Observation of tropospheric NO_2 by airborne multi-axis differential optical absorption spectroscopy in the Pearl River Delta region,south China

An airborne multi-axis differential optical absorption spectroscopic （AMAX-DOAS） instrument was developed and applied to measure tropospheric NO2 in the Pearl River Delta region in the south of China. By combining the measurements in nadir and zenith directions and analyzing the UV and visible spectral region using the DOAS method, information about tropospheric NO2 vertical columns was obtained. Strong tropospheric NO2 signals were detected when flying over heavilly polluted regions and point sources like plants. The AMAX-DOAS results were compared with ground-based MAX-DOAS observations in the southwest of Zhuhai city using the same parameters for radiative transport calculations. The difference in vertical column data between the two instruments is about 8%. Our data were also compared with those from OMI and fair agreement was obtained with a correlation coefficient R of 0.61. The difference between the two instruments can be attributed to the different spatial resolution and the temporal mismatch during the measurements.     

Synchrotron radiation VUV double photoionization of some small molecules

The VUV double photoionizations of small molecules (NO,CO,CO2 ,CS2 ,OSC and NH3 ) were investigated with photoionization mass spectroscopy using synchrotron radiation. The double ionization energies of molecules were determined with photoionization efficiency spectroscopy. The total energies of these molecules and their parent dications (NO2+ ,CO2+ ,CO2+2 ,CS2+2 ,OSC2+ and NH2+3 ) were calculated using the Gaussian 03 program and Gaussian 2 calculations. Then,the adiabatic double ionization energies of the molecules were predicated by using high accuracy energy mode. The experimental double ionization energies of these small molecules were all in reasonable agreement with their respective calculated adiabatic double ionization energies. The mechanisms of double photoionization of these molecules were discussed based on a comparison of our experimental results with those predicted theoretically. The equilibrium geometries and harmonic vibrational frequencies of molecules and their parent dications were calculated by using the MP2 (full) method. The differences in configurations between these molecules and their parent dications were also discussed on the basis of theoretical calculations.     

Influence of Ba^2＋ and Pb^2＋ Ions on the Raman Dominating Active Vibronic Mode in Strontium Nitrate Crystals

The compositions of Sr(NO3)2 crystals grown from an aqueous solution doped with Ba^2 and Pb^2 were characterized by the electron probe microanalysis technique.It was found that Ba^2 is enriched in {100} sectors and Pb^2 in {111} sectors.The Raman spectra of different parts of these crystals at room temperature in the ranges of 1038-1070cm^-1 and 650-1150cm^-1 were investigated.The results indicated that barium and lead shift the Raman dominating peaks to the lower frequency and broaden the full width at half maximum.Furthermore,barium probably degrades the properties of the Sr(NO3)2 Raman shifter while lead is anticipated to improve it.     

Effects of rapid thermal annealing on the room-temperature NO2-sensing properties of WO3 thin films under LED radiation

WO3 thin films were sputtered onto alumina substrates by DC facing-target magnetron sputtering.One sample was rapid-thermal-annealed(RTA) at 600℃ in a gas mixture of N2:O2=4:1,and as a comparison,another was conventionally thermal-annealed at 600℃ in air.The morphology of both was investigated by scanning electron microscopy(SEM) and atomic force microscopy(AFM),and the crystallization structure and phase identification were characterized by X-ray diffraction(XRD).The NO2-sensing measurements were taken under LED light at room temperature.The sensitivity of the RTA-treated sample was found to be high,up to nearly 100,whereas the sensitivity of the conventionally thermal-annealed sample was about five under the same conditions.From the much better selectivity and response-recovery characteristics,it can be concluded that compared to conventional thermal annealing,RTA has a greater effect on the NO2-sensing properties of WO3 thin films.     

XAFS CHARACTERIZATION ON THE ACTIVE SITES OF Ni／γ—Al2O3 CATALYSTS FOR NO—SCR BY PROPENE

Ni/γ-Al2O3 catalysts show high catalytic activity for the selective catalytic reduction of NO by C3H6.The microstructures of nickel species were characterized by the spectroscopy of X-ray Absorption Near Edge Structures(XANES) and Extended X-ray Absorption Fine Structures(EXAFS).The resuts of XANES and EXAFS indicate that the nickel species in the sample calcined at 500℃mainly exist as highly dispersed NiO phase,Whereas in the samples calcined at750 and 950℃,the nickel species mainly exist as NiAl2O4-like spinel.The surace NiAl2O4-like spinel is the main active site for the selective reduction of No,and the highly dispersed NiO phase is the main active site for C3H6 oxidation. The formation of subsurface or buld NiAl2O4 spinel results in the reduction of surface spinel and cuases the decrease of activity for the selective catalytic reduction of NO by propene.     

近物所在产生金属离子束方面的研究

Since 1998,many experiments for metallic ion production have been done on LECR2(Lanzhou ECR ion source NO.2),LECR3(Lanzhou ECR ion source NO.3)and SECRAL(Superconductiong ECB ion source Advanced design in Lanzhou)at Institute of Modern Physics.The very heavy metallic ion beams such as those of uranium were also produced by the plasma sputtering method,and supplied for HIRFL(Heavy Ion Research Facility in Lanzhou)accelerators successfully.During the test,11.SeμAU~(28 ),9eμAU~(24 ) were obtained.Some ion beams of the metal having lower melting temperature such as Ni and Mg ion beams were produced by oven method on LECR3 too.The consumption rate was controlled to be lower for ~(26)Mg ion beams production,and the minimum consumption was about 0.3mg per hour.In this paper,the main experimental results are given.Some discussions are made for some experimental phenomena and results,and some conclusions are drawn.     

Laser-induced damage threshold in n-on-1 regime of Ta_2O_5 films at 532,800,and 1064 nm

Ta_2O5 films were prepared with conventional electron beam evaporation and annealed in O_2 at 673 K for 12h.Laser-induced damage thresholds(LIDTs)of the films were performed at 532 and 1064 nm in 1-on-1 regime firstly,and then were performed at 532,800,and 1064 nm in n-on-1 regime,respectively- The results showed that the LIDTs in n-on-1 regime were higher than that in 1-on-1 regime at 532 and 1064 nm.In addition,in n-on-1 regime,the LIDT increased with the increase of wavelength.Furthermore, both the optical property and LIDT of Ta_2O_5 films were influenced by annealing in O_2.     

Simultaneous measurement of SO2 and NO2 concentration using an optical fiber-based LP-DOAS system

SO2 and NO2 are the most important pollution in atmosphere.An optimized long path(LP)differential optical absorption spectroscopy(DOAS)system of high light intensity at an ultraviolet(UV)wavelength is proposed and used to measure the concentration of SO2 and NO2 simultaneously.In contrast to the traditional DOAS,the system adopted a Y-type optical fiber structure instead of a combination of mirrors in the telescope.The UV light intensity test shows that the light intensity of UV can arrive to above 80% of the max measuring range when the light path reaches 135 m,and the integral time of the spectrograph is only 15 ms.The system is proved to be efficacious through laboratory calibration.The maximum error of SO2 calibration is 4.19%,and is 5.22% for NO2.The error of the SO2 and NO2 mixture calibration is within 10%.Field measurement is implemented in a wastewater treatment plant in winter.The measurement light path is 738 m.The concentration of SO2 varies from 6μg/m^3(2.26 ppb)to 20μg/m^3(7.52 ppb),and the concentration of NO2varies from 100μg/m^3(53.2 ppb)to 200μg/m^3(106.4 ppb)approximately.The results are in accordance with the data from a monitoring station nearby in magnitude order and variation tendency mostly.     

High-precision detection technology of NO concentration based on UV differential-adaptive interference cancellation北大核心CSCD

In order to realize high-precision monitoring of vehicle emission, a high-precision and wide-range NO measurement method was proposed. Aiming at the problem that the absorption peaks of SO2 and NO in emission overlapping in the UV band, and it was impossible to directly perform single-component gas inversion, the differential optical density (DOD) of mixed gas in the NO sensitive band (200 nm～230 nm) was first calculated by the ultraviolet differential optical absorption spectroscopy (UV-DOAS) method. Then, the adaptive interference cancellation technology was introduced to achieve rapid separation of mixed gas DOD. Finally, the least square method was used to perform the concentration inversion of separated NO. This method could achieve rapid inversion of NO concentration (volume fraction of gas) in the range of 100×10−6 to 3 000×10−6. After testing, the absolute value of the relative error of inversion is less than 10% in the concentration range of 100×10−6 to 200×10−6, and less than 5% in the concentration range of 300×10−6 to 3 000×10−6. This method has the characteristics of large measurement range and fast speed, and can meet the measurement requirements of NO concentration in the range of 3 000×10−6 in vehicle emission. © 2022 Editorial office of Journal of Applied Optics. All rights reserved.     

Low-temperature heat capacities and standard molar enthalpy of formation of N-methylnorephedrine C11H17NO（s）

This paper reports that low-temperature heat capacities of N-methylnorephedrine C11H17NO（s） have been measured by a precision automated adiabatic calorimeter over the temperature range from T=78K to T=400K. A solid to liquid phase transition of the compound was found in the heat capacity curve in the temperature range of T=342-364 K. The peak temperature, molar enthalpy and entropy of fusion of the substance were determined. The experimental values of the molar heat capacities in the temperature regions of T=78-342 K and T=364-400 K were fitted to two poly- nomial equations of heat capacities with the reduced temperatures by least squares method. The smoothed molar heat capacities and thermodynamic functions of N-methylnorephedrine C11H17NO（s） relative to the standard refer- ence temperature 298.15 K were calculated based on the fitted polynomials and tabulated with an interval of 5 K. The constant-volume energy of combustion of the compound at T=298.15 K was measured by means of an isoperibol precision oxygen-bomb combustion calorimeter. The standard molar enthalpy of combustion of the sample was calculated. The standard molar enthalpy of formation of the compound was determined from the combustion enthalpy and other auxiliary thermodynamic data through a Hess thermochemical cycle.     

基于紫外吸收的烟气中NO和NO2成分浓度的同时测量

利用高分辨率光栅单色仪测量到的不同浓度的NO和NO2混合气体综合紫外吸收光学厚度,将光学厚度中的快变离散吸收与NO浓度相关,将慢变连续吸收与NO2浓度相关,同时反演NO和NO2的摩尔浓度。研究结果表明:(1)当气体总压接近一个大气压时,NO2反映出很强的转换为N2O4的倾向,转化率R最大值约为22.5%,远大于低气压下的R值,导致NO2吸收截面主要取决于N2O4的吸收特性,表现为慢变的连续吸收特征;(2)离散吸收截面随NO分压增大产生谱线增宽现象,吸收截面在增宽区域的积分值和NO浓度的线性相关性优于吸收截面峰值。测量和反演结果表明:当NO2分压在17～100Pa范围变化时,NO2摩尔浓度反演的平均相对误差为11.7%。当NO分压在63.8～181.62Pa范围变化时,基于积分法的NO浓度反演的最大相对误差为16.9%,平均相对误差为9.6%,而基于峰值法的NO浓度反演的最大相对误差为38.2%,平均相对误差为14.4%。因此,积分法反演较峰值反演具有更好的线性度和更高的精确度。利用上述测量技术,采用相对简单的测试装备,实现了NO和NO2多种成分浓度的同时测量。     

北京边界层大气中HONO和NO2垂直廓线的测量与分析

基于扫描长程差分吸收光谱(DOAS)系统于2007年8月27日～9月4日期间对北京市郊区进行了大气污染物HONO和NO2等垂直廓线的连续监测,详细探讨了HONO,NO2和HONO/NO2比值的垂直分布特征,重点研究了HONO的形成途径.结果显示HONO和NO2浓度随着高度的增加而降低,而HONO浓度梯度下降的更加剧烈;...     

O2/CO2气氛下CO对煤焦异相还原NO影响的研究

为揭示O₂/CO₂燃烧过程中高浓度的CO对煤焦异相还原NO的影响,在1073 K温度下使用山西褐煤在卧式炉上进行了实验。分别对O₂/CO₂浓度比及CO浓度下NO的还原特性进行详细实验研究。研究结果表明:在O₂/CO₂气氛下,O₂浓度为30%时具有较高的还原率;相同O₂浓度下O₂/CO₂气氛较空气气氛NO还原率高,表明在CO存在的条件下,高浓度的CO₂会促进NO的还原;当CO浓度从1.5%逐渐升高时,NO的还原率逐渐降低,到CO浓度为5%时,NO还原率比没有加入CO时还要低,而在空气气氛下CO浓度的变化对NO的还原率影响较小。     

硝酸镍-硝酸镧基体改进剂石墨炉原子吸收测定硫磺中痕量砷

本文研究了以硝酸镍 硝酸镧为基体改进剂 ,石墨炉原子吸收法测定硫磺中痕量砷 ,还研究了硫磺的控温电热酸消解和高压坩埚酸消解。试验表明 ,硫磺试样经硝酸 高氯酸消解后测砷 ,用硝酸镍 硝酸镧基体改进剂 ,比只用硝酸镍基体改进剂 ,灵敏度明显提高。试样的分析结果与HG ICP AES相吻合 ,方法检出限为0 0 34 μg·mL- 1 ,RSD≤ 2 1% (n =4) ,回收率 97 5 %～ 110 %。     

14N chemical shifts and quadrupole coupling constants of inorganic nitrates

The isotropic chemical shift and the nuclear quadrupole coupling constant for (14)N were obtained for 14 inorganic nitrates by solid-state MAS NMR measurements at two different field strengths, 9.4 and 11.7 T. The compounds studied were polycrystalline powders of AgNO(3), Al(NO(3))(3), Ba(NO(3))(2), Ca(NO(3))(2), CsNO(3), KNO(3), LiNO(3), Mg(NO(3))(2), NaNO(3), Pb(NO(3))(2), RbNO(3), Sr(NO(3))(2), Th(NO(3))(4)center dot4H(2)O, and UO(2)(NO(3))(2)center dot3H(2)O. Even though the spectra show broadening due to (14)N quadrupole interactions, linewidths of a few hundred hertz and a good signal-to-noise ratio were achieved. From the position of the central peaks at the two fields, the chemical shifts and the nuclear quadrupole coupling constants were calculated. The chemical shifts for all compounds studied range from 282 to 342 ppm with respect to NH(4)Cl. The nuclear quadrupole coupling constants range from 429 kHz for AgNO(3) to 993 kHz for LiNO(3). These data are compared with those available in the literature.     

Quantum Number Dependence of Lineshift Coefficients Induced by Collisions with Noble Gas Perturbers in the nu(3) Band of NO(2)

To complete our study concerning lineshift in the rovibrational spectrum of (14)N(16)O(2), a pulse-driven three-channel lead salt diode laser spectrometer was applied to record high-resolution spectra at room temperature in the 6.2-μm region corresponding to the nu(3) band at low NO(2) concentrations. The shift was studied for collisions with the noble gases He, Ne, Ar, Kr, and Xe. This paper extends our recently published data in order to analyze the quantum number dependence of the shift effect more precisely. Therefore, in this paper, additionally eight unresolved NO(2) doublets covering an enlarged quantum number range (10 相似文献   

均相条件下NO与CO、NCO的反应机理研究

基于量子化学密度泛函理论研究了NO与CO、NCO在均相条件下的反应机理并进行了动力学和平衡常数的分析. CO与NO的均相反应存在两条反应路径：两者首先反应形成中间体CNO₂,CNO₂不易稳定存在,其继续与CO、NO反应分别生成NCO、N₂O. NCO的生成速率大于N₂O,但两条反应路径的反应速率常数都很小.与已发现的反应路径相比,反应中间体CNO₂可以降低均相条件下CO与NO的反应能垒,分析发现CNO₂中的N原子是易发生反应的活性位点. NCO与NO的反应同样存在两条路径,优势反应路径随温度升高而改变,但非优势路径对反应的贡献不能忽略,分析平衡常数可知N₂的存在对反应影响可以忽略,因此燃烧环境中NCO与NO的反应既生成N₂O和CO,也生成N₂和CO₂.     

Rg·NO(Rg=He、Ne、Ar和Kr)团簇的理论研究

利用从头计算方法研究Rg·NO团簇(Rg=He,Ne,Ar和Kr)．采用CCSD(T)计算方法和cc-PVDZ基组计算中性Rg·NO团簇的的结构和振动频率．计算结果显示，中性的Rg·NO团簇呈现歪斜的T型结构，Rg原子靠近NO分子中O原子的一侧，Rg-N-O键角随质量的增加而增加．利用G2方法和高精度能量模型计算中性Rg·NO团簇基态的离解能和电离能，以及Rg·NO+团簇的离解能．计算结果表明，随着Rg原子极化率的增加，Rg·NO的电离能呈线性降低，而Rg·NO+的解离能呈线性增加， 电荷/诱导的偶极子相互作用对Rg·NO+中的NO+和Rg之间的相互作用能有重要贡献．     

NO（D^2∑）共振增强的多光子离化谱

利用皮秒Nd：YAG激光器泵浦的光学参量发生傲大器作激发源，获得了NO分子在460～570nm波长范围内的多光子离化谱，测量了离化信号随激光强度的关系，其近五次方关系表明在460～570nm波长范围内NO分子吸收5个光子而离化。通过对谱线的归属，确认在此波长范围内，NO分子的离化过程是通过高激发态D^2∑的共振增强的多光子离化过程。用最小二乘法拟合，获得了D^2∑态的基振动频率和相互作用的力常数。     

Effects of fly ash on NOx removal by pulsed streamers

NO_x removal methods using plasma chemical reactions in nonthermal plasmas have been widely studied. In this paper, the effects of the addition of fly ash on NO_x removal using short-pulsed discharge plasmas are described. Fly ash which had been collected from a coal-burning thermal electrical power plant was used. Experiments were performed using four different mixtures of gases which included NO. These were (N₂+NO), (N₂+NO+O₂), (N₂+NO+H₂O), and (N₂+NO+O₂+H ₂O). These gas mixtures were used either with or without the addition of fly ash. The initial concentration of NO was fixed at 200 ppm (NO parts per million of the gas mixture), The study of the NO_x (NO+NO₂) removal was performed with the fly ash, as it is relevant to real situations in coal power plants. The results show that the presence of fly ash decreased the NO_x removal rate slightly in the case of dry gas mixtures while it increased the NO_x removal rate substantially in the case of wet gas mixtures. These results suggest that the presence of fly ash in the flue gases, which also contain a few percentages of moisture, would be advantageous to the treatment of flue gases emitted from thermal power plants for the removal of nitrogen oxides