基于SAW气敏阵列的火电厂排放物SO2与NO2监测装置设计

针对大气污染监测的迫切需求,设计了基于SAW气敏阵列的SO₂与NO₂监测装置,并采用人工神经网络算法进行气体浓度测量。对所构建的监测装置进行了实验验证和实际测试,结果表明,装置具有良好的检测性能和自动监测优势,可推广应用到各种生产行业的大气污染监测体系中。     

Room temperature nitrogen dioxide chemresistor using ultrathin vanadyl-phthalocyanine film as active layer

A room temperature nitrogen dioxide (NO₂) chemresistor using 1.8 nm ultrathin vanadyl-phthalocyanine (VOPc) film as active layer has been prepared by Weak Epitaxy Growth (WEG) method. Its gas sensing properties to NO₂ have been compared with a 7 nm polycrystalline VOPc chemresistor. The ultrathin film device shows stronger response and better recovery character. Further results reveal that the two-dimensional transport film provides an effective charge transfer system after NO₂ adsorption and it gets rid of bulk diffusion at the same time. Kelvin probe force microscopy (KPFM) results suggest that grain boundaries are easily doped by analyte but is slow in desorption compared with crystal grains. The ultrathin film device shows advanced sensing mechanism compared with the polycrystalline film.     

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.     

Carbon dioxide gas sensor using a graphene sheet

In this article, we report on a high-performance graphene carbon dioxide (CO₂) gas sensor fabricated by mechanical cleavage. Unlike other solid-state gas sensors, the graphene sensor can be operated under ambient conditions and at room temperature. Changes in the device conductance are measured for various concentrations of CO₂ gas adsorbed on the surface of graphene. The conductance of the graphene gas sensor increases linearly when the concentration of CO₂ gas is increased from 10 to 100 ppm. The advantages of this sensor are high sensitivity, fast response time, short recovery time, and low power consumption.     

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.     

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.     

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.     

Modification of the oxygen diffusivity in limiting current oxygen sensors

Effect of sacrificial carbon on microstructure of protective layer and sensing properties of limiting current oxygen sensors were studied. Graphite and carbon nanofiber with different concentrations were examined as sacrificial layer. Therefore, several YSZ-based electrochemical gas sensors were fabricated with dissimilarity in the diffusivity of the layer covering their measuring electrodes.Gas sensors were tested as potentiometric and amperometric devices under O₂-N₂ mixtures, and synthetic gases similar to the exhaust gas mixtures from combustion engines. Sensors with low diffusivity (low concentration of sacrificial material) exhibit more abrupt and O₂-sensitive potentiometric responses. Indeed, less O₂-linear amperometric responses and higher response times are their characteristics. Sensors with high diffusion in their layers (high concentration of sacrificial material) show a less abrupt step-drop potentiometric response but a more linear O₂ dependence for the amperometric response and, in general, lower response times.Results suggest that the configuration of the diffusive layer shall be controlled in terms of the expected performance of the sensor, as an amperometric or potentiometric device. The controlling parameters are discussed and given in this study.     

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).     

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.     

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.     

Adsorption of NO2 molecules on armchair phosphorene nanosheet for nano sensor applications – A first-principles study

The electronic and NO₂ adsorption properties of hydrogenated armchair phosphorene nanosheet device is investigated through density functional theory (DFT) and non-equilibrium Green’s function method (NEGF). The armchair phosphorene nanosheet is used for the detection of NO₂ gas in phosphorene molecular device. The DOS spectrum demonstrates the change in peak maxima due to transfer of electrons between NO₂ gas and phosphorene base material. The change in the peak amplitude is observed along the valance band as well as in the conduction band in the transmission spectrum of phosphorene device. I–V characteristics support the change in the current upon adsorption of NO₂ gas molecule on phosphorene molecular device. Using formation energy, structural stability of phosphorene nanosheet has been studied. The adsorption properties of NO₂ on phosphorene nanosheet have also been investigated with the help of adsorption energy, Mulliken charge and Bader charge analysis. In order to ascertain the selectivity of NO₂ gas along phosphorene molecular device in the ambient condition, the adsorption behavior of O₂ and CO₂ is also studied. The findings of the present work confirm that phosphorene molecular device can be used as a NO₂ gas sensor and also the influence of Al substitution in phosphorene nanosheet device is explored and reported.     

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.     

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).     

Electrostatic sprayed SnO2 and Cu-doped SnO2 films for H2S detection

This paper presents the ability of electrostatic sprayed tin oxide (SnO₂) and tin oxide doped with copper oxide (1, 2, and 4 at.% Cu) films to detect different pollutant gases, i.e., H₂S, SO₂, and NO₂. The influence of a copper oxide dopant on the SnO₂ morphology is studied using scanning electron microscopy (SEM) technique, which reveals a small decrease in the porosity and particle size when the amount of dopant is increased. The sensing properties of the SnO₂ films are greatly improved by doping, i.e., the Cu-doped SnO₂ films have large response to low concentration (10 ppm) of H₂S at low operating temperature (100 °C). Furthermore, no cross-sensitivity to 1 ppm NO₂ and 20 ppm SO₂ is observed. Among the studied films, the 1 at.% Cu-doped SnO₂ layer is the most sensitive in the detection of all the studied gases.     

High-sensitivity NO2 gas sensors based on flower-like and tube-like ZnO nanomaterials

Hierarchical flower-like and 1D tube-like ZnO architectures were synthesized by a microemulsion-based solvothermal method. Technologies of XRD, SEM and TEM were used to characterize the morphological and structural properties of the products. The influence of the flower-like and tube-like morphologies on their NO₂ sensing properties was investigated. The experimental results showed that high-sensitivity NO₂ gas sensors were fabricated. The sensitivity of the tube-like ZnO gas sensor was much higher than that of the flower-like ZnO gas sensor and the tube-like ZnO gas sensor exhibited shorter response time. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technique was employed to investigate the NO₂ sensing mechanisms. Free nitrate ions, nitrate and nitrite were the main adsorbed species during the adsorption, and NO also existed in the initial period of surface reoxidation. Furthermore, N₂O was formed via NO⁻ and N₂O₂⁻ stemmed from NO and increased upon rising temperature. Moreover, the PL spectra and the XPS spectra further proved that the intensity of donors (oxygen vacancy (V_O) and zinc interstitial (Zn_i)) and surface oxygen species (O₂⁻ and O₂) involved in the gas sensing mechanism leaded to the different sensitivities.     

Gas sensing properties of platinum derivatives of single-walled carbon nanotubes: A DFT analysis

The limitations of intrinsic carbon nanotube (CNT) based devices to examine toxic gases motivate us to investigate novel sensors which can possibly overcome sensitivity problems. Pt–CNT assemblies (with Pt deposited externally as well as internally Pt-doped ones) interacting with NO₂ and NH₃ are studied and compared with unmodified CNTs. DFT calculations show that Pt can enhance adsorption and charge transfer processes to a very large degree. Incoming gas molecules cause changes in the electronic structure and charge distribution of the Pt-substituted CNTs that are both larger and more far-reaching than in their unmodified counterparts. Their relatively high stability is unaffected by the complexation with NO₂ and NH₃. CNTs with defective surface were also investigated. The sensing performance of Pt-doped CNT is found to be superior to defected CNTs.     

Design and experimental validation of an extended Kalman filter-based NOx concentration estimator in selective catalytic reduction system applications

This paper presents an extended Kalman filter (EKF) based approach of integrating NO_x and NH₃ sensors to estimate the NO_x concentrations in Diesel engine selective catalytic reduction (SCR) aftertreatment systems. NO_x sensors have been commonly used by vehicles for aftertreatment system control and onboard diagnostics (OBD) purposes. However, most currently available NO_x sensors are cross-sensitive to ammonia. Based on the experimental observations and physical inferences, the cross-sensitivity characteristics may change with temperature and is hard to be predicted by a model. This feature limits the applications of NO_x sensors on urea-SCR systems where ammonia is the reductant for NO_x conversions. Grounded in the insight into SCR dynamics and NO_x sensor properties, a novel approach of using an extended Kalman filter to estimate the actual exhaust gas NO_x concentration was proposed. The estimator was examined by NO_x measurements from a Horiba gas analyzer under different engine operating conditions. The experimental results show that the EKF-based approach can significantly improve the accuracy of NO_x concentration measurements from the original NO_x sensor readings.     

Highly sensitive NO2 sensor based on square-like tungsten oxide prepared with hydrothermal treatment

The square-like WO₃ nanosheets were synthesized by hydrothermal treatment of irregular WO₃ nanosheets prepared through acidification of Na₂WO₄·2H₂O. The obtained square-like and irregular WO₃ nanosheets were characterized with field emission scanning electron microscopy, X-ray powder diffraction and transmission electron microscopy. The gas sensing properties of sensors based on as-prepared samples were investigated. The results indicated that both samples exhibited high response to NO₂. The sensor based on square-like WO₃ nanosheets exhibited remarkably enhanced response and faster response/recovery time for NO₂ compared with that based on irregular nanosheets. Especially, the sensor based on square-like WO₃ nanosheets could detect NO₂ down to 40 ppb, which covered environmental standard. A possible reason for the influence of unique structure on the sensing properties of sensors based on square-like WO₃ was proposed.     

Glucose-mediated hydrothermal synthesis and gas sensing characteristics of WO3 hollow microspheres

Tungsten-coated carbon microspheres were prepared by one-pot hydrothermal reaction of an aqueous solution containing glucose and sodium tungstate. The spheres were converted into WO₃ hollow microspheres by the decomposition of their core carbon. The [glucose]/[sodium tungstate] ratio of the stock solution determined not only the morphology of the precursors but also the phase of the powders after calcination. The WO₃ hollow microspheres showed a higher gas response and more selective detection of 0.5–2.5 ppm NO₂ than WO₃ solid and nano-porous microspheres did. The enhanced NO₂ sensing characteristics are explained in relation to the surface area, pore volume, and hollow morphology.