Effect of La2CuO4 electrode area on potentiometric NOx sensor response and its implications on sensing mechanism

The intent of this work is to look at the effects of varying the La₂CuO₄ electrode area and the asymmetry between the sensing and counter electrode in a solid state potentiometric sensor with respect to NO_x sensitivity. NO₂ sensitivity was observed at 500-600 °C with a maximum sensitivity of ∼22 mV/decade [NO₂] observed at 500 °C for the sensor with a La₂CuO₄ electrode area of ∼30 mm². The relationship between NO₂ sensitivity and area is nearly parabolic at 500 °C, decreases linearly with increasing electrode area at 600 °C, and was a mixture of parabolic and linear behavior 550 °C. NO sensitivity varied non-linearly with electrode area with a minima (maximum sensitivity) of ∼−22 mV/decade [NO] at 450 °C for the sensor with a La₂CuO₄ electrode area of 16 mm². The behavior at 400 °C was similar to that of 450 °C, but with smaller sensitivities due to a saturation effect. At 500 °C, NO sensitivity decreases linearly with area.We also used electrochemical impedance spectroscopy (EIS) to investigate the electrochemical processes that are affected when the sensing electrode area is changed. Changes in impedance with exposure to NO_x were attributed to either changes in La₂CuO₄ conductivity due to gas adsorption (high frequency impedance) or electrocatalysis occurring at the electrode/electrolyte interface (total electrode impedance). NO₂ caused a decrease in high frequency impedance while NO caused an increase. In contrast, NO₂ and NO both caused a decrease in the total electrode impedance. The effect of area on both the potentiometric and impedance responses show relationships that can be explained through the mechanistic contributions included in differential electrode equilibria.     

Mixed-potential-type zirconia-based NO2 sensor with high-performance three-phase boundary

This paper focuses on the gas sensing properties of the mixed-potential-type NO₂ sensor based on yttria stabilized zirconia (YSZ) and NiO electrode. The sensing performance of the sensor was improved by modifying the three-phase boundary (TPB). Hydrofluoric acid with different concentrations (10%, 20% and 40%) was used to corrode YSZ substrate to obtain large superficial area of TPB. The scanning electron microscope and atomic force microscopic images showed that the 40% HF could form the largest superficial area at the same corroding time (3 h). The sensitivity of the sensor using the YSZ plate corroded with 40% hydrofluoric acid to 20-500 ppm NO₂ was 76 mV/decade at 850 °C, which was the largest among the examined HF concentrations. It was also seen that the sensor showed a good selectivity and speedy response kinetics to NO₂. On the basis of the measurements of anodic and cathodic polarization curves, as well as the complex impedance of the device, the sensing mechanism was confirmed to involve a mixed potential at the oxide sensing electrode.     

Fabrication of N-type Fe2O3 and P-type LaFeO3 nanobelts by electrospinning and determination of gas-sensing properties

N-type Fe₂O₃ nanobelts and P-type LaFeO₃ nanobelts were prepared by electrospinning. The structure and micro-morphology of the materials were characterized by X-ray diffraction (XRD) and scanning of electron microscopy (SEM). The gas sensing properties of the materials were investigated. The results show that the optimum operating temperature of the gas sensors fabricated from Fe₂O₃ nanobelts is 285 °C, whereas that from LaFeO₃ nanobelts is 170 °C. Under optimum operating temperatures at 500 ppm ethanol, the response of the gas sensors based on these two materials is 4.9 and 8.9, respectively. The response of LaFeO₃-based gas sensors behaves linearly with the ethanol concentration at 10-200 ppm. Sensitivities to different gases were examined, and the results show that LaFeO₃ nanobelts exhibit good selectivity to ethanol, making them promising candidates as practical detectors of ethanol.     

Nanostructured spinel ZnCo2O4 for the detection of LPG

Nanostrucutred spinel ZnCo₂O₄ (∼26-30 nm) was synthesized by calcining the mixed precursor (consisting of cobalt hydroxyl carbonate and zinc hydroxyl carbonate) in air at 600 °C for 5 h. The mixed precursor was prepared through a low cost and simple co-precipitation/digestion method. The transformation of the mixed precursor into nanostructured spinel ZnCo₂O₄ upon calcinations was confirmed by X-ray diffraction (XRD) measurement, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HRTEM). To demonstrate the potential applicability of ZnCo₂O₄ spinel in the fabrication of gas sensors, its LPG sensing characteristics were systematically investigated. The ZnCo₂O₄ spinel exhibited outstanding gas sensing characteristics such as, higher gas response (∼72-50 ppm LPG gas at 350 °C), response time (∼85-90 s), recovery time (∼75-80 s), excellent repeatability, good selectivity and relatively lower operating temperature (∼350 °C). The experimental results demonstrated that the nanostructured spinel ZnCo₂O₄ is a very promising material for the fabrication of LPG sensors with good sensing characteristics. Plausible LPG sensing mechanism is also discussed.     

Enhanced H2S sensing characteristics of Pt doped SnO2 nanofibers sensors with micro heater

Gas sensors were designed and fabricated using oxide nanofibers as the sensing materials on micro platforms using micromachining technology. Pure and Pt doped SnO₂ nanofibers were prepared by electrospinning and their H₂S gas sensing characteristics were subsequently investigated. The sensing temperatures of 300 and 500 °C could be attained at the heater powers of 36 and 94 mW, respectively, and the sensors showed high and fast responses to H₂S. The responses of 0.08 wt% Pt doped SnO₂ nanofibers to 4-20 ppm H₂S, were 25.9-40.6 times higher than those of pure SnO₂ nanofibers. The gas sensing characteristics were discussed in relation to the catalytic promotion effect of Pt, nano-scale morphology of electrospun nanofibers, and sensor platform using micro heater.     

Diesel engine dynamometer testing of impedancemetric NOx sensors

Prototype solid-state electrochemical sensors using a dense gold sensing electrode, porous yttria-stabilized zirconia (YSZ) electrolyte, and a platinum counter electrode (Au/YSZ/Pt) were evaluated for measuring NO_x (NO and NO₂) in diesel exhaust. Both electrodes were exposed to the test gas (i.e., there was no reference gas for the counter electrode). An impedancemetric method was used for NO_x measurements, where the phase angle was used as the response signal. A portion of the tailpipe exhaust from the dynamometer test stand was extracted and fed into a furnace containing the experimental sensor. The prototype sensor was tested along with a commercially available NO_x sensor. Simultaneous measurements for NO_x, O₂, CO₂, H₂O, CO, and CH₄ in a separate feed stream were made using Fourier transform infrared (FTIR) spectroscopy and an oxygen paramagnetic analyzer. The experimental sensor showed very good measurement capability for NO in the range of 25-250 ppm, with a response paralleling that of the FTIR and commercial sensor. The prototype sensor showed better sensitivity to NO_x at the lower concentration ranges. O₂ is an interferent for the experimental sensor, resulting in decreased sensitivity for measurement of NO_x. Methods to overcome this interference are discussed.     

The influence of catalytic activity on the response of Pt/SnO2 gas sensors to carbon monoxide and hydrogen

The article presents the results of research studies on ceramics SnO₂ sensors with Pt catalysts. The role of catalysis in gas sensing mechanisms was investigated. In order to obtain samples with different catalytic activity but with identical Pt loading, the Pt/SnO₂ catalysts were calcined at different temperatures (400-800 °C). Structural analysis of these samples was performed. Among the sensors manufactured with Pt/SnO₂, the highest sensitivity was shown for the sensor obtained with Pt/SnO₂ sample sintered at 800 °C. The correlation between catalytic activity and sensor sensitivity is given.     

Au-doped WO3-based sensor for NO2 detection at low operating temperature

Pure and Au-doped WO₃ powders for NO₂ gas detection were prepared by a colloidal chemical method, and characterized via X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The NO₂ sensing properties of the sensors based on pure and Au-doped WO₃ powders were investigated by HW-30A gas sensing measurement. The results showed that the gas sensing properties of the doped WO₃ sensors were superior to those of the undoped one. Especially, the 1.0 wt% Au-doped WO₃ sensor possessed larger response, better selectivity, faster response/recovery and better longer term stability to NO₂ than the others at relatively low operating temperature (150 °C).     

Gas sensing properties of SnO2 nanowires on micro-heater

The SnO₂ nanowires (NWs) network gas sensors were fabricated on a micro-electrode and heater suspended in a cavity. The sensors showed selective detection to C₂H₅OH at a heater power during sensor operation as low as 30-40 mW. The gas response and response speed of the SnO₂ NWs sensor to 100 ppm C₂H₅OH were 4.6- and 4.7-fold greater, respectively, than those of the SnO₂ nanoparticles (NPs) sensor with the same electrode geometry. The reasons for these enhanced gas sensing characteristics are discussed in relation to the sensing materials and sensor structures.     

In2O3 + xBaO (x = 0.5-5 at.%) - A novel material for trace level detection of NOx in the ambient

Indium oxide (In₂O₃) doped with 0.5-5 at.% of Ba was examined for their response towards trace levels of NO_x in the ambient. Crystallographic phase studies, electrical conductivity and sensor studies for NO_x with cross interference for hydrogen, petroleum gas (PG) and ammonia were carried out. Bulk compositions with x ≤ 1 at.% of Ba exhibited high response towards NO_x with extremely low cross interference for hydrogen, PG and ammonia, offering high selectivity. Thin films of 0.5 at.% Ba doped In₂O₃ were deposited using pulsed laser deposition technique using an excimer laser (KrF) operating at a wavelength of (λ) 248 nm with a fluence of ∼3 J/cm² and pulsed at 10 Hz. Thin film sensors exhibited better response towards 3 ppm NO_x quite reliably and reproducibly and offer the potential to develop NO_x sensors (Threshold limit value of NO₂ and NO is 3 and 25 ppm, respectively).     

Solid-state potentiometric SO2 sensor combining NASICON with V2O5-doped TiO2 electrode

A compact tubular sensor based on NASICON (sodium super ionic conductor) and V₂O₅-doped TiO₂ sensing electrode was designed for the detection of SO₂. In order to reduce the size of the sensor, a thick-film of NASICON was formed on the outer surface of a small Al₂O₃ tube; furthermore, a thin layer of V₂O₅-doped TiO₂ with nanometer size was attached on the NASICON as a sensing electrode. This paper investigated the influence of V₂O₅ doping and sintering temperature on the characteristics of the sensor. The sensor attached with 5 wt% V₂O₅-doped TiO₂ sintered at 600 °C exhibited excellent sensing properties to 1–50 ppm SO₂ in air at 200–400 °C. The EMF value of the sensor was almost proportional to the logarithm of SO₂ concentration and the sensitivity (slope) was −78 mV/decade at 300 °C. It was also seen that the sensor showed a good selectivity to SO₂ against NO, NO₂, CH₄, CO, NH₃ and CO₂. Moreover, the sensor had speedy response kinetics to SO₂ too, the 90% response time to 50 ppm SO₂ was 10 s, and the recovery time was 35 s. On the basis of XPS analysis for the SO₂-adsorbed sensing electrode, a sensing mechanism involving the mixed potential at the sensing electrode was proposed.     

Temperature dependent H2S and Cl2 sensing selectivity of Cr2O3 thin films

The conductometric gas sensing characteristics of Cr₂O₃ thin films - prepared by electron-beam deposition of Cr films on quartz substrate followed by oxygen annealing - have been investigated for a host of gases (CH₄, CO, NO₂, Cl₂, NH₃ and H₂S) as a function of operating temperature (between 30 and 300 °C) and gas concentration (1-30 ppm). We demonstrate that these films are highly selective to H₂S at an operating temperature of 100 °C, while at 220 °C the films become selective to Cl₂. This result has been explained on the basis of depletion of chemisorbed oxygen from the surface of films due to temperature and/or interaction with Cl₂/H₂S, which is supported experimentally by carrying out the work function measurements using Kelvin probe method. The temperature dependent selectivity of Cr₂O₃ thin films provides a flexibility to use same film for the sensing of Cl₂ as well as H₂S.     

Fe2O3 modified thick films of nanostructured SnO2 powder consisting of hollow microspheres synthesized from pyrolysis of ultrasonically atomized aerosol for LPG sensing

Nanostructured hollow spheres of SnO₂ with fine nanoparticles were synthesized by ultrasonic atomization. Thick film gas sensors were fabricated by screen printing technique. Different surface modified films (Fe₂O₃ modified SnO₂) were obtained by dipping them into an aqueous solution (0.01 M) of ferric chloride for different intervals of time followed by firing at 500 °C. The structural and microstructural studies of the samples were carried out using XRD, SEM, and TEM. The sensing performance of pure and modified films was studied by exposing various gases at different operating temperatures. One of the modified sample exhibited high response (1990) to 1000 ppm of LPG at 350 °C. Optimum amount of Fe₂O₃ dispersed evenly on the surface_, adsorption and spillover of LPG on Fe₂O₃ misfits and high capacity of adsorption of oxygen on nanostructured hollow spheres may be the reasons of high response.     

Necked ZnO nanoparticle-based NO2 sensors with high and fast response

The NO₂ gas sensing characteristics of semiconductor type gas sensors with channels composed of necked ZnO nanoparticles (NPs) were investigated in this study. The heat treatment of the NPs at 400 °C led to their necking and coarsening. The response of the necked-NP-based sensors was as high as 100 when exposed to 0.2 ppm of NO₂ at 200 °C. As the concentration of NO₂ increased to 5 ppm, their response was enhanced to approximately 400. During the repeated injection of NO₂ gas with a concentration of 0.4 ppm, the sensors exhibited stable response characteristics. Furthermore, the 90% response and recovery times of the gas sensor were as fast as 13 and 10 s, respectively. These observations indicate that the non-agglomerated necking of the NPs induced by the heat treatment significantly enhances the gas sensing characteristics of the NP-based gas sensors.     

Synthesis of ZnO nanorods and its application in NO2 sensors

One-dimensional (1D) ZnO nanorods with pencil-like shape and high aspect ratio were successfully synthesized using a cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process at 90 °C. The surface morphology and structure of nanocrystals were characterized by FE-SEM, XRD and XPS analysis. Experimental results show that the surfactant and base concentration play important roles in the formation and growth orientation of ZnO nanorods. The ZnO nanorods synthesized exhibits high response and selectivity to NO₂, the highest response to 40 ppm NO₂ reached 206 and the selectivity with respect to CO and CH₄ at same concentration reached 10.3 and 30 times, respectively. The effects of synthesis method, surfactant and calcination condition on sensing properties were systematically investigated. The results indicate that the CTAB-assisted low temperature hydrothermal process is a potentially facile method for synthesis of 1D ZnO nanorods and excellent potential candidates as gas sensing materials.     

Development of SAW-based multi-gas sensor for simultaneous detection of CO2 and NO2

A 440 MHz wireless and passive surface acoustic wave (SAW)-based multi-gas sensor integrated with a temperature sensor was developed on a 41° YX LiNbO₃ piezoelectric substrate for the simultaneous detection of CO₂, NO₂, and temperature. The developed sensor was composed of a SAW reflective delay lines structured by an interdigital transducer (IDT), ten reflectors, a CO₂ sensitive film (Teflon AF 2400), and a NO₂ sensitive film (indium tin oxide). Teflon AF 2400 was used for the CO₂ sensitive film because it provides a high CO₂ solubility, with good permeability and selectivity. For the NO₂ sensitive film, indium tin oxide (ITO) was used. Coupling of mode (COM) modeling was conducted to determine the optimal device parameters prior to fabrication. Using the parameters determined by the simulation results, the device was fabricated and then wirelessly measured using a network analyzer. The measured reflective coefficient S₁₁ in the time domain showed high signal/noise (S/N) ratio, small signal attenuation, and few spurious peaks. The time positions of the reflection peaks were well matched with the predicted values from the simulation. High sensitivity and selectivity were observed at each target gas testing. The obtained sensitivity was 2.12°/ppm for CO₂ and 51.5°/ppm for NO₂, respectively. With the integrated temperature sensor, temperature compensation was also performed during gas sensitivity evaluation process.     

NO2 gas sensing properties of amorphous InGaZnO4 submicron-tubes prepared by polymeric fiber templating route

One-dimensional (1D) amorphous InGaZnO₄ (a-IGZO) submicron-tubes were synthesized in a method involving an electrospun polymeric fiber template and the direct RF-sputter-coating of a-IGZO films combined with subsequent calcination at 450 °C. The a-IGZO hollow fibers with a diameter of 300 nm and a shell thickness of 20–30 nm showed an amorphous structure, as confirmed by XRD and HR-TEM analyses. Gas sensors using semiconducting a-IGZO tube networks exhibited n-type gas sensing characteristics and a 3.7-fold higher gas response (R_gas/R_air = 109.5 at 2 ppm NO₂) compared to (R_gas/R_air = 29.4) planar a-IGZO thin films at an operating temperature of 300 °C. The enhanced gas response of a-IGZO tubes is attributed to the greater space charge modulation depth associated with the thin shell structures and the porous networks which are readily accessible by gas.     

Selectivity of flame-spray-made Nb/ZnO thick films towards NO2 gas

Unloaded ZnO and Nb/ZnO nanoparticles containing 0.25, 0.5 and 1 mol.% Nb were produced in a single step by flame-spray pyrolysis (FSP) technique. The nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The BET surface area (SSA_BET) of the nanoparticles was measured by nitrogen adsorption. FSP yielded small Nb particles attached to the surface of the supporting ZnO nanoparticles, indicating a high SSA_BET. The morphology and accurate size of the primary particles were further investigated by TEM. Nb/ZnO nanoparticles paste composed of ethyl cellulose and terpineol as binder and solvent respectively was coated on Al₂O₃ substrate interdigitated with gold electrodes to form thick films by spin coating technique. After the sensing tests, the morphology and the cross-section of sensing film were analyzed by SEM and EDS analyses. The influence on a low dynamic range of Nb concentration on NO₂ response (0.1-4 ppm) of thick film sensor elements was studied at the operating temperatures ranging from 250 to 350 °C in the presence of dry air. The optimum Nb concentration was found be 0.5 mol.% and 0.5 mol.% Nb exhibited an optimum NO₂ response of ∼1640 and a short response time (27 s) for NO₂ concentration of 4 ppm at 300 °C.     

Facile synthesis of hierarchical SnO2 semiconductor microspheres for gas sensor application

Hierarchical SnO₂ microspheres were synthesized by a hydrothermal method at 140 °C using stannic chloride hydrate and sodium hydroxide as starting materials. The individual hierarchical SnO₂ microsphere ranged from 700 to 900 nm in diameter. After these microspheres were heated at 600 °C for 2 h, the spheres were cross-linked into clusters by short SnO₂ nanorods as revealed by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Most importantly, SnO₂ hierarchical microsphere sensor exhibits excellent selectivity and fast response to ethanol. Response and recovery times were 0.6 s and 11 s when the sensor was exposed to 50 ppm ethanol at an operating temperature of 300 °C. Thus, hierarchical structures play a significant role in the field of gas sensing.     

Vanadia doped tungsten-titania SCR catalysts as functional materials for exhaust gas sensor applications

Urea-SCR systems (selective catalytic reduction) are required to meet future NO_x emission standards of heavy-duty and light-duty vehicles. It is a key factor to control the SCR systems and to monitor the catalysts’ functionalities to achieve low emissions. The novel idea of this study is to apply commercially available SCR catalyst materials based on vanadia-doped tungsten-titania as gas sensing films for impedimetric thick-film exhaust gas sensor devices. The dependence of the impedance on the surrounding gas atmosphere, especially on the concentrations of NH₃ and NO₂, is investigated, as well as cross interferences from other components of the exhaust. The sensors provide a good NH₃ sensitivity at 500 °C. The sensor behavior is explained in light of the literature combining the fields of catalysts and semiconducting gas sensors.