Unraveling SO2-tolerant mechanism over Fe2（SO4）3/TiO2 catalysts for NOx reduction

Developing low-temperature SO₂-tolerant catalysts for the selective catalytic reduction of NO_x is still a challenging task. The sulfation of active metal oxides and deposition of ammonium bisulfate deactivate catalysts, due to the difficult decomposition of the as-formed sulfate species at low temperatures（<300 °C）. In recent years, metal sulfate catalysts have attracted increasing attention owing to their good catalytic activity and strong SO₂ tolerance at hi...     

Kinetics of photoelectrocatalytic degradation of humic acid using B2O3·TiO2/Ti photoelectrode

An innovative photoelectrode, B₂O₃·TiO₂/Ti electrode, was prepared by galvanostaticanodisation. The morphology and crystalline texture of the B₂O₃·TiO₂ film on electrode were examined by acomic force microscopy (AFM) and X-ray diffraction respectively. The examination results indicated that the anatase was the dominant component. The kinetics of photoelectrocatalytic(PEC) degradation of humic acid(HA) was investigated; the results demonstrated that effects from strongness to weakness on the photoelectrocatalytic degraded rate of humic acid: power of UV-lamp, area of TiO₂ film, bias, original concentration of humic acid solution. The optimum conditions were power of UV-lamp 125 W, area of TiO2 film 42.0 cm² , bias 1.4 V, original concentration of humic acid solution 5 mg/L in this PEC reaction system.     

Photodegradation of 2,4-D induced by NO2- in aqueous solutions：The role of NO2

To elucidate the effect of nitrite ion （NO2^-） on the photodegradation of organic pollutants, a 300 W mercury lamp and Pyrex tubes restricting the transmission of wavelengths below 290nm were used to simulate sunlight, and the photodegradation processes of 2,4-dichlorophenoxyacetic acid （2,4-D） with different concentrations of NO2^- in freshwater and seawater were studied. The effect of reactive oxygen species （ROS） on the photolysis of 2,4-D was also demonstrated using electron paramagnetic resonance （EPR）. The results indicated that the 2,4-D photolysis reaction followed the first-order kinetics in freshwater and seawater under different concentrations of NO2^-. Meanwhile, the photochemical reaction rate of 2,4-D increased with increasing concentration of NO2^-. When the concentration of NO2^- was lower than 23 mg/L, the photodegradation rate of 2,4-D in seawater was higher than that in freshwater. However, when the concentration of NO2^- was reached 230 mg/L, 2,4-D degradation slowed down in seawater. It was important to note that EPR spectra showed NO2 radical was generated in the NO5 solution under simulated sunlight irradiation, indicating that 2,4-D photodegradation could be induced by NO2. These results show the key role of NO2^- in photochemistry and are helpful for better understanding of the phototransformation of environmental contaminants in natural aquatic systems.     

Ag–AgBr/TiO2/RGO nanocomposite: Synthesis, characterization, photocatalytic activity and aggregation evaluation

Ag–AgBr/TiO_2 supported on reduced graphene oxide(Ag–AgBr/TiO_2/RGO) with different mass ratios of grapheme oxide(GO) to TiO_2 were synthesized via a facile solvothermal-photo reduction method. Compared to the single-, two-and three-component nanocomposites,the four-component nanocomposite, Ag–AgBr/TiO_2/RGO-1 with mass ratio of GO to TiO_2at 1%, exhibited a much higher photocatalytic activity for the degradation of penicillin G(PG)under white light-emitting diode(LED-W) irradiation. The PG degradation efficiency increased with the increase of mass ratio of GO to TiO_2 from 0.2% to 1%, then it decreased with the increase of mass ratio of GO to TiO_2 from 1% to 5%. The zeta potentials of RGO-nanocomposites became more negative with the presence of humic acid(HA) due to the negatively charged HA adsorption, resulting in the shift of points of zero charge to lower values of pH. The aggregations of nanocomposites were more significant due to the bridging effect of HA. Furthermore, the aggregated particle sizes were larger for RGO-nanocomposites compared to other nanoparticles, due to the bindings of the carboxylic and phenolic functional groups in HA with the oxygen-containing functional groups in the RGO-nanocomposites.The microfiltration(MF) membrane was effective for the nanocomposites separation. In the continuous flow through submerged membrane photoreactor(sMPR) system, backwashing operation could efficiently reduce membrane fouling and recover TiO_2, and thus indirectly facilitate the PG removal.     

Photocatalytic degradation of C. I. Reactive Red 24 solution with K6SiW11O39SnⅡ

Environmental friendly materials, K₆SiW₁₁O₃₉Sn (SiWSn), was synthesized. SiWSn photocatalytic decomposition of C. I. Reactive Red 24 (RR24) with the UV-lamp (253.7 nm, 20 W), Xenon lamp filtered less than 390 nm light (500 W) and sun light was investigated. The results showed that RR24 solution could be effectively decolorized with the SiWSn photocatalyst. The photocatalytic degradation efficiency of RR24 with SiWSn was affected by the initial concentration of RR2 solution, the amount of SiWSn and the photolysis time. It is demonstrated that the process of photodegradation of RR24 with SiWSn is a pesudo first-order reaction, which can be described by Langmuir-Hinshelwood equation. Hydroxyl radicals and holes are both the main oxidants in the photocatalytic reaction of RR24 with SiWSn.     

Activity and hydrothermal stability of CeO2–ZrO2–WO3 for the selective catalytic reduction of NOx with NH3

A series of CeO_2–ZrO_2–WO_3(CZW)catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction(SCR)of NO with NH_3 over a wide temperature of 150–550°C.The effect of hydrothermal treatment of CZW catalysts on SCR activity was investigated in the presence of 10% H_2O.The fresh catalyst showed above 90% NO_x conversion at 201–459°C,which is applicable to diesel exhaust NO_x purification(200–440°C).The SCR activity results indicated that hydrothermal aging decreased the SCR activity of CZW at low temperatures(below 300°C),while the activity was notably enhanced at high temperature(above 450°C).The aged CZW catalyst(hydrothermal aging at 700°C for 8 hr)showed almost 80% NO_x conversion at 229–550°C,while the V_2O_5–WO_3/TiO_2 catalyst presented above 80% NO_x conversion at 308–370°C.The effect of structural changes,acidity,and redox properties of CZW on the SCR activity was investigated.The results indicated that the excellent hydrothermal stability of CZW was mainly due to the CeO_2–ZrO_2 solid solution,amorphous WO_3 phase and optimal acidity.In addition,the formation of WO_3 clusters increased in size as the hydrothermal aging temperature increased,resulting in the collapse of structure,which could further affect the acidity and redox properties.     

Enhanced dechlorination of 2,4-dichlorophenol by recoverable Ni/Fe–Fe3O4 nanocomposites

Ni/Fe-Fe_3O_4 nanocomposites were synthesized for dechlorination of 2,4-dichlorophenol(2,4-DCP). The effects of the Ni content in Ni/Fe-Fe_3O_4 nanocomposites, solution pH, and common dissolved ions on the dechlorination efficiency were investigated, in addition to the reusability of the nanocomposites. The results showed that increasing content of Ni in Ni/Fe–Fe_3O_4 nanocomposites, from 1 to 5 wt.%, greatly increased the dechlorination efficiency; the Ni/Fe–Fe_3O_4 nanocomposites had much higher dechlorination efficiency than bare Ni/Fe nanoparticles. Ni content of 5 wt.% and initial p H below 6.0 was found to be the optimal conditions for the catalytic dechlorination of 2,4-DCP. Both 2,4-DCP and the intermediate product 2-chlorophenol(2-CP) were completely removed, and the concentration of the final product phenol was close to the theoretical phenol production from complete dechlorination of 20 mg/L of 2,4-DCP, after 3 hr reaction at initial p H value of 6.0,3 g/L Ni/Fe-Fe_3O_4 , 5 wt.% Ni content in the composite, and temperature of 22℃. 2,4-DCP dechlorination was enhanced by Cl-and inhibited by NO3-and SO_4~(2-). The nanocomposites were easily separated from the solution by an applied magnetic field. When the catalyst was reused, the removal efficiency of 2,4-DCP was almost 100% for the first seven uses, and gradually decreased to 75% in cycles 8–10. Therefore, the Ni/Fe–Fe_3O_4 nanocomposites can be considered as a potentially effective tool for remediation of pollution by 2,4-DCP.     

Photocatalytic degradation of carbofuran in TiO2 aqueous solution：Kinetics using design of experiments and mechanism by HPLC/MS/MS

The photocatalytic degradation kinetics of carbofuran was optimized by central composite design based on response surface methodology for the first time. Three variables, TiO2 concentration, initial pH value and the concentration of carbofuran, were selected to determine the dependence of degradation efficiencies on independent variables. Response surface methodology modeling results indicated that the degradation efficiency of carbofuran was highly affected by the initial pH value and the concentration of carbofuran. Then nine degradation intermediates were detected by HPLC/MS/MS. The Frontier Electron Densities of carbofuran were calculated to predict the active sites on carbofuran attacked by hydroxyl radicals and photoholes. Point charges were used to elucidate the chemisorption pattern on TiO2 catalysts during the photocatalytic process. By combining the experimental results and calculation data, the photocatalytic degradation pathways of carbofuran were proposed, including the addition of hydroxyl radicals and the cleavage of the carbamate side chain.     

Highly selective catalytic reduction of NOxby MnOx–CeO2–Al2O3 catalysts prepared by self-propagating high-temperature synthesis

We first present preparation of MnOx–CeO_2–Al_2O_3 catalysts with varying Mn contents through a self-propagating high-temperature synthesis(SHS) method, and studied the application of these catalysts to the selective catalytic reduction of NOxwith NH3(NH_3-SCR).Using the catalyst with 18 wt.% Mn(18 MnCe1Al2), 100% NO conversion was achieved at 200°C and a gas hourly space velocity of 15384 hr-1, and the high-efficiency SCR temperature window, where NO conversion is greater than 90%, was widened to a temperature range of 150–300°C. 18 MnCe1Al2 showed great resistance to SO_2(100 ppm)and H_2O(5%) at 200°C. The catalysts were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller(BET) analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, and H_2 temperature programmed reduction. The characterization results showed that the surface atomic concentration of Mn increased with increasing Mn content, which led to synergism between Mn and Ce and improved the activity in the SCR reaction. 18 MnCe1Al2 has an extensive pore structure,with a BET surface area of approximately 135.4 m~2/g, a pore volume of approximately 0.16 cm~3/g, and an average pore diameter of approximately 4.6 nm. The SCR reaction on 18 MnCe1Al2 mainly followed the Eley-Rideal mechanism. The performances of the MnOx–CeO_2–Al_2O_3 catalysts were good, and because of the simplicity of the preparation process,the SHS method is applicable to their industrial-scale manufacture.     

Competitive sorption between 17α-ethinyl estradiol and bisphenol A/4-n-nonylphenol by soils

The sorption of 17α-ethinyl estradiol(EE2),bisphenol A(BPA),and 4-n-nonylphenol(NP) in single systems and the sorption of EE2 with different initial aqueous concentrations of BPA or NP were examined using three soils.Results showed that all sorption isotherms were nonlinear and fit the Freundlich model.The degree of nonlinearity was in the order BPA(0.537-0.686) > EE2(0.705-0.858) > NP(0.875-0.0.951) in single systems.The isotherm linearity index of EE2 sorption calculated by the Freundlich model for Loam,Silt Loam and Silt increased from 0.758,0.705 and 0.858,to 0.889,0.910 and 0.969,respectively,when BPA concentration increased from 0 to 1000 μg/L,but the effect of NP was comparably minimal.Additionally,EE2 significantly suppressed the sorption of BPA,but insignificantly suppressed that of NP.These findings can be attributed to the difference of sorption affinity of EE2,NP and BPA on the hard carbon(e.g.,black carbon) of soil organic matter that dominated the sorption in the low equilibrium aqueous concentration range of endocrine-disrupting chemicals(EDCs).Competitive sorption among EDCs presents new challenges for predicting the transport and fate of EDCs under the influence of co-solutes.     

离子色谱方法在分析大气湿沉降中的应用

使用ISC-90美国戴安离子色谱仪,采用AS14阴离子分离柱,分析大气湿沉降中无机阴离子F^-、Cl^-、NO2^-、NO3^-、PO4^-等七种,共检出F^-、Cl^-、NO2^-、NO3^-和SO4^2-五种无机阴离子,它具有分析快速,准确、灵敏高、噪声小,基线稳定,背景电导低,线性范围宽,样品用量少,无污染等优点,同时进行多组份测定,是目前分析大气湿沉降组份首选的分析方法之一。     

无机阴离子对TiO_2-膨润土紫外光降解SDBS的影响

TiO2-膨润土光催化降解水溶液中阴离子表面活性剂十二烷基苯磺酸钠(SDBS)的效率较高,Cl-、SO42-、NO3-、HCO3-、H2PO4-是水体中常见的阴离子,这些阴离子对降解效果的影响直接影响该技术的实际应用。分别投加36 mmol/L上述阴离子的钠盐到SDBS水溶液中,紫外光照射溶液2 h,比较投加与不投加的SDBS去除效果差异,结果表明:(1)水溶液中上述阴离子对TiO2-膨润土降解SDBS的效果都有不利影响,其中HCO3-影响最大,其次是H2PO4-,再次是NO3-,SO42-和Cl-。紫外光照射2 h后,投加HCO3-、H2PO4-、NO3-、SO42-、Cl-的水溶液中SDBS的浓度分别比不投加的高2.63倍、1.63倍、0.73倍、0.52倍和0.46倍。原因有三方面:这几种无机阴离子与有机分子竞争表面活性位置;在接近催化剂颗粒表面的地方产生高极性环境;溶液pH值的改变。(2)投加这些无机阴离子的溶液COD值比不投加的都高,反应2 h投加Cl-、SO42-、NO3-、HCO3-、H2PO4-分别比不投加的溶液COD值高6.62倍,0.26倍,0.03倍,0.29倍,0.45倍。     

丽江市夏季降水化学组成分析

运用相关分析、趋势分析、海盐示踪法和HYSPLIT模型,对2006-05-23～2006-07-02云南丽江市夏季降水常量离子的化学特征分析表明,降水中离子浓度的大小顺序为SO^2-₄>Ca²⁺>Cl^->NO^-₃>Na⁺>K⁺>Mg²⁺,其中SO^2-₄和Ca²⁺是夏季降水中的高浓度离子,分别占离子总浓度的65.5%和15.6%;13次降水中阴离子总浓度显著高于阳离子总浓度.夏季降水中SO^2-₄∶NO^-₃变化范围为7.2～37.1, 平均值为15.7, 表明SO^2-₄为该区降水酸度的主要贡献者.由于离子在大气中的相互反应和来源的相似性,离子间相关性水平较好,其中SO^2-₄和NO^-₃的相关系数为0.74;离子浓度与同期降水和平均风速表现负相关.研究区夏季降水中NO^-₃、 SO^2-₄、 K⁺、Ca²⁺主要是陆源物质输入,NO^-₃、 SO^2-₄、 K⁺、Ca²⁺、Mg²⁺和Cl^-陆源物质贡献比例依次为100%、 98.8%、 96%、 99.3%、 46.7%和50.3%.人类经济活动导致的一些污染是该区大气环境变化的主要原因;丽江周边工业区的污染物质主要通过局地环流输入,南亚、东南亚和我国东南沿海工业区的污染物质主要随季风环流输入.     

田湾核电站大气中水溶性阴离子的观测研究

Cl-、SO24-和NO3-是滨海大气中的主要水溶性阴离子.2005年6月～2006年5月期间,对连云港田湾核电站滨海大气中主要水溶性阴离子Cl-、SO24-和NO3-进行了监测.研究表明,田湾核电站大气中Cl-、SO24-和NO3-的年均值分别为(33.12±53.63)、(53.34±30.34)和(8.34±4.47)μg·m-3;季节变化分析表明,Cl-、SO24-浓度在夏季高、冬季低,NO3-浓度在秋冬季高、夏春季低.气象因素分析表明,风向、风速、气温、相对湿度等对大气阴离子浓度有一定影响.本研究首次对我国滨海核电大气中主要腐蚀性阴离子进行了同时监测,为防止海洋大气腐蚀,保证我国核电工业安全经济运行提供了依据.     

水质对UV/H2O2降解17α-乙炔基雌二醇（EE2）的影响

采用UV/H₂O₂间歇式光氧化反应器,研究了溶液pH值、腐殖酸及水中常见阴离子HCO₃^-、NO₃^-、CO₃^2-、Cl^-和SO₄^2-对UV/H₂O₂工艺降解17α-乙炔基雌二醇(EE2)的影响.结果表明,UV/H₂O₂工艺可以有效地去除水中的EE2,光降解过程符合一级反应动力学模型.双氧水投加量为5 mg/L时,在14W低压汞灯照射下,EE2在自来水和蒸馏水中的光降解一级反应速率常数为0.063 0min^-1和0.132 4min^-1.溶液中的腐殖酸和阴离子HCO₃^-、NO₃^-、Cl^-、SO₄^2-对EE2的光降解反应有抑制作用,4种阴离子浓度为5 mmol/L时,抑制作用依次为HCO₃^->SO₄^2->Cl^->NO₃^-,HCO₃^-可使光降解速率常数降低到50%.自来水中的光降解速率常数低于蒸馏水中的光降解速率常数是水中多种离子影响的结果.     

崇明东滩湿地降水化学特征及来源解析

2009年5月~2010年4月收集了崇明东滩湿地降水,测定了样品的pH值、电导率和主要水溶性离子的浓度,并利用富集因子法和后向轨迹分析对降水中无机离子成分进行源解析.结果表明,崇明东滩整体空气质量良好,大气污染物浓度较低.降水的pH值和电导率的加权均值分别为5.24,17.49μS/cm,为轻度污染的弱酸性水平;SO42?和NO3?是主要的致酸离子,加权浓度分别为52.27,21.39μeq/L;NH4+和Ca2+是主要的碱性离子,加权浓度分别为33.36,27.13μeq/L;离子来源分析表明,Na+和Cl?主要来自于海洋,NH4+的中和作用大于Ca2+和Mg2+,大气颗粒物主要以(NH4)2SO4、NH4HSO4、NH4NO3的形式存在;后向轨迹分析表明降水主要受海洋风向影响,西北、西南方向和长江三角洲地区的人为污染物的中长尺度传输是造成崇明东滩酸雨的重要原因.     

Application of ion chromatography to the determination of water-soluble inorganic and organic ions in atmospheric aerosols

A simple, sensitive and convenient ion chromatography(IC) method was established for the simultaneous determination of twelve water-soluble inorganic anions(F^-, Cl^-, NO2^-, NO3^-, SO3^2-, SO4^2-, PO4^3- ), and fifteen water-soluble organic ions(formate, acetate, MSA, oxalate, malonate, succinate, phthalates, etc. ) in atmospheric aerosols. The linear concentrations ranged from 0.005 μg/m^3 to 500 μg/m^3 (r = 0.999--0.9999). The relative standard deviation(RSD) were 0.43%--2.00% and the detection limits were from 2.7 ng/m^3 to 88 ng/m^3. The proposed method was successfully applied to the simultaneous determination of those inorganic ions and organic ions in PM2.5 of Beijing.     

大气降水化学特征分析——以佛山市禅城区为例

为了解佛山市禅城区大气降水化学特征,该研究于2018年1~12月采集禅城区大气降水样品,测定降雨量、pH值、电导率和SO4^2?、NO3^?、NO^2?、F^?、Cl^?、Ca2^+、Mg2^+、K^+、Na^+和NH4^+等阴阳离子。结果表明,2018年佛山市禅城区降雨量为2058.6 mm,主要集中在5~9月份;pH值在3.95~6.47之间,年均值为5.35,pH值春、夏季较低,秋、冬季较高,酸雨频率为46.0%;电导率在3.51~100.40μS/cm之间,年均值为22.48μS/cm;降水离子浓度所占比例大小顺序为:NO3^?>SO4^2?>Cl^?>NH4^+>Ca2^+>NO2^?>K^+>Na^+>Mg2^+>F^?,其中NO3^?和SO4^2?是降水中主要的阴离子,NH4^+和Ca2^+是主要的阳离子,这4种离子占总离子的76.0%;除个别离子外,春季和冬季各离子浓度较秋季高,而夏季最低,阴阳离子之间存在着显著或极显著正相关关系。     

均相Co/PMS系统降解吡虫啉的影响因素及降解途径研究

过渡态Co^2+-催化分解KHSO₅(Co/PMS)系统是一种新型的高级氧化技术,其反应体系可以产生强氧化性的硫酸自由基(SO^·-₄).以杀虫剂吡虫啉为目标污染物,重点研究了溶液中PMS浓度、Co^2+-浓度和无机阴离子(H₂PO^-₄、HCO^-₃、NO^-₃和Cl^-)对Co/PMS系统降解吡虫啉的影响.结果表明,吡虫啉的降解遵循准一级动力学,其降解速率与氧化剂PMS浓度和催化剂Co^2+-的浓度呈正相关.吡虫啉的降解速率随着PMS和Co^2+-浓度的增加而增大,但是当PMS与吡虫啉的摩尔比大于20时,增加PMS的浓度对吡虫啉的降解速率反而有一定程度的抑制.H₂PO^-₄能促进Co/PMS系统对虫啉的降解;低浓度的HCO^-₃促进吡虫啉的降解,高浓度则为抑制作用;Cl^-抑制吡虫啉的降解,而NO^-₃则对整个降解过程影响不明显.研究中采用GC/MS分析吡虫啉降解的中间产物,得到了6-氯烟酸和6-氯烟酰胺2种主要的中间产物,并由此推测其可能的降解途径.     

Effects of common inorganic anions on the rates of photocatalytic degradation of sodium dodecylbenzenesulfonate over illuminated titanium dioxide

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