电场与MnxCey催化剂在苯氧化反应中的协同效应及机理探究

挥发性有机物（VOCs）大量排放已成为日益严重的环境问题,为了实现VOCs的高效去除,本文采用自蔓延燃烧合成法制备了一系列锰铈复合氧化物催化剂,将稳恒直流电场引入典型VOCs气体苯的催化氧化过程,并基于不同电场条件下催化剂的理化性质表征结果进行机理分析.实验结果表明,Mn_xCe_y催化剂对含苯废气的去除有良好的效果,稳恒直流电场显著促进了催化剂的活性,其中Mn₁Ce₃的催化性能最佳,电流为5 mA时,Mn₁Ce₃催化剂在155℃可达到50%的苯转化率,在202.4℃可达到90%的苯转化率,对应的转化温度T₅₀和T₉₀比传统方法分别降低了62.4℃和48.3℃,且电场中的反应活化能由52.32 kJ·mol^-1降低至32.31 kJ·mol^-1.根据实验现象及表征结果,发现协同效应与活性位点的快速持续再生及活性氧物种的转化有关,由此提出苯在Mn_xCe_y催化剂上的氧化机理及电场协同催化的反应模型.     

Preparation of hydrophobic hierarchical pore carbon–silica composite and its adsorption performance toward volatile organic compounds

Carbon–silica materials with hierarchical pores consisting of micropores and mesopores were prepared by introducing nanocarbon microspheres derived from biomass sugar into silica gel channels in a hydrothermal environment.The physicochemical properties of the materials were characterized by nitrogen physical adsorption(BET),scanning electron microscopy(SEM),and thermogravimetric(TG),and the adsorption properties of various organic waste gases were investigated.The results showed that microporous carbon materials were introduced successfully into the silica gel channels,thus showing the high adsorption capacity of activated carbon in high humidity organic waste gas,and the high stability and mechanical strength of the silica gel.The dynamic adsorption behavior confirmed that the carbon–silica material had excellent adsorption capacity for different volatile organic compounds(VOCs).Furthermore,the carbon–silica material exhibited excellent desorption characteristics:adsorbed toluene was completely desorbed at 150℃,thereby showing superior regeneration characteristics.Both features were attributed to the formation of hierarchical pores.     

Tuning the fill percentage in the hydrothermal synthesis process to increase catalyst performance for ozone decomposition

The performance of Ce-OMS-2 catalysts was improved by tuning the fill percentage in the hydrothermal synthesis process to increase the oxygen vacancy density. The Ce-OMS-2 samples were prepared with different fill percentages by means of a hydrothermal approach (i.e. 80%, 70%, 50% and 30%). Ce-OMS-2 with 80% fill percentage (Ce-OMS-2-80%) showed ozone conversion of 97%, and a lifetime experiment carried out for more than 20?days showed that the activity of the catalyst still remained satisfactorily high (91%). For Ce-OMS-2-80%, Mn ions in the framework as well as K ions in the tunnel sites were replaced by Ce⁴⁺, while for the others only Mn ions were replaced. O₂-TPD and H₂-TPR measurements proved that the Ce-OMS-2-80% catalyst possessed the greatest number of mobile surface oxygen species. XPS and XAFS showed that increasing the fill percentage can reduce the AOS of Mn and augment the amount of oxygen vacancies. The active sites, which accelerate the elimination of O₃, can be enriched by increasing the oxygen vacancies. These findings indicate that increasing ozone removal can be achieved by tuning the fill percentage in the hydrothermal synthesis process.     

Effects of SO2 and H2O on low-temperature NO conversion over F-V2O5-WO3/TiO2 catalysts

F-V_2 O_5-WO3/Ti02 catalysts were prepared by the impregnation method.As the content of F ions increased from 0.00 to 0.35 wt.%,the NO conversion of F-V_2 O_5-WO_3/TiO_2 catalysts initially increased and then decreased.The 0.2 F-V_2 O_5-WO_3/TiO_2 catalyst(0.2 wt.% F ion)exhibited the best denitration(De-NOx) performance,with more than 95% NO conversion in the temperature range 160-360℃,and 99.0% N2 selectivity between 110 and 280℃.The addition of an appropriate amount of F ions eroded the surface morphology of the catalyst and reduced its grain size,thus enhancing the NO conversion at low temperature as well as the sulfur and water resistance of the V_2 O_5-WO3/Ti02 catalyst.After selective catalytic reduction(SCR) reaction in a gas flow containing SO_2 and H_2 O,the number of NH3 adsorption sites,active component content,specific surface area and pore volume decreased to different degrees.Ammonium sulfate species deposited on the catalyst surface,which blocked part of the active sites and reduced the NO conversion performance of the catalyst.On-line thermal regeneration could not completely recover the catalyst activity,although it prolonged the cumulative life of the catalyst.In addition,a mechanism for the effects of S02 and H_2 O on catalyst NO conversion was proposed.     

An investigation of changes in water quality throughout the drinking water production/distribution chain using toxicological and fluorescence analyses

Changes in water quality from source water to finished water and tap water at two conventional drinking water treatment plants(DWTPs) were monitored.Beside the routine water quality testing,Caenorhabditis elegans-based toxicity assays and the fluorescence excitation–emission matrices technique were also applied.Both DWTPs supplied drinking water that met government standards.Under current test conditions,both the investigated finished water and tap water samples exhibited stronger lethal,genotoxic and reprotoxic potential than the relative source water sample,and the tap water sample was more lethal but tended to be less genotoxic than the corresponding finished water sample.Meanwhile,the nearly complete removal of tryptophan-like substances and newly generated tyrosine-like substances were observed after the treatment of drinking water,and humic-like substances were identified in the tap water.Based on these findings,toxic pollutants,including genotoxic/reproductive toxicants,are produced in the drinking water treatment and/or distribution processes.Moreover,further studies are needed to clarify the potentially important roles of tyrosine-like and humic-like substances in mediating drinking water toxicity and to identify the potential sources of these contaminants.Additionally,tryptophan-like fluorescence may be adopted as a useful parameter to monitor the treatment performance of DWTPs.Our observations provided insights into the importance of utilizing biotoxicity assays and fluorescence spectroscopy as tools to complement the routine evaluation of drinking water.     

Recent advances in catalytic decomposition of ozone

Ozone (O₃), as a harmful air pollutant, has been of wide concern. Safe, efficient, and economical O₃ removal methods urgently need to be developed. Catalytic decomposition is the most promising method for O₃ removal, especially at room temperature or even subzero temperatures. Great efforts have been made to develop high-efficiency catalysts for O₃ decomposition that can operate at low temperatures, high space velocity and high humidity. First, this review describes the general reaction mechanism of O₃ decomposition on noble metal and transition metal oxide catalysts. Then, progress on the O₃ decomposition performance of various catalysts in the past 30 years is summarized in detail. The main focus is the O₃ decomposition performance of manganese oxides, which are divided into supported manganese oxides and non-supported manganese oxides. Methods to improve the activity, stability, and humidity resistance of manganese oxide catalysts for O₃ decomposition are also summarized. The deactivation mechanisms of manganese oxides under dry and humid conditions are discussed. The O₃ decomposition performance of monolithic catalysts is also summarized from the perspective of industrial applications. Finally, the future development directions and prospects of O₃ catalytic decomposition technology are put forward.     

Effects of calcination temperature on physicochemical property and activity of CuSO4/TiO2 ammonia-selective catalytic reduction catalysts

CuSO_4/TiO_2 catalysts with high catalytic activity and excellent resistant to SO_2 and H_2 O,were thought to be promising catalysts used in Selective catalytic reduction of nitrogen oxides by NH_3.The performance of catalysts is largely affected by calcination temperature.Here,effects of calcination temperature on physicochemical property and catalytic activity of CuSO_4/TiO_2 catalysts were investigated in depth.Catalyst samples calcined at different temperatures were prepared first and then physicochemical properties of the catalyst were characterized by N2 adsorption-desorption,X-ray diffraction,thermogravimetric analysis,Raman spectra,Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,temperature-pro grammed desorption of NH_3,temperature-programmed reduction of H_2 and in situ diffuse reflectance infrared Fourier transform spectroscopy.Results revealed that high calcination temperature had three main effects on the catalyst.First,sintering and anatase transform into rutile with increase of calcination temperature,causing a decrement of specific surface area.Second,decomposition of CuSO_4 under higher calcination temperature,resulting in disappears of Br(?)nsted acid sites(S-OH),which had an adverse effect on surface acidity.Third,CuO from the decomposition of CuSO_4 changed surface reducibility of the catalyst and favored the process of NH_3 oxidation to nitrogen oxides(NO_x).Thus,catalytic activity of the catalyst calcined under high temperatures(≥600℃) decreased largely.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

达里诺尔湖水体DOM荧光特征及其来源解析

达里诺尔湖（简称“达里湖”）是内蒙古自治区高原地区重要的生态屏障,探究达里湖水质状况及污染来源,对加强流域水环境治理、改善水环境质量具有十分重要的意义.于2018年9月及2019年6月对湖水进行采样,并通过三维荧光光谱结合PARAFAC（平行因子分析）模型,探究达里湖水体DOM（溶解性有机质）来源及其与水质的关系.结果表明:①达里湖水体中pH较高,ρ（DOC）（DOC为溶解性有机碳）、ρ（NH₄+-N）、ρ（TP）相对较高,均超过GB 3838—2002《地表水环境质量标准》Ⅴ类水质标准限值.②水体中DOM含4种荧光组分.夏季水体DOM主要分布于河流入湖口附近,其中,类腐殖质荧光组分（紫外区类富里酸和可见区类富里酸）占总组分的62.93%,类蛋白类荧光组分（类色氨酸和类酪氨酸）占总组分的36.07%;秋季水体DOM主要分布于东南侧,其中,类腐殖质荧光组分占总组分的40.52%,类蛋白类荧光组分占总组分的59.48%.③达里湖采样点荧光参数表明,达里湖DOM自生源特征较强,腐殖化程度较低.类腐殖质荧光组分与ρ（DOC）、ρ（Chla）均呈正相关,类色氨酸荧光组分与pH呈正相关,类络氨酸与ρ（DTN）、ρ（NH4+-N）、ρ（DTP）均呈正相关.研究显示,达里湖DOM具有陆源与生物源双重特性,DOM的形成与微生物、细菌、浮游生物的生命活动密切相关.      

嘉兴地区农村生活污水时空分布及处理设施现状分析

研究选取嘉兴市下辖农村的160座生活污水处理设施进出水为研究对象,分析了区域农村生活污水污染物时空分布特征及其处理设施现状,以期提高处理设施效率。结果表明:嘉兴市农村生活污水中氮、磷污染较有机污染更严重,ρ（COD）、ρ（TP）、ρ（TN）、ρ（NH₄+-N）年均值分别为142.23,4.02,44.19,27.74 mg/L,各污水处理设施处理效果有很大优化空间,COD、TP、TN、NH₄+-N年均去除率分别为50.5%、29.7%、36.8%、51.7%。农村生活污水空间上呈自西向东、由北至南逐渐减小的分布特征,时间上表现为冬季 > 春季 > 秋季 > 夏季。相关性分析表明,COD、TP、TN、NH₄+-N之间呈极显著正相关（P<0.01）,相关系数为0.688±0.946。设施进水C/N、NH₄+-N/TN年均值分别为3.21、68.9%,传统的单一A2/O处理工艺对低碳源污水处理效果不理想,可通过组合工艺设计、规范运营管理、加强后期监测等有效措施来进一步加强污水处理设施处理效果。