SO₂, have been found to have only a slight influence on the sensor response to NO. The influence of O₂ and H₂O is also negligible, except for the cases of 0% H₂O and fuel-rich conditions. In accordance with these results, the sensor probe operates satisfactority in the exhaust gas of various combustion conditions without interference from the various kinds of gas species in the exhaust gases.     

Gas-sensing property and mechanism of CaxLa1−xFeO3 ceramics

LaFEO₃ and Ca_xLa_1−xFeO₃ ceramic powders have been prepared by the coprecipitation method from La(NO₃)₃, Fe(NO₃)₃ and Ca(NO₃)₂ aqueous solutions. The orthorhombic perovskite phases of LaFeO₃ and Ca_xLa_1−xFeO₃ are characterized by X-ray diffraction patterns. The sensors fabricated with those powders have high sensitivity to alcohol. Partial substitution of La³⁺ in LaFeO₃ with Ca²⁺ can enhance the sensitivity of the materials to reducing gases. The resistance of an LaFeO₃ sensor in air, vacuum and alcohol-containing air has been measured. Complex impedance spectroscopy has been used to try and analyse the gas-sensing mechanism. According to the experimental results, it can be deduced that the surface adsorptive and lattice oxygen govern the sensing properties of LaFeO₃ and Ca_xLa_1−xFeO₃ ceramics.     

Ceria-doped SnO2 sensor highly selective to ethanol in humid air

In our earlier study, we reported that at 300 °C, a 2.0 wt.% CeO₂-doped SnO₂ sensor is highly selective to ethanol in the presence of CO and CH₄ gases [F. Pourfayaz, A. Khodadadi, Y. Mortazavi, S.S. Mohajerzadeh, CeO₂ doped SnO₂ sensor selective to ethanol in presence of CO, LPG and CH₄, Sens. Actuators B 108 (2005) 172–176]. In the present investigation, we report the influence of ambient air humidity on the ethanol selective SnO₂ sensor doped with 2.0 wt.% CeO₂. Maximum response to ethanol occurs at 300 °C which decreases with the relative humidity. The relative humidity was changed from 0 to 80% for different ambient air temperatures of 30, 40 and 50 °C and the response of the sensor was monitored in a 250–450 °C temperature range. As the relative humidity in 50 °C air increased from 0 to 30%, a 15% reduction in the maximum response to ethanol was observed. A further increase in the relative humidity no longer reduced the response significantly. The presence of humidity improved the sensor response to both CO and CH₄ up to 350 °C after which the extent of improvement became smaller and at 450 °C was almost diminished. The sensor is shown to be quite selective to ethanol in the presence of humid air containing CO and CH₄. The selectivity passes a maximum at 300 °C; however it declines at higher operating temperatures.