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.     

Preparation of gas sensors via dip-pen nanolithography

In the present work, a conducting polymer, doped polypyrrole, was used to develop a gas sensor by dip-pen nanolithography (DPN). The response time of the sensor to 18 ppm CO₂ was 9 s. The sensor response increased linearly as the CO₂ concentration increased. A possible mechanism for the CO₂ sensing was discussed.     

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.     

Continuous monitoring of gastric carbon dioxide with optical fibres

An optical fibre sensor for the continuous monitoring of gastric carbon dioxide is described, based on the utilisation of a sensing layer, in which the colour of the layer is dependent on the CO₂ concentration. The CO₂-sensitive layer consists basically of a dye/quaternary ammonium ion pair, dissolved in a thin layer of ethylcellulose. The sensor was thoroughly characterised in laboratory and its performances were compared with those of Tonocap, the instrument based on gastric tonometry, which is the present method for detecting partial pressure of gastric carbon dioxide. Its measurement range, 0–150 h Pa, its accuracy, ±2.5 h Pa, and its response time, less than 1 min, were capable of satisfying the physicians’ requirements for clinical application. The clinical tests, carried out on volunteers and on intensive care patients, showed that the developed sensor is definitely superior to the sensor that is at present available on the market: thanks to its short response time, the optical fibre sensor is able to detect rapid changes in pCO₂, currently unknown because of the lack of a tool with which to measure them.     

Calorimetric hydrocarbon sensor for automotive exhaust applications

We have developed a calorimetric sensor utilizing a thermoelectric device supported on a planar alumina substrate. By using a highly selective carbon monoxide (CO) oxidation catalyst and a non-selective platinum (Pt) catalyst, the device can be built to detect either CO or hydrocarbons with high selectivity. The CO oxidation catalyst comprises lead-modified platinum and exhibits excellent selectivity over the 200–400 °C temperature range. The thermoelectric device consists of two thick film junctions made of niobium pentoxide (Nb₂O₅)-doped titanium dioxide (TiO₂) and a lithiated nickel (Ni), which are supported on a planar alumina substrate. The thermocouple detects the difference in temperature due to different catalytic reactions over the two junctions and shows a high output signal because of the high Seebeck coefficient of Nb₂O₅-doped TiO₂ (−400 μV/°C). In gas bench tests, the sensor has a linear output of 0–2.75 mV over 0–1000 ppm of propylene and a response time of 2.5 s (at 90% of amplitude) at a gas temperature of 350 °C. An engine dynamometer evaluation shows that the response of the sensor parallels the change in CO and hydrocarbon constituent concentrations when the engine air-to-fuel ratio is varied.     

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.     

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.     

Room temperature hydrogen response kinetics of nano–micro-integrated doped tin oxide sensor

The nano–micro-integrated sensor has been fabricated by sol–gel depositing the nanocrystalline indium oxide (In₂O₃)-doped tin oxide (SnO₂) thin film on microelectromechanical systems (MEMS) device having interdigitated electrode configurations with two different electrode spacing (10 μm and 20 μm) and two different number of fingers (8 and 20). The present nano–micro-integrated sensor exhibits high H₂ sensitivity range (S = 3–10⁵) for the H₂ concentration within the range of 100–15,000 ppm at room temperature. It has been demonstrated that, the room temperature response kinetics of the present nano–micro-integrated sensor is a function of finger spacing, H₂ concentration and air-pressure, but independent of number of fingers. Such dependence has been explained on the basis of Le Chatelier's principle applied to the associated H₂ sensing mechanism and the role of above parameters in shifting the dynamic equilibrium of the involved surface reactions under the described test conditions. A new definition of the response time has been proposed, which is not only suitable for the theoretical analysis but also for the practical applications, where a gas-leak detection alarm is required to be triggered.     

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.     

Characterization of protective coatings for planar automotive gas sensors

Alumina support material suitable for use as a planar automotive gas sensor support was coated in thin films of yttria-stabilised zirconia (YSZ) and titania. The morphology, composition, thickness and homogeneity of the coating was measured. The coating was applied to the ‘green’ form of a tape cast alumina substrate which was subsequently fired at 1500 °C to produce the final form of the coated alumina. The YSZ coating gave a continuous 5 μm thick coating with no evidence of mixed oxide formation between the YSZ and the alumina substrate. XRD indicated a face centred cubic Y doped ZrO₂ or primitive tetragonal Zr_0.9Y_0.1O_1.95 phase. The titania coatings were much thinner (<1 μm) with signs of trace amounts of aluminium titanium oxide (Al₂TiO₅) as well as rutile titania in XRD. Spot analysis using X-ray photoelectron spectroscopy showed a fairly regular titania coverage. Atomic force microscopy analysis showed a particle size of 1–3 μm for the YSZ coating and 0.5 μm for titania.     

Development of a bienzyme system based on sugar–lectin biospecific interactions for amperometric determination of phenols and aromatic amines

Bienzyme electrode with horseradish peroxidase (HRP) and glucose oxidase (GOD) multilayers was constructed based on sugar–lectin biospecific interactions for amperometric determination of phenolic compounds and aromatic amines. Atomic force microscopy (AFM) was applied to monitor the uniform layer-by-layer assembly of concanavalin A (Con A) and HRP or GOD on polyelectrolyte precursor film-modified Au electrode. Substituted phenolic compounds and aromatic amines could be determined with in situ generation of H₂O₂ by GOD-catalyzed oxidation of glucose. The parameters of the biosensor including the number of assembled HRP and GOD layer, and the concentrations of glucose were optimized. The linear range for the determination of catechol and p-phenyldiamine was 6.0–60.0 μmol L⁻¹ and 7.6–68.4 μmol L⁻¹ with detection limit of 0.9 μmol L⁻¹ and 0.4 μmol L⁻¹, respectively. The biosensor possessed high sensitivity and fast response for phenolic compounds and 95% of the maximum response could be reached in about 3 s. Glucose, ascorbic acid, tartaric acid, citric acid and starch exhibited no interference for the detection. The biosensor presented high stability due to the design for in situ generation of H₂O₂ with bienzyme system.     

Fire detection with low power fet gas sensors

Gas sensors based on hybrid suspended gate field effect devices are used for the detection of specific gases occurring in test fires. This sensor type can be operated with a power consumption < 1 mW and is therefore best suited for the use in fire detectors. Different floating gate FET (FGFET) sensors designed for the detection of CO, CO₂ and NO₂ were tested in standard test fires regarding EN54. Significant sensor signals were obtained for all test fires enabling a reliable and fast detection of fires. In addition, a separation of fire types is possible by signal evaluation combining signals of different sensors.     

Fast response of undoped and Li-doped titania thick-films at low temperature

The fast response of undoped and Li-doped TiO₂ operating at low temperature to hydrogen and oxygen is investigated. The TiO₂ sensors are fabricated using thick-film technique. The prepared materials exhibit the presence of only rutile phase of TiO₂ but enlarged crystal lattice parameters were confirmed by X-ray diffraction (XRD). Scanning electron microscopy (SEM) shows that the grain size of the material has not obviously changed with different Li-doping (2–4 mol%), but the undoped is much smaller. Kroger–Vink model indicates that Li mainly substitutes for the lattice point of Ti. Because the material resistance decreases as the oxygen pressure increases, Li-doped samples can be regarded as a p-type semiconductor compared with pure TiO₂. The operating temperature of the Li-doped TiO₂ samples is found to be lower than that of pure TiO₂ in H₂ and O₂ environment. At less than 3 mol% Li content, the response time of the Li-doped TiO₂ gas sensors is much shorter than that of pure TiO_2, at the same temperature under both H₂ and O₂ environment. Moreover, the sample of 3 mol% Li-doping exhibits the best response characteristics. The response mechanism is suggested to arise from the conduction holes ionized by Li and the surface potential barrier change in different gas environments.     

A fibre-optic oxygen sensor based on contact charge-transfer absorption

A fibre-optic oxygen (O₂) sensor monitoring at a wavelength of 400 nm has been successfully developed for the determination of gaseous O₂. Its working principle is based on the contact charge-transfer absorption of N,N-dimethyl-p-toluidine and O₂. The response to changes in O₂ concentrations is reversible and in good agreement with the Beer-Lambert law. The response and recovery times are 12 and 26 min, respectively. The sensor can detect a wide range of O₂ concentrations, ranging from 4.3 to 100% O₂. The precision is 1.45% (n=5) in a gas mixture of 95% O₂ in N₂ and the limit of detection is 4.3% O₂ (3σ_b). The sensor is stable with a 0.53% change in sensitivity per hour. There is a 0.25% °C⁻¹ decrease of the sensitivity of the sensor to O₂ in the range 20–34°C. Water vapour and nitrogen dioxide interfere slightly, whereas hydrogen sulphide and hydrogen chloride have moderate interference on the sensor. However, chlorine and sulphur dioxide seriously interfere with the sensor.     

Fabrication and characterization of low temperature sintering PMN–PZN–PZT step-down multilayer piezoelectric transformer

For the fabrication as step-down multilayer piezoelectric transformer, piezoelectric properties of Pb(Mg_1/3Nb_2/3)O₃–Pb(Zn_1/3Nb_2/3)O₃–Pb(Zr_0.52Ti_0.48)O₃ (PMN–PZN–PZT) ceramics were optimized by ZnO–Li₂CO₃ (ZL) and Pb₃O₄ content. Effects of the additions on the structure, bulk density and electrical properties of ceramics were investigated. The results revealed that the proper additions of ZL with Pb₃O₄ content could modify the electrical properties of the PMN–PZN–PZT ceramics. The composition sintered at 995 °C with 0. 01 wt.% ZL and 0.10 wt.% Pb₃O₄ content showed higher values, which were listed as follows: d₃₃ = 256 pC/N, K_p = 0.60, Q_m = 1910, _r = 1032, tan δ = 0.0070 and r = 2.09 Ω. In addition, the step-down piezoelectric transformers with optimized PMN–PZN–PZT composites were fabricated and the characteristics as the output power and resistance loads were measured. Meanwhile, the step-down piezoelectric transformers sintered at 995 °C showed the favorable characteristics with a higher gain G of 0.204 and a lower temperature rise of 6 °C when the output power was 5 W, and the driving frequency were approximately constant (≈126 kHz) when the output power was from 5 to 13 W. Moreover, the maximum efficiency (90.2%) was obtained at load resistance of 10 Ω.     

Ozone sensors on the base of SnO2 films deposited by spray pyrolysis

The gas-sensing properties of SnO₂-based thin films designed for ozone detection are discussed in this paper. The influence of film characteristics on sensor performance is analyzed. SnO₂ films with thickness 30–200 nm were deposited by spray pyrolysis. The SnO₂ films have a response to ozone that is quantitative and rapid and sufficient for use in ozone control and monitoring applications. Sensor performance is compared with similarly prepared sensors fabricated from In₂O₃- and WO₃-based films. The mechanism of the processes controlling the sensor response characteristics is proposed. The data support our conclusion that the reaction with ozone using the SnO₂-film sensors is limited by the adsorption/desorption processes.     

Perchlorate selective membrane electrodes based on synthesized platinum(II) complexes for low-level concentration measurements

Three synthesized platinum(II) complexes, [PtR₂(NN)] (R = Me, p-MeC₆H₄ and p-MeOC₆H₄; NN = 2,2′-bipyridyl), were studied to characterize their ability as an anion carrier in a PVC membrane electrode. The polymeric membrane electrodes (PME) and also coated glassy carbon electrodes (CGCE) prepared with [Pt(p-MeOC₆H₄)₂(NN)] showed excellent response characteristics to perchlorate ions. The electrodes exhibited Nernstian responses to ClO₄⁻ ions over a wide concentration range from 5 × 10⁻⁷ to 4.0 × 10⁻¹ M for PME and 1.5 × 10⁻⁷ to 2.7 × 10⁻¹ M for CGCE with low detection limits (4.0 × 10⁻⁷ M for PME and 1.0 × 10⁻⁷ M for CGCE). The electrodes possess fast response time, satisfactory reproducibility, appropriate lifetime and, most importantly, good selectivity toward ClO₄⁻ relative to a variety of other common anions. The potentiometric response of the electrodes is independent of the pH of the test solution in the pH range 2.5–9.5. The proposed sensors were used in potentiometric determination of perchlorate ions in mineral water, urine samples and also samples containing interfering anions. The interaction of the ionophore with perchlorate ions was shown by UV–vis spectroscopy.     

Sol–gel derived polycrystalline Cr1.8Ti0.2O3 thick films for alcohols sensing application

The powder sample of Cr_1.8Ti_0.2O₃ (CTO) was obtained by a sol–gel method. The thick films were developed on identical ceramic tubes of 4 mm length comprising of two Au-electrodes and printing an eight-layer film prepared by mixing CTO with glass powder and -terpinol as an organic vehicle. X-ray powder diffraction (XRD) patterns showed the formation of a single phase. The scanning electron microscope (SEM) images of the ceramic sensor treated at 850 °C revealed that the grain size was larger than 400 nm for the individual isolated grains on the surface, and the agglomerated dense spheroidal platelets had the size of 1–4 μm in diameter. The AC impedance measurement in ambient air showed that the resistance decreased nearly by two orders of magnitude with an increase in temperature in the range of 400–600 °C for both the powder sample and the thick film, and the activation energy E_a derived from the measurement was found to be 0.35 and 0.36 eV for the powder and the film, respectively. The films were exposed to various concentrations of alcohols (0.4–1.2 ppm of methanol and 1.0–5.0 ppm of ethanol), followed by determination of sensor response, sensitivity and reversibility and reproducibility. The origin of the gas response was attributed to the surface reaction of R-OH (R = methyl and ethyl group) with O⁻_(ads) to form adsorbed R-CHO, which was desorbed as a gas at 400 °C after the sensor departing from the gas.     

SnO2 thin films for gas sensors modified by hexamethyldisilazane after rapid thermal annealing

Simple method of SnO₂ layer modification, using very small quantity of hexamethyldisilazane and rapid thermal annealing in the range 800–1200 °C is proposed. The distribution profile of the dopant elements of C, N, Si in the SnO₂/SiO₂/Si structure is investigated. Penetration of Si in the whole depth of SnO₂ is revealed and formation of SiO₂ regions in the SnO₂ bulk is assumed. Simultaneously, Sn diffusion in the SiO₂ layer is observed. The combination of standard AES and XPS techniques with a hollow cathode discharge method appears to be very useful for detection of traces of dopants in the layers.     

Direct electrochemistry and electrocatalysis of myoglobin immobilized in zirconium phosphate nanosheets film

Myoglobin (Mb) is incorporated on a novel matrix—zirconium phosphate nanosheets (ZrPNS) and immobilized at a glassy carbon electrode surface. UV–vis spectra and electrochemical measurements show that the matrix is well biocompatible and can retain the bioactivity of immobilized Mb. The direct electron transfer between Mb and electrode exhibits a couple of well-defined redox peaks. The cathodic and anodic peaks are located at −0.340 and −0.280 V vs. Ag/AgCl, respectively. The ZrPNS can improve the electron transfer between Mb and electrode with an electron transfer constant of 5.6 s⁻¹. Meanwhile, the catalytic ability of the protein toward the reduction of H₂O₂, O₂, NaNO₂, trichloroacetic acid (TCA) is also studied and a third-generation biosensor is subsequently fabricated. The linear range of biosensor to H₂O₂ is from 8 × 10⁻⁷ to 1.28 × 10⁻⁵ M with the limit detection of 1.4 × 10⁻⁷ M. The small apparent Michaelis–Menten constant (34 μM) suggests that Mb/ZrPNS film performs good affinity with H₂O₂. The biosensor also exhibits acceptable stability and reproducibility. This work paves a way to develop other biologic active materials in this kind of nanosheets for constructing novel biosensors.