SO2和NO2在高岭石表面的反应和协同效应

高岭石是一种含铝的层状硅酸盐矿物,研究大气中常见的气体在其表面的非均相反应具有一定的实际意义,在一定程度上可揭示大气环境中化学反应过程。文章采用自行搭建的原位漫反射红外傅里叶光谱(DRIFTS)检测系统,考察了在干态和湿态条件下,对照SO_2和NO_2分别在高岭石颗粒物表面发生的非均相反应过程,以及SO_2和NO_2协同反应效应。实验结果表明,SO_2与高岭石颗粒物的非均相反应均较弱,仅在干态下检测到亚硫酸盐物种,并且存在较大的CO_2的红外吸收峰。NO_2在干态和湿态条件下均检出了硝酸盐物种,适宜的湿度有利于硝酸盐的生成。在SO_2和NO_2共同与高岭石反应的过程中,发现四氧化二氮(N_2O_4)取代了亚硝酸盐成为反应的中间体,同时亚硫酸盐被氧化为硫酸盐。SO_2和NO_2在高岭石颗粒物表面的反应中相互影响,协同作用。     

漫反射光谱法测定环境样品中的微量汞

基于Hg^2＋与KI-CuSO4反应生成橙红色Cu2HgI4,用漫反射光谱直接测定汞沉淀物.探讨了该方法的影响因素及测定条件.方法的线性范围0.1-6.0μg,检测限为0.01μg,用于污水及土壤样品中微量汞的测定回收率达96%-102%.     

汽车尾气净化催化剂Ag/SAPO-34选择性催化还原NO

评价了Ag/SAPO-34分子筛催化剂选择性还原NO的活性,并运用漫反射红外光谱原位研究NO在Ag/SAPO-34催化剂上的选择性催化还原机理.结果表明Ag/SAPO-34有良好的低温活性,在氧气浓度为3.6%和温度为573K～673K时NO还原成N2的转化率达70%;催化剂活性随C3H6浓度的增加而升高,随空速的增加而稍有下降.基于漫反射红外光谱,认为反应机理为:NO、丙烯和氧反应,在Ag/SAPO-34催化剂上生成吸附的有机-氮氧化物,再由这些吸附物种分解成N₂,催化还原的关键是形成有机-氮氧化物中间体.氧的作用是充分促进丙烯活化以及增加NO_x吸附态含量,并且氧的存在是有效产生一系列中间物不可缺少的条件.     

光照对SO2在矿质氧化物表面非均相反应的影响

使用原位漫反射红外傅里叶变换光谱(DRIFTS)研究了SO_2在α-Al_2O_3、TiO_2、CaO和α-Fe_2O_3颗粒物表面的非均相反应,考察了紫外光光照(波长约365 nm)对SO_2在不同氧化物表面反应的影响.结果表明,无紫外光照射条件下,SO_2在TiO_2、α-Al_2O_3、CaO颗粒物表面反应的主要产物为亚硫酸盐;有紫外光照射条件下,SO_2在TiO_2、α-Al_2O_3、CaO颗粒物表面反应的主要产物为硫酸盐;但紫外光照射对SO_2在α-Fe_2O_3表面的反应并没有明显的影响.推测机理可能是光照促进了颗粒物表面的亚硫酸盐向硫酸盐的转化.     

Laboratory simulation of SO2 heterogeneous reactions on hematite surface under di erent SO2 concentrations

The variations of sulfate formation and optical coe cients during SO2 heterogeneous reactions on hematite surface under di erent SO2 concentrations were examined using in situ di use reflectance infrared Fourier transform spectroscopy (DRIFTS) and ion chromatograph (IC). Laboratory experiments revealed that within ambient SO2 of 0.51–18.6 ppmv, sulfate product, producing velocity, absorption and backward scattering coe cients showed an increasing trend with SO2 concentration. Under given SO2 concentration, the velocity of sulfate producing performed an evolution of initial increasing, midterm decreasing and final stabilizing. The reactive uptake and Brunauer-Emmett-Teller (BET) uptake coe cients of heterogeneous reactions rose with SO2 and exhibited high reactivities. Considering global warming, this result is important for the knowledge of heterogeneous reactions of SO2 on mineral particle surface in the atmosphere and the assessment of their impacts on radiative forcing.     

Pure and Mg-doped self-assembled ZnO nano-particles for the enhanced photocatalytic degradation of 4-chlorophenol

A novel self-assembled pure and Mg doped ZnO nano-particles （NPs） were successfully synthesized by a simple low temperature co-precipitation method. The prepared photocatalysts were characterized by X-ray diffraction, high resolution scanning electron mi- croscopy, high resolution transmission electron microscopy, diffuse reflectance spectroscopy and photoluminescence （PL） spectroscopy. The results indicated that the prepared photocatalysts showed high crystallinity with a uniform size distribution of the NPs. The degradation of cholorphenols is highly mandatory in today＇s scenario as they are affecting the environment adversely. Thus, the photocatalytic degradation of 4-chlorophenol （4-CP）, a potent endocrine disrupting chemical in aqueous medium was investigated by both pure and Mg-doped ZnO NPs under UV-light irradiation in the present study. The influence of the Mg content on the structure, morphology, PL character and photocatalytic activity of ZnO NPs were investigated systematically. Furthermore,the effect of different parameters such as 4-CP concentration, photocatalyst amount, pH and UV-light wavelength on the resulting photocatalytic activity was investigated.     

In situ DRIFTS study of hygroscopic behavior of mineral aerosol

In situ difflusion reflectance infrared Fourier transform spectroscopy was used to study the water adsorption on mineral oxides(SiO2,α-Al2O3,MgO,Fe2O3,TiO2).The results showed that all the water adsorption isotherms were well fitted with the Brunauer-EmmettTeller(BET)-Ⅲ type equation,with the calculated monolayers occurring at 24%-30% relative humidity.It showed that about 1-5 layers of water adsorbed on oxides surfaces in ambient relative humidity(20%-90%).The measured deliquescence relative humidity of NaCl was(74 ± 1)%,which demonstrated that DRIFTS is a useful method for the study the hygroscopic behavior of mineral dust.In addition,the limits of DRIFTS were also discussed.     

常温条件下O2和NO2对Ca(OH)2吸附SO2产物的影响

在100℃的无水蒸气条件下研究以Ca（OH）₂为吸收剂同时脱硫脱硝过程中SO₂的固定和氧化过程,以及O₂和NO₂的作用。分别用原位漫反射傅里叶红外光谱和固定床反应器,研究过程中Ca（OH）₂表面和气相的成分变化。结果表明:SO₂吸附在Ca（OH）₂表面形成的CaSO₃不易被O₂氧化,但可以被NO₂氧化。同时脱除过程中,NO₂对CaSO₃的氧化具有选择性:930~936 cm-1位置的红外吸收峰在反应过程中先升高后降低,980~995 cm-1位置的红外吸收峰只升高不降低。无O₂条件下,参与反应的NO₂以接近1∶1的比例转化为NO,而有O₂条件下Ca（OH）₂同时脱除NO₂和SO₂时,Ca（NO₃）₂的含量明显增加,且反应前期CaSO₄的生成速率加快。     

Fe掺杂对MnO_x催化剂结构性质及低温SCR反应机制的影响

采用Fe对MnOx催化剂的低温选择性催化还原（SCR）活性进行改性,并通过N2吸附、X射线衍射（XRD）、X射线光电子能谱（XPS）及原位漫反射傅里叶红外（insituDRIFTS）重点探讨了Fe引入后催化剂结构性质的变化及对低温SCR反应机制的影响.结果表明,Fe的掺杂能显著提高催化剂的低温SCR性能,Fe/（Fe＋...     

大气化学非均相反应摄取系数的测定

摄取系数是表征大气非均相反应的重要物理化学参数,也是大气颗粒物表面摄取气体能力的重要量化指标.本文综述了摄取系数的主要概念、主要测定方法和影响因素,以NaCl与NO2非均相反应为例,讨论了用漫反射傅立叶转换红外原位反应器扩散实验方式测定反应摄取系数的方法和误差,分析了气体扩散深度与红外穿透厚度对测定结果的影响,并测定了初始反应摄取系数.