漂浮型B、N共掺杂TiO_2光催化剂的制备及柴油降解性能

以膨胀珍珠岩为载体,采用溶胶-凝胶法制备硼、氮共掺杂漂浮型Ti O_2,采用XRD、BET、SEM、UV-vis DRS、XPS等分析手段进行材料表征并考察其对柴油的光降解性能.结果表明,B-N-Ti O_2/EP复合光催化剂表面有明显的Ti O_2覆层,晶型为锐钛矿型Ti O_2,Ti O_2负载有利于比表面积的提升.制得的B-N-Ti O_2/EP的可见光区响应高于N-Ti O_2/EP和Ti O_2/EP,该结果与3种材料的柴油光降解效果相一致.B-N-Ti O_2/EP对柴油的9h降解率将近50%,GC-MS分析表明,光降解过程中柴油各特征组分(C_9~C_(23))均得到不同程度降解,其中C_(11)以下的短链有机分子降解效果明显.     

CTMAB/TiO_2表面修饰膨胀珍珠岩制备及降解苯酚研究

用溴化十六烷基三甲铵(CTMAB)和/或TiO2对膨胀珍珠岩(EP)进行表面修饰,获得不同表面修饰膨胀珍珠岩(EP、TiO2-EP、CTMAB-EP和TiO2/CTMAB-EP)。并研究了其对水中苯酚的吸附降解动力学方程以及去除效果和影响因素。结果表明,膨胀珍珠岩对苯酚的吸附去除能力很小,CTMAB对其进行表面修饰后可小幅提高对苯酚的去除率,同时负载CTMAB和TiO2的膨胀珍珠岩对水中苯酚的去除率有很大提高;修复材料投加量、振荡时间、苯酚初始浓度和pH值等对苯酚的去除效果有较大影响;在溶液初始pH小于8时,TiO2对苯酚的光催化降解能力随pH增加而提高,强酸或强碱环境均不适合苯酚的光催化降解。在膨胀珍珠岩上同时负载CTMAB和TiO2可望成为一种高效去除环境中有机污染物的新型环境修复材料。     

CTMAB/TiO_2表面修饰膨胀珍珠岩光催化降解水中对硝基苯酚

用溴化十六烷基三甲铵(CTMAB)和/或TiO2对膨胀珍珠岩(EP)进行表面修饰,获得不同表面修饰膨胀珍珠岩(CTMAB-EP,TiO2/CTMAB-EP,TiO2-EP和EP),研究其对水中对硝基苯酚的去除效果、吸附降解动力学以及最适条件.结果表明:膨胀珍珠岩对对硝基苯酚的吸附去除能力很小,对其用CTMAB进行表面修饰或负载TiO2均可显著提高对硝基苯酚的去除率,同时负载CTMAB和TiO2的膨胀珍珠岩对对硝基苯酚的去除率最高;环境修复材料用量、振荡时间、初始ρ(对硝基苯酚)和pH等对去除效果有一定影响.膨胀珍珠岩上负载的TiO2对对硝基苯酚的光催化降解能力受pH的影响不大,表面活性剂CTMAB在pH为8时对对硝基苯酚的吸附能力较强,pH为8时修复材料对对硝基苯酚的去除效果最好.     

金属离子掺杂TiO_2薄膜光催化去除气相中甲醛

采用溶胶-凝胶法在普通玻璃表面制备TiO2,Fe3+/TiO2,La3+/TiO2三种光催化剂,研究了煅烧温度、煅烧时间、涂膜层数、Fe3+和La3+加入量等因素对光催化剂降解气相甲醛的影响。结果表明,La3+/TiO2光催化性能略好于TiO2,Fe3+/TiO2光催化性能最佳。当掺Fe3+的TiO2催化剂煅烧温度为450℃,煅烧时间为2h,Fe:T(imol)=0.3%,涂覆层数为4层,光催化反应3h,实验封闭体系中甲醛的降解率可达49.24%。     

碱热-酸热法合成二氧化钛-钛酸纳米管复合纳米材料对Cd(Ⅱ)和苯酚的同步去除

以P25型Ti O2为原料,经碱热和酸热反应合成了Ti O2/TNTs复合纳米材料,该材料皆具钛酸纳米管(TNTs)和Ti O2晶相.Cd(Ⅱ)在Ti O2/TNTs上的吸附动力学过程很快,30 min即可达到吸附平衡,此外,Langmuir等温模型拟合所得最大吸附量达120.34 mg·g-1,其主要吸附机制为Cd2+与复合材料中TNTs层间Na+/H+的离子交换.Ti O2/TNTs对苯酚的吸附量较低(0.36 mg·g-1),因此光催化反应以实现苯酚的降解是必需的.构建的吸附-光催化系统可实现Cd(Ⅱ)和苯酚的同步有效去除,180 min时二者的去除率分别可达到99.6%和99.7%.Cd(Ⅱ)的去除源于暗室下复合材料中TNTs相的吸附,而苯酚的去除在于后续复合材料中Ti O2相的光催化.Cd(Ⅱ)的共存可提高苯酚的光催化降解效率,原因在于Cd(Ⅱ)吸附进入材料层间后有助于材料光催化性能的提升.共存Na+对Cd(Ⅱ)和苯酚在Ti O2/TNTs上的同步去除影响极小;而共存Ca2+由于竞争吸附和促进材料团聚的原因,会轻微抑制Cd(Ⅱ)在Ti O2/TNTs上的吸附,但对苯酚的光催化降解影响较小.此外,Ti O2/TNTs可有效循环利用,经HNO3解吸和Na OH再生后,3次循环后材料对Cd(Ⅱ)和苯酚的去除率依然可达91.7%和98.1%.该研究提供了一种合成皆具吸附和光催化性能的钛系材料的方法,对于应用纳米材料实现水体环境中重金属和有机物的同时去除具有一定的借鉴意义.     

Ag、N共掺杂TiO2漂浮型催化剂的光催化性能

采用溶胶-凝胶法,制备出银氮共掺杂TiO_2负载膨胀珍珠岩的催化剂,通过电子显微镜扫描(SEM)、比表面积及孔径分析(BET)和X射线衍射(XRD)对其结构进行表征,并以罗丹明B溶液为目标降解物,研究所制备催化剂的光催化性能。结果表明:复合材料成功负载了Ag和N元素,且掺杂增强了TiO_2对可见光的响应能力;复合材料存在少量的微孔和大孔,同时存在大量的介孔;掺杂氮后材料的光催化活性大幅度提高,继续掺杂Ag后光催化活性进一步提高,当n(Ag)∶n(Ti)=0. 50%时光催化性能最佳,4 h内处理罗丹明B降解率可达99. 3%,材料的光催化反应符合一级反应动力学方程,表明其在环境净化实际应用中的巨大潜力。     

H2O2引发的UV/Fenton苯酚光催化降解

研究了H2O2引发光催化降解方法对废水中微量苯酚的去除效果,应用传感技术分析了降解过程中H2O2浓度变化,及其H2O2引发光催化降解苯酚的机理,考察了影响苯酚光催化降解的因素,确定了最佳降解试验条件为:H2O2 0.075~0.30mmol/L,Fe3+ 0.1~0.15mmol/L,pH值 4~5.在此条件下,苯酚初始浓度为50mg/L的含酚废水反应2h,苯酚降解率达到95%,矿化去除率达77%.     

Fe2O3/TiO2负载膨胀珍珠岩光催化降解罗丹明B

为获得高效催化活性的光催化材料,研究不同煅烧氛围对材料在可见光下催化性能的影响,以膨胀珍珠岩（EP）为载体,采用溶胶-凝胶法,在不同煅烧氛围（O₂和/或NH₃）下制备Fe₂O₃/TiO₂负载EP的光催化复合材料〔Fe₂O₃-TEP（O₂）、Fe₂O₃-TEP（NH₃）、Fe₂O₃-TEP（O₂,NH₃）、Fe₂O₃-TEP（NH₃,O₂）〕,采用EDS（X-射线色散能谱）、BET（比表面积及孔径分析）、XRD（X射线衍射）、SEM（扫描电子显微镜）、XPS（X射线光电子能谱）等对复合材料进行表征,并研究了其在可见光下对罗丹明B的光催化降解效果.结果表明:①复合材料成功负载了Ti、Fe元素,负载的TiO₂以锐钛矿型存在,Fe₂O₃的掺杂增强了TiO₂对可见光的响应能力;②不同的煅烧氛围明显影响复合材料的晶粒尺寸、比表面积和光催化性能,其中,Fe₂O₃-TEP（O₂,NH₃）的光催化性能最好,4 h后罗丹明B降解率达到87.59%,Fe₂O₃-TEP（NH₃,O₂）、Fe₂O₃-TEP（O₂）和Fe₂O₃-TEP（NH₃）4 h后对罗丹明B的降解率则分别为65.02%、62.48%和47.48%;③在试验条件下,复合材料的光催化反应符合一阶反应动力学方程,Fe₂O₃-TEP（O₂,NH₃）、Fe₂O₃-TEP（NH₃,O₂）、Fe₂O₃-TEP（O₂）和Fe₂O₃-TEP（NH₃）相应的降解速率常数分别为0.008 3、0.004 3、0.004 3和0.002 7 min-1.研究显示,通过溶胶-凝胶法所制备的复合材料（Fe₂O₃-TEP）经煅烧后所得矿相均一;Fe₂O₃掺杂TiO₂可形成Ti—O—Fe键,减小TiO₂固有的禁带宽度;复合材料光催化性能也受到煅烧氛围的影响,先O₂后NH₃煅烧条件下所得材料的光催化性能最佳.      

光催化与Fenton试剂对硝基苯酚降解的研究

文章对光催化/Fenton试剂联合降解硝基苯酚模拟废水进行了研究。探讨了硝基苯酚溶液的初始浓度、pH、亚铁离子浓度、双氧水浓度、催化剂量等对对硝基苯酚降解效果影响。结果表明,对于200mL,浓度为100mg/L的硝基苯酚溶液,当加入Fe2+为20mg/L,5mmol/LH2O2,催化剂TiO2为0.6g/L,紫外灯功率为250W且反应40min后,对硝基苯酚的降解率达到约100%。通过对比试验,发现光催化和Fenton试剂对对硝基苯酚的降解起协同作用,并通过GC/MS技术测定中间产物并给出了可能的降解途径。     

类Fenton催化剂处理苯酚废水的研究

以MIL-101为载体,采用浸渍法制备Fe-Cu/MIL-101类Fenton催化剂,并采用X射线衍射和电子扫描电镜对催化剂进行表征。考察了进水p H、Fe/Cu摩尔比、H_2O_2浓度及催化剂投加量对催化剂性能的影响。结果表明,制备的Fe-Cu/MIL-101保持了MIL-101的骨架结构,且具有较大的比表面积,催化剂在参与反应的同时发挥了MIL-101材料的吸附作用;H_2O_2+Cu/MIL-101体系中的Cu2+不能有效分解H_2O_2生成·OH自由基,但Cu~(2+)能大大提高H_2O_2+Fe-Cu/MIL-101体系降解苯酚的速率;非均相Fe-Cu/MIL-101催化剂拓宽了Fenton反应的p H范围,在室温的条件下,p H为2～5、苯酚初始浓度100 mg/L、催化剂加入量0.5 g/L、H_2O_2浓度4.38 mmol/L,苯酚的去除率接近100%;分析降解后废水表明,Fe-Cu/MIL-101类Fenton催化剂可能将苯酚降解为烯烃、羧酸等有机物中间体。     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Oxidation of As(Ⅲ) by potassium permanganate

The oxidation of As(Ⅲ) with potassium permanganate was studied under conditions including pH, initial As(Ⅲ) concentration and dosage of Mn(Ⅶ). The results have shown that potassium permanganate was an effective agent for oxidizing of As(Ⅲ) in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As(Ⅲ) by Mn(Ⅶ). Although theoretical redox analyses suggest that Mn(Ⅶ) should have better performance in oxidization of As(Ⅲ) within lower pH ranges, the experimental results show that the oxidation efficiencies of As(Ⅲ) under basic and acidic conditions were similar, which may be due to the adsorption of As(Ⅲ) on the Mn(OH)2 and MnO2 resulting from the oxidation of As(Ⅲ).     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Chlorobenzenes in waterweeds from the Xijiang River （Guangdong section） of the Pearl River

The Xijiang River is the major source of water for about 4.5 millions of urban population and 28.7 millions of rural population. The water quality is very important for the health of the rural population. The concentration and distribution of chlorobenzenes (CBs) in both water and waterweeds collected from 4 stations in the Xijiang River (Gangdong section) of the Pearl River in April and November were determined. The result showed that nearly every congener of CBs was detected. The total contents of CBs (∑CBs) in the river water ranged from 111.1 to 360.0 ng/L in April and from 151.9 to 481.7 ng/L in November, respectively. The pollution level of CBs in the water in April was higher than that in November. The contents of ∑ CBs in waterweeds ranged from 13.53×102 μg/g to 38.27×102μg/g dry weight (dw). There was no significant difference between April and November in waterweeds. The distribution of CBs in roots, caulis, and leaves of Vallisneria spiralis L. showed different patterns. The leaves mainly contained low-molecular-weight CBs(DCBs), whereas the roots accumulated more PCBs and HCBs. The average lgBCFlip (bioconcentration factor) of CBs ranged from 0.64 to 3.57 in the waterweeds. The spatial distribution character of CBs in the Xijiang River was: Fengkai County ＜ Yunan County ＜Yun'an County ＜ Gaoyao County according to the ∑CBs, and the pollution deteriorated from the upstream to the downstream of the Xijiang River. Further analysis demonstrated that the discharge of waste containing CBs may be the main source of CBs pollution in the Xijiang River.     

Degradation of 2,4-dichlorophenol with a novel TiO2/Ti-Fe-graphite felt photoelectrocatalytic oxidation process

Degradation of 2,4-dichlorophenol(2,4-DCP)was studied in a novel three-electrode photoelectrocatalytic(PEC)integrative oxidation process,and the factors influencing the degradation rate,such as applied current,flow speed of O_2,pH,adscititious voltage and initial 2,4-DCP concentration were investigated and optimized.H_2O_2 was produced nearby cathode and Fe~(2 )continuously generated from Fe anode in solution when current and O_2 were applied,so,main reactions,H_2O_2-assisted TiO_2 PEC oxidation and E-Fenton reaction,occurred during degradation of 2,4-DCP in this integrative system.The degradation ratio of 2,4-DCP was 93% in this integrative oxidation process,while it was only 31% in E-Fenton process and 46% in H_2O_2-assisted TiO_2 PEC process.So,it revealed that the degradation of 2,4-DCP was improved greatly by photoelectrical cooperation effect.By the investigation of pH,it showed that this integrative process could work well in a wide pH range from pH 3 to pH 9.     

Effect of copper on the degradation of pesticides cypermethrin and cyhalothrin

The influence of coexisting copper (Cu) ion on the degradation of pesticides pyrethroid cypermethrin and cyhalothrin in soil and photodegradation in water system were studied.Serial concentrations of the pesticides with the addition of copper ion were spiked in the soil and incubated for a regular period of time,the analysis of the extracts from the soil was carried out using gas chromatography (GC).The photodegradation of pyrethroids in water system was conducted under UV irradiation.The effect of Cu~(2 ) on the pesticides degradation was measured with half life (t_(0.5)) of degradation.It was found that a negative correlation between the degradation of the pyrethroid pesticides in soil and Cu addition was observed.But Cu~(2 ) could accelerate photodegradation of the pyrethroids in water.The t_(0.5) for cyhalothrin extended from 6.7 to 6.8 d while for cypermethrin extended from 8.1 to 10.9 d with the presence of copper ion in soil.As for photodegradation,t_(0.5) for cyhalothrin reduced from 173.3 to 115.5 rain and for cypermethrin from 115.5 to 99.0 min.The results suggested that copper influenced the degradation of the pesticides in soil by affecting the activity of microorganisms.However, it had catalyst tendency for photodegradation in water system.The difference for the degradation efficiency of pyrethroid isomers in soil was also observed.Copper could obviously accelerate the degradation of some special isomers.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.