Structural effect on photocatalytic degradation of metallised azo dyes in aqueous TiO2 suspension

Three metallised azo dyes were investigated under TiO₂‐photocatalytic and photosensitised conditions in aqueous buffering solutions. The degradation follows apparent first‐order kinetics. The size and strength of intramolecular conjugation determine the light‐fastness of the investigated dyes. Compared with ¹O₂ produced in photosensitised process, the more powerful *OH radicals in TiCO₂ photocatalytic process are highly reactive towards the investigated azo dyes. And as a result, the TiO₂‐photocatalysis makes little less distinction in the degradation kinetic data of the azo dyes compared with the photosensitised degradation of them.     

纳米TiO2光催化降解有机磷农药的研究

通过实验,探讨了用纳米TiO2光催化处理有机磷农药模拟废水和实际应用的有机磷农药的可行性.实验表明,以测定不同时间PO43-的浓度来衡量有机磷的降解率,并以此来衡量有机磷农药及其中间产物降解的程度是合理的.光催化降解甲胺磷和水胺硫磷的结果,显示了有机磷农药的降解率与其结构有关.实际应用的有机磷农药也可用光催化降解.     

二氧化钛/石墨烯复合光催化剂的制备及其对水中双酚A的降解

双酚A污染问题日益严峻,已经威胁到人类的健康.半导体光催化技术可以有效去除水体中双酚A污染.近年来,二氧化钛/石墨烯复合材料,因其优越的光催化性能受到广泛关注.尤其石墨烯等新型纳米碳基材料,有较大的比表面积和丰富的官能团,为二氧化钛的负载创造了良好的条件,其表面可以形成化学键,为双酚A的吸附降解提供了更多的活性位点.本文重点介绍了国内外二氧化钛/石墨烯复合材料的制备方法及各种制备方法的优缺点;讨论了二氧化钛/石墨烯复合材料对双酚A的降解效果及其降解机理;分析了二氧化钛/石墨烯复合材料的再生性能.最后总结这种材料在实际应用中存在的问题及其前景展望.     

Photocatalytic degradation of aqueous methyl-tert-butyl-ether (MTBE) in a supported-catalyst reactor

Contamination of groundwater by methyl-tert-butyl ether (MTBE) poses increasing problems to water companies. Here we demonstrate the feasibility of using a cylindrical, supported-catalyst reactor for photocatalytic degradation of MTBE in water. It was shown that photocatalytic degradation of MTBE follows pseudo first-order kinetics. The maximum reaction rate constant observed was 0.47 hr^–1. The reaction rate increases linearly with increasing light intensity. It was also found that the reaction rate is linearly proportional to the ratio of catalyst surface area to volume of reactor. Complete degradation of MTBE was reached with an excess supply of oxygen.     

TiO2 photocatalyzed degradation of diazinon in an aqueous medium

The photocatalytic degradation of diazinon was studied over TiO₂ catalysts. The kinetics obtained demonstrated that powder titania (t_1/2 = 9.7 min) was more efficient compared to pure titania thin film catalysts (t_1/2 = 29.4 min). Mineralization of organic carbon to CO₂ after 360 min of irradiation was found to be 75% while heteroatoms (P, S, N) were mineralized into phosphate, sulfate and nitrate ions, respectively. A microtox test was performed to evaluate the toxicity of solutions treated by catalysts. Illumination of diazinon in the presence of TiO₂ gave rise to several intermediates that have been identified by means of solid phase extraction and gas chromatography-mass spectrometry, while a simple degradation pathway is proposed.     

光催化降解对抗生素藻类毒性效应影响研究进展

抗生素滥用带来环境中残留抗生素及其抗性基因的问题,近年来已成为全球关注的热点问题.光催化氧化技术是当前研究领域广泛采用的有效降解水环境中残留抗生素的热门方法;但光催化氧化无法使水环境中抗生素完全矿化,存在生态风险,探明光催化降解抗生素对其藻类毒理效应影响及内在机制,对研发高效、安全的光催化技术具有重要意义.本文在总结水...     

MoO3/TiO2纳米管的制备及其光催化降解多环芳烃的机制

本研究将热分解法制备的MoO_3与水热法制备的TiO_2纳米管复合,得到具有高太阳光催化活性的MoO_3/TiO_2纳米管异质结催化剂.研究中以芘为模型多环芳烃(polycyclic aromatic hydrocarbons,PAHs),探究了MoO_3/TiO_2纳米管模拟在太阳光下催化降解PAHs的效果及效率提升的机制.结果表明,MoO_3和TiO_2纳米管间形成的p-n异质结结构,降低了材料的能带间隙而获得更高的可见光利用效率,并有效促进了电子和空穴的分离,从而提高了复合材料的光催化活性.1%MoO_3/TiO_2纳米管催化降解芘速率(k)较MoO_3和TiO_2(锐钛矿)分别提升了5.3倍和1.5倍.催化体系中产生的·OH和光生空穴在芘的降解中起主要作用.     

新型双槽光电化学反应器对活性艳红的降解研究

用热氧化法制备了TiO2/Ti薄膜电极,并用XRD和AFM对TiO2/Ti薄膜电极的晶形和表面形貌进行了表征。结果表明：热氧化法制备的TiO2主要为锐钛型纳米颗粒,直径在40 nm左右。设计了一种新型双槽光电化学反应器,用于废水的处理。以热氧化法制备的TiO2/Ti薄膜电极为阳极进行光电催化反应,同时以石墨电极为阴极用于产生双氧水,并与紫外光组成UV/H2O2体系。考察了双槽反应器中活性艳红X-3B在不同条件下的降解效果。降解结果表明：在新型反应器的阴阳两极槽中,活性艳红不仅在TiO2/Ti阳极槽中被降解,而且在石墨阴极槽中也得到降解;活性艳红在酸性条件下的降解效果最好;相对于单纯的电化学氧化和光催化,光电化学协同作用对X-3B的降解效果最好。     

Mechanistic insights into the selective photocatalytic degradation of dyes over TiO2/ZSM-11

● TiO₂/ZSM-11 was prepared by a facile solid state dispersion method. ● Mechanism for photocatalytic degradation of dyes was investigated. ● Both experimental and MD simulations were conducted. ● Chemisorption instead of electrostatic interaction played a critical role. Photocatalytic degradation is a promising way to eliminate dye contaminants. In this work, a series of TiO₂/ZSM-11 (TZ) nanocomposites were prepared using a facile solid state dispersion method. Methyl orange (MO), methylene blue (MB), and rhodamine B (RhB) were intentionally chosen as target substrates in the photocatalytic degradation reactions. Compared to pristine TiO₂, negative effect was observed on MO degradation while promoted kinetics were collected on MB and RhB over TZ composites. Moreover, a much higher photocatalytic rate was interestingly achieved on RhB than MB, which indicated that a new factor has to be included other than the widely accepted electrostatic interaction mechanism to fully understand the selective photodegradation reactions. Systematic characterizations showed that TiO₂ and ZSM-11 physically mixed and maintained both the whole framework and local structure without chemical interaction. The different trends observed in surface area and the photo-absorption ability of TZ composites with reaction performance further excluded both as the promotion mechanism. Instead, adsorption energies predicted by molecular dynamics simulations suggested that differences in the adsorption strength played a critical role. This work provided a deep mechanistic understanding of the selective photocatalytic degradation of dyes reactions, which helps to rationally design highly efficient photocatalysts.     

Effect of titanium dioxide nanoparticles on the expression of apoptotic markers in mouse blastocysts

Oocyte maturation, embryo development and expression of apoptotic-specific genes were evaluated in blastocysts of mice treated with titanium dioxide nanoparticles. Female mice received 0, 50 or 100?mg/kg/day titanium dioxide intraperitoneally for five consecutive days. After the last injection, pregnant mare serum gonadotropin and, 48?h later, human chorionic gonadotropin were administered intraperitoneally for induction of ovulation. After 14?h, mice were sacrificed and oocytes were collected. The number of mature oocytes was evaluated and then fertilization was carried out in vitro and the numbers of fertilized and cleaved oocytes and of blastocysts and the expression of Bax, caspase 3, and Bcl-xL genes in blastocysts were evaluated. The number of mature, fertilized and cleaved oocytes and of blastocyst embryos in the experimental groups were not different from control. The expression of Bax and caspase 3 genes was significantly elevated in the experimental groups compared to control, while expression of the Bcl-xL gene was significantly lower in the high dose group. Uptake of titanium dioxide nanoparticles at daily doses of 50?mg/kg and more may affect embryo development by alteration of pro-apoptotic and anti-apoptotic gene expression.     

Effect of iron speciation on the photodegradation of Monuron in combined photocatalytic systems with immobilized or suspended TiO2

Photodegradation kinetics of Monuron (3-(4-chlorophenyl)-1,1-dimethylurea) in photoreactor with immobilized and suspended TiO₂ photocatalyst were studied. The effect of addition of ferric or ferrous perchlorate was investigated. Whatever the concentration of Fe(III/II) added there is no significant negative effect on the photodegradation rate of pollutants. On the contrary, depending on speciation and concentration of iron salts, slight or marked acceleration of the photodegradation kinetics was observed. This positive influence was more pronounced in the case of TiO₂ suspensions than for TiO₂ layers. Fe(III) was generally more effective than Fe(II).     

不同活性物种对光催化降解水中邻苯二甲酸二甲酯动力学的贡献研究

采用光催化氧化技术对邻苯二甲酸二甲酯（DMP）进行降解研究,并在基础上考察了催化剂量,溶液pH和溶液初始浓度对降解速率的影响。且采用Langmuir-Hinshelwood动力学模型来描述DMP的光催化降解,研究表明DMP的光催化降解符合假一级动力学。系统研究了光催化降解DMP过程中不同活性物种对光催化反应速率的贡献,实验结果表明：在TiO2光催化降解DMP的过程中,？OH为主要的活性物种,其对DMP的降解速率贡献高于94%,而其它活性物种（ecb-,hvb＋,O2？-和H2O2）对光催化贡献较小。     

氯化消毒过程对抗生素的降解行为及其毒性效应的影响研究进展

抗生素的大量使用导致其通过各种途径进入到污水处理厂、地表水甚至饮用水源水中.在污水处理厂二级出水排放之前以及自来水的生产和供应过程中,都必须进行氯化消毒处理以杀灭病原微生物.在此过程中,抗生素一方面可能被氯化降解,另一方面也可能转化成毒性更高的降解产物.因此,了解抗生素在氯化消毒过程中的降解行为对于明确其生态和健康风险...     

球磨零价镁/石墨(ZVMg/C)降解水中三氯乙烯

利用机械球磨法制备了零价镁/石墨(ZVMg/C)材料,并将其用于水溶液中三氯乙烯(TCE)的降解.研究通过SEM、BET和XRD等分析手段解析了ZVMg/C的表面形态结构和成分组成;采用正交实验方法优化了ZVMg/C的制备参数,比较了石墨含量对材料性能的影响;并考察了ZVMg/C投加量、溶液初始pH和地下水中常见阴(C...     

Effect of TiO2 nanoparticles and multiwall carbon nanotubes on the freshwater diatom Nitzschia frustulum: evaluation of growth,cellular components and morphology

Great attention should be paid to the possible impacts of various nanoparticles on aquatic organism. Freshwater diatoms are essential components of phytoplankton and play a critical role in bioassessment of nanoparticle exposure in the environment. In this study, cell growth was inhibited by TiO₂-NPs and MWCNTs, the 24?h EC₅₀ values of TiO₂-NPs and MWCNTs to Nitzschia frustulum were 20.75 and 24.64?mg?L^?1, respectively. Significant decreases of Chl a content after TiO₂-NPs exposures were detected and the Chl a content of N. frustulum was obviously increased by MWCNTs treatment at lower concentration. The ROS was detected in N. frustulum after TiO₂-NPs and MWCNTs exposures. The MDA content was significantly induced by TiO₂-NPs at lower concentrations of 24 and 48?h exposure; meanwhile, it increased at all tested concentrations at 24?h MWCNTs exposure. The SOD enzyme was induced by 72 and 96?h TiO₂-NPs exposure, and increased by MWCNTs treatment at 96?h in N. frustulum. Scanning electron microscopy results revealed that N. frustulum had obvious cell deformation after TiO₂-NPs treatment. The result showed that the physiological and biochemical response mechanisms after NPs exposure of diatom were species-specific, and in relation to the exposure concentration and time.     

阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）对磷钨酸(PW12)光催化还原降解偶氮染料直接耐晒黑G的影响

以磷钨酸H3PW12O4（PW12）为光催化剂,异丙醇（IS）作为电子给体,研究阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）对PW12光催化还原降解直接耐晒黑G（DB19）的影响.考察了CTAB浓度、pH值、DB19初始浓度等因素对反应的影响,并采用一级反应动力学对反应过程进行分析.结果表明CTAB增强了PW12对直接耐晒黑G的还原脱色作用,CTAB浓度增加,DB19的光催化脱色速率提高.PW12用量对DB19还原脱色的影响程度和趋势与溶液中CTAB浓度有关,当CTAB浓度为0.10 mmol.L-1时,DB19的脱色速率随PW12用量的增加而增加;CTAB浓度为0.05 mmol.L-1,PW12用量为200 mg.L-1时DB19的脱色速率最快,继续增加反而降低.DB19还原脱色速率随其初始浓度升高而降低.另外,通过循环伏安法和暗反应明确还原态杂多蓝对染料的还原脱色作用,并借助UV-Vis光谱研究DB19、PW12、CTAB之间的相互作用,探索CTAB对PW12/IS光催化还原降解DB19的作用机理.该研究结果表明阳离子表面活性剂CTAB能够增强偶氮染料废水的PW12催化还原脱色处理.     

Effect of two TiO2 nanoparticles on the growth of unicellular green algae using the OECD 201 test guideline: influence of the exposure system

This work aimed at assessing the influence of different exposure systems to perform the commonly used OECD 201 freshwater algal growth inhibition test in the context of nanoparticles hazard assessment. Two distinct TiO₂ nanoparticles were considered and three different exposure systems were investigated: Erlenmeyers flasks and 24-well microplates (both using an orbital shake system), and an alternative system using cylindrical vials and magnetic stirring. All three systems are in accordance with the OECD 201 test guideline recommendations. We concluded that the exposure systems applied to achieve the test can substantially affect the ecotoxicological results and the subsequent calculated ECx. The selected systems influenced both the interaction between algal cells and TiO₂ nanoparticles as well as the growth inhibition recorded. Disparities in ecotoxicity relative to the TiO₂ nanoparticles tested were also observed and are finally discussed.     

Investigation of the effects of humic acid and H 2 O 2 on the photocatalytic degradation of atrazine assisted by microwave

A solution of atrazine in a TiO₂ suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s⁻¹, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H₂O₂ displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.     

Effect of humic acids on the Fenton degradation of phenol

We show that the degradation of phenol by Fe(III) and hydrogen peroxide is faster in the presence of humic acids. This is most likely due to faster reduction of Fe(III)-humate complexes by H₂O₂/HO₂^·/O₂^–· when compared with Fe(III)-H₂O complexes. The fact that humic acids, a major class of naturally occurring compounds, favour the Fenton reaction has great relevance in the field of water and soil decontamination, where organic compounds usually have a negative effect. Furthermore, it adds insight into the self-depuration processes of natural aquifers.     

异丙隆在土壤和小麦中的降解与残留

在扬州和聊城两地进行了除草剂异丙隆在小麦上和麦田土壤中的残留动态和最终残留量试验，结果表明，异丙隆在小麦植株和土壤中消解较快，消解半衰期分别为３～４ｄ和８～１４ｄ；收获时小麦籽粒中异丙隆残留量小于０．０４ｍｇ／ｋｇ。推荐暂定异丙隆在小麦上ＭＲＩＬ值为０．５ｍｇ／ｋｇ。２５％异丙隆可湿性粉剂，按７．５ｋｇ／ｈｍ￣２用量，在次年早春（２月）使用，籽粒中异丙隆最终残留量不会超过ＭＲＬ值，对小麦是安全的。