Dependence of NO2 sensitivity on thickness of oxide-sensing electrodes for mixed-potential-type sensor using stabilized zirconia

The effect of thickness of oxide-sensing electrode (SE) on NO₂ sensitivity of the planar sensor based on yttria-stabilized zirconia (YSZ) was examined at high temperatures. The sensitivity of the sensor increased with decreasing thickness of SE, and the highest sensitivity was obtained by using the thinnest layer of Cr₂O₃–SE (2.7 μm) at 700 °C. In the case of NiO–SE, the highest sensitivity was observed for the sensor using the 4-μm-thick SE even at a high temperature of 850 °C. Based on the results of the measurements for the complex impedances, the polarization curves, and the gas-phase NO₂ decomposition catalysis, it was confirmed that the catalytic activity to the gas-phase NO₂ decomposition on the oxide–SE matrix played an important role in determining the NO₂ sensitivity of the present sensors.     

Switching effect at a platinum electrode on stabilized zirconia during oxygen reduction in the presence of NO

A galvanic cell based upon the use of stabilized zirconia as solid oxygen ion conductor has been used to measure cathodic reduction currents at a porous platinum electrode in both nitrogen-oxygen gas mixtures with and without small amounts of NO (up to 5450 ppm). Adding small amounts of NO to the N₂/O₂ mixture induced a considerable cathodic current peak at the working electrode in the first moment after addition. After interruption of the NO exposure, the opposite effect, a high current pulse in anodic direction, was observed. The switching effect is reproducible and its magnitude depends on the concentrations of oxygen and nitrogen monoxide in the gas. As the main contribution to the current results from the reduction of the excess oxygen in the gas, it must be concluded that the presence of NO strongly affects the steady state, in particular the adsorbed oxygen at the electrode/electrolyte interface. These experimental results are interpreted in terms of a reversible change of the interface which may be due to a reconstruction of the platinum surface in the presence of NO and corresponding drastic change in the amount of adsorbed oxygen at the platinum surface. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994     

Further experimental evidences of thermal spreading of tungsten oxide on zirconia

The effects brought about by the time of thermal treatment as well as the water content in the gas phase during the thermal spreading of WO₃ on zirconia were investigated. Diffuse reflectance UV-vis spectroscopy evidenced the thermal spreading phenomenon and revealed the formation of polymeric tungsten dispersed species. Neither the thermal treatment time nor the water content showed to influence the nature of the dispersed species, which reveal to present thermodynamically preferential molecular structures. Infrared spectroscopy analysis of adsorbed pyridine evidenced that the polytungstate species lead to the generation of Brönsted acid sites. Lewis acid sites stronger than those naturally present on zirconia could also be detected in addition to weaker Lewis sites, which were associated to the WO₃ still present in the catalysts as showed by X-ray diffraction.     

Dependence of NO<Subscript>2</Subscript> sensitivity on thickness of oxide-sensing electrodes for mixed-potential-type sensor using stabilized zirconia

The effect of thickness of oxide-sensing electrode (SE) on NO₂ sensitivity of the planar sensor based on yttria-stabilized zirconia (YSZ) was examined at high temperatures. The sensitivity of the sensor increased with decreasing thickness of SE, and the highest sensitivity was obtained by using the thinnest layer of Cr₂O₃–SE (2.7 μm) at 700 °C. In the case of NiO–SE, the highest sensitivity was observed for the sensor using the 4 μm-thick SE even at high temperature of 850 °C. Based on the results of the measurements for the complex impedances, the polarization curves, and the gas-phase NO₂ decomposition catalysis, it was confirmed that the catalytic activity to the gas-phase NO₂ decomposition on the oxide–SE matrix played an important role in determining the NO₂ sensitivity of the present sensors. This artice was accidentally published twice. This is the second publication, please cite only the authoritative first one which is available at . An additional erratum is available at . An erratum to this article can be found at     

Electrode reactions of La0.8Sr0.2MnO3±δ-electrodes on stabilized zirconia with oxygen and the nitrogen oxides NO and NO2

The kinetics for the electrode reactions with oxygen and with NO and NO₂ in the presence of oxygen has been studied for La_0.8Sr_0.2MnO_3±δ-electrodes on stabilized zirconia (8 mol% Y₂O₃=YSZ) in the temperature range between 500°C and 900°C for oxygen partial pressures between 1 kPa and 20 kPa by means of electrochemical methods (impedance, I-U characteristics) and temperature programmed desorption (TPD). For oxygen reduction below 900°C a mechanism is proposed which describes the formation of peroxidic ions at the electrode surface and a subsequent rate-determining electron transfer at the three-phase-boundary. At temperatures below 650°C the electrode reaction between NO and NO₂ is much faster than the oxygen reduction. The results for the NO₂-reduction to NO can be explained by a two-step mechanism consisting of a fast one-electron transfer to adsorbed NO₂ at the electrode surface and a subsequent rate-determining transfer of the second electron to NO₂ at the three-phase-boundary. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994     

On the behavior of a dense indium oxide/yttria-stabilized zirconia electrode

The electrical, structural and electrochemical properties of a dense In₂O₃ layer in contact with a single crystal YSZ electrolyte were studied. As a result of dc and ac investigations, it was found that under anodic polarization the rate of Faraday reaction at the surface of the In₂O₃ electrode is as low as in an ionically blocked electrode. Under cathodic polarization, however, the electrochemical activity of the electrode improves depending on the magnitude of the polarization voltage. Likewise, the electrode polarization resistance decreases after platinum or praseodymium oxide having been deposited on the surface of the In₂O₃ layer. The possible mechanism responsible for such a peculiar behaviour and the limiting step of the electrode reactions are discussed.     

Mixed-potential-type NOx sensor based on YSZ and zinc oxide sensing electrode

Electrochemical sensors using tubular yttria-stabilized zirconia (YSZ) and oxide sensing electrode (SE) were fabricated and examined for NO_x detection at high temperatures. The mixed-potential-type NO_x sensor using ZnO-SE gave the highest sensitivity to NO_x among other single-type oxides tested as SEs in the temperature range of 600–700 °C. The response of the ZnO-attached device was a linear for the logarithm of NO₂ (NO) concentrations from 40 to 450 ppm. The sensing mechanism of the sensor was discussed on the basis of the gas adsorption-desorption behavior, the catalytic activity data, and electrochemical behavior for oxides examined.     

Low-temperature zirconia oxygen gauges based on RuO2 electrode

A low temperature oxygen gauge based on zirconia electrolyte has been developed. It makes use of RuO₂ as electrode material in place of platinum in conventional gauges. The low interfacial impedance of the RuO₂ electrode makes it possible to keep the cell resistance below 10⁶ ω even at low temperatures. Nernst's law tests indicate that this cell can give theoretical outputs down to 498 K campared to 923 K for gauges with platinum electrodes. Faraday's law tests confirm its good performance over a wide range of oxygen concentrations. High electronic conductivity, single oxide phase, slight non-stoichiometry and good adherence are responsible for the good performance of RuO₂ as electrode. An activation energy of 90.95 kJ/mole observed for the interface shows that the vacancy movement in the electrolyte is the rate controlling step. The evaporation of RuO₂ as RuO₄ gives rise to flow dependent output. This can be overcame by operating the cells at low temperatures though at the cost of speedy response. The low operating tempratures lead to a compact gauge with good stability.     

基于银纳米线电极-rGO敏感材料的柔性NO2气体传感器

使用银纳米线作为材料制备柔性叉指电极,用还原氧化石墨烯(reduced graphene oxide, rGO)作为气体敏感材料制备出柔性气体传感器,并研究其对二氧化氮气体的响应特性以及柔韧性能.实验结果表明,制备的以银纳米线作为电极的r GO气体传感器可以实现室温下对浓度为5-50 ppm (1 ppm=10^–6)的NO2气体的检测,对50 ppm的NO2的响应能够达到1.19,传感器的重复性较好,恢复率能够保持在76%以上,传感器的灵敏度是0.00281 ppm^-1,对浓度为5 ppm的NO2气体的响应时间是990 s,恢复时间是1566 s.此外,传感器在0°-45°的弯曲角度下仍表现出优异的电学特性与气体传感性能,所制备的器件具有相对稳定的导电性和较好的弯曲耐受性.     

Temperature dependence of NO2 sensitivity of YSZ-based mixed potential type sensor attached with NiO sensing electrode

A mixed potential type yttria-stabilized zirconia-based sensor using NiO sensing electrode and Pt reference electrode was fabricated, and its NO₂ sensing characteristics were examined at various operating temperatures in the range of 700–950 °C. It was observed that the sensitivity to NO₂ strongly depends on the operating temperature of the sensor; the sensitivity decreases with increasing operating temperature, while the response/recovery rates increase. To rationalize this temperature dependence of NO₂ response, polarization curves and complex impedances of the sensor were measured in the base gas and in the sample gas (400 ppm NO₂?+?base gas) at various operating temperatures. It turned out that the operating temperature had a strong influence on the rate of anodic reaction of oxygen; the increased rate of anodic reaction leads to lower NO₂ sensitivity and quicker response/recovery at higher operating temperature.     

Defect structures and electronic properties in cubic stabilized zirconia

EPR and optical absorption measurements have been performed to detect the defects activated by X-rays in single crystals of zinconium dioxide, stabilized in the cubic phase by the addition of Y₂O₃ in two different concentrations (12 and 24 mol%). Production yield and thermal stability confirm the attribution of the 375 nm optical absorption band to the defect responsible for the EPR T-signal. Deviations from a random distribution of the stoichiometric oxygen vacancies are evidenced. These results agree with the existence of ordering processes in the vacancy system, as predicted by recent structural models.     

Structure and electrical behavior in air of TiO2-doped stabilized tetragonal zirconia ceramics

2 -doped YTZP ([%mol]3 Y₂O₃) compositions sintered in the temperature range of 1300 to 1450 °C, the tetragonal zirconia solid solutions field for the ZrO₂-Y₂O₃-TiO₂ system was established. The solubility of TiO₂ in YTZP was found to be about 12–[%mol]14 at 1450 °C. Structural characterization of the Ti-YTZP tetragonal zirconia solid solutions was carried out using X-ray absorption spectroscopy (EXAFS and XANES) to provide information on the environment of Ti atoms. The electrical behavior in air of the TiO₂-doped tetragonal zirconia solid solutions was studied by impedance spectroscopy in the temperature range of 300 to 800 °C, and it was found that the ionic conductivity decreases with increasing titania content. EXAFS and XANES results show that as the Ti⁴⁺ ions dissolve into the tetragonal zirconia YTZP matrix, a displacement of Ti ions from the center of symmetry takes place, leading to a non-random substitution of Ti⁴⁺ ions on Zr⁴⁺ lattice sites. Ti-O bond distances derived from EXAFS indicate that the Ti ion can be in a square-pyramidal arrangement, i.e., fivefold oxygen-coordinated. As a consequence two kinds of cation–oxygen vacancy associations are created; the high-mobility oxygen-vacancy–eightfold-coordinated cation (Zr⁴⁺) and the low-mobility oxygen-vacancy–fivefold-coordinated cation (Ti⁴⁺). This results in a decrease in the global concentration of moving oxygen vacancies and, therefore, in a decrease of the electrical conductivity. Received: 1 April 1998/Accepted: 28 September 1998     

Structure and phase composition studies of partially stabilized zirconia

Zirconia single crystals doped with 2.8, 3.2, 3.7, and 4.0 mol % of Y₂O₃ have been studied. The phase composition and structure have been studied by X-ray diffraction analysis and transmission electron microscopy. It has been established that all investigated samples has two ZrO₂ tetragonal phases with tetragonality c/a = 1.006–1.007 and c/a = 1.014–1.015 independent of the stabilizing impurity content. The former phase is not transformed, whereas the latter is transformed into a monoclinic one. In all cases the samples have a developed twin structure. Twinning hierarchy is observed: there are first-, second-, third-order, etc., twins, each of them containing the next-order twins inside them. Elastic stress relaxation occurs by twinning rather than by generation of dislocations. The stabilizing impurity content affects the structure nonmonotonically; the minimum dimensions of the twin lamellas refer to the Y₂O₃ concentration of 3.2 mol %.     

Effect of palladium oxide electrode on potentiometric sensor response to carbon monoxide

Ionics - This study aims to explore the potential merits of palladium oxide sensing electrode. PdO is applied on a solid-state potentiometric sensor on an yttria-stabilized zirconia (YSZ)...     

High-temperature sensor using a Fabry-Perot interferometer based on solid-core photonic crystal fiber

A micro Fabry-Perot interferometer(M-FPI) is constructed by splicing a short section of polarizationmaintaining photonic crystal fiber(PM-PCF) to an end-cleaved single-mode fiber with controllable offset. Due to the high effective optical path difference induced by the solid core of the PCF,the M-FPI has an ultrasmall cavity of approximately 110μm.The temperature sensitivity within a range from 33℃to approximately 600℃is measured to be 13.8 pm/℃,which shows good agreement with the theoretical result.This proposed sensor has the advantages of ultracompact size and high stability.Therefore,it is suitable for various space-limited sensing applications in harsh environments.     

Electrochemical water splitting using nano-zeolite Y supported tungsten oxide electrocatalysts

Zeolites are often used as supports for metals and metal oxides because of their well-defined microporous structure and high surface area. In this study, nano-zeolite Y (50–150 nm range) and micro-zeolite Y (500–800 nm range) were loaded with WO₃, by impregnating the zeolite support with ammonium metatungstate and thermally decomposing the salt thereafter. Two different loadings of WO₃ were studied, 3 wt.% and 5 wt.% with respect to the overall catalyst. The prepared catalysts were characterized for their morphology, structure, and surface areas through scanning electron microscope (SEM), XRD, and BET. They were further compared for their electrocatalytic activity for hydrogen evolution reaction (HER) in 0.5 M H₂SO₄. On comparing the bare micro-zeolite particles with the nano-form, the nano-zeolite Y showed higher currents with comparable overpotentials and lower Tafel slope of 62.36 mV/dec. WO₃ loading brought about a change in the electrocatalytic properties of the catalyst. The overpotentials and Tafel slopes were observed to decrease with zeolite-3 wt.% WO₃. The smallest overpotential of 60 mV and Tafel slope of 31.9 mV/dec was registered for nano-zeolite with 3 wt.% WO₃, while the micro-zeolite gave an overpotential of 370 mV and a Tafel slope of 98.1 mV/dec. It was concluded that even with the same metal oxide loading, nano-zeolite showed superior performance, which is attributed to its size and hence easier escape of hydrogen bubbles from the catalyst.     

Highly sensitive electrochemical sensor for paeonol using NMP-exfoliated grapheme-modified electrode

Ionics - Graphene nanosheets (GS) were easily prepared from graphite powder by one-step ultrasonic exfoliation in N-methyl-2-pyrrolidone (NMP). The resulting GS was used to modify the surface of...     

A study of the switching mechanism and electrode material of?fully CMOS compatible tungsten oxide ReRAM

Tungsten oxide (WO _X ) resistive memory (ReRAM), a two-terminal CMOS compatible nonvolatile memory, has shown promise to surpass the existing flash memory in terms of scalability, switching speed, and potential for 3D stacking. The memory layer, WO _X , can be easily fabricated by down-stream plasma oxidation (DSPO) or rapid thermal oxidation (RTO) of W plugs universally used in CMOS circuits. Results of conductive AFM (C-AFM) experiment suggest the switching mechanism is dominated by the REDOX (Reduction-oxidation) reaction??the creation of conducting filaments leads to a low resistance state and the rupturing of the filaments results in a high resistance state. Our experimental results show that the reactions happen at the TE/WO _X interface. With this understanding in mind, we proposed two approaches to boost the memory performance: (i) using DSPO to treat the RTO WO _X surface and (ii) using Pt TE, which forms a Schottky barrier with WO _X . Both approaches, especially the latter, significantly reduce the forming current and enlarge the memory window.