TiO2光催化降解低浓度溴氰菊酯

用高压汞灯为光源,以二氧化钛光催化降解有机溴杀虫剂－溴氰菊酯,研究了ＴｉＯ２用量、ＰＨ值、等对降解的影响及采用太阳光做光源处理溴氰菊酯的可行性。说明以高压汞灯及太阳光作光源,ＴｉＯ２催化降解敌杀死是有效的。     

可见光下 H2La2Ti3O10/TiO2光催化降解有机染料的研究

通过固相反应、离子交换、粒子插入等一系列反应合成一种层状纳米光催化复合材料H2La2Ti3O10/TiO2.可见光照射下,对选定的染料模型--甲基橙溶液(20 mg/L)、汽巴克隆黄(100mg/L)、依利尼尔红(100 mg/L)溶液做光降解实验.结果表明,在可见光照射下,H2La2Ti3O10/TiO2均能对溶液中甲基橙、汽巴克隆黄、依利尼尔红有效降解,光照30min后,其对溶液中甲基橙、汽巴克隆黄、依利尼尔红的降解率分别可达60.4%、60.7%和72.0%,而标准TiO2(P-25)仅为6.2%、10.6%和12.3%.     

Fe/TiO2光催化降解水溶液中的4-氯苯酚

以TiO2-P25及FeC2O4为前驱物制备了Fe3 掺杂TiO2光催化剂--Fe/TiO2.X射线衍射结果表明,500 ℃煅烧温度下的Fe/TiO2主要是锐态矿晶型,当掺Fe3 量为0.5%(质量分数,下同)时,Fe3 以取代掺杂形式进入TiO2晶格,而当掺Fe3 量达5.0%时,则出现α-Fe2O3的特征衍射峰;900 ℃煅烧温度下的Fe/TiO2则均为金红石晶型,掺Fe3 量达2.0%～5.0%时,出现Fe2TiO5的特征衍射峰.4-氯苯酚的光催化实验结果表明,煅烧温度及Fe3 掺杂量对Fe/TiO2的光催化活性有显著影响,以煅烧温度500 ℃及掺Fe3 量0.5%的Fe/TiO2为光催化剂,反应80 min,4-氯苯酚的降解率达100%,总有机碳去除率约95%.     

TiO2/GeO2复合膜光催化氧化降解农药废水的研究

提出了一种新的TiO2/GeO2复合膜圆形光催化氧化反应器,研究了该反应器对经物化处理后的农药废水进行降解的过程。研究表明,光催化氧化的最佳条件是锌片镀TiO2/GeO2复合膜、pH=6.7、过氧化氢（H2O2）浓度为400 mg/L。并对其他氧化剂对该过程的影响进行了探讨。有机废水通过该反应器处理后,其COD值降为57mg/L。能使有机污染物全部降解为小分子无机物,废水达到国家一级排放标准。     

可见光下H2La2Ti3O10／TiO2光催化降解有机染料的研究

通过固相反应、离子交换、粒子插入等一系列反应合成一种层状纳米光催化复合材料H2La2Ti3O10／TiO2。可见光照射下，对选定的染料模型——甲基橙溶液(20mg／L)、汽巴克隆黄(100mg／L)、依利尼尔红(100mg／L)溶液做光降解实验。结果表明，在可见光照射下，H2La2Ti3O10／TiO2均能对溶液中甲基橙、汽巴克隆黄、依利尼尔红有效降解，光照30min后，其对溶液中甲基橙、汽巴克隆黄、依利尼尔红的降解率分别可达60．4％、60．7％和72．0％，而标准TiO2(P-25)仅为6．2％、10．6％和12．3％。     

TiO2/SiO2/γ-Fe2O3的表征及其光催化降解染料废水

以γ-Fe2O3为磁性核心,通过溶胶-凝胶法制备出三层结构的复合光催化剂TiO2/SiO2/γ-Fe2O3.通过X射线衍射、扫描电镜、透射电镜、振动样品磁强计和紫外-可见分光光谱分析进行表征.SiO2包覆膜可以减弱内层γ-Fe2O3对光催化效果的不利影响,有效地阻隔高温时γ-Fe2O3磁核与TiO2之间的熔结.以亚甲基...     

负载型纳米TiO2光催化降解水中微量溶解性间二甲苯

以高压汞灯为光源，采用浸涂-烧结法制备的负载型纳米TiO2作为光催化剂，通过对水中微量溶解性间二甲苯的光催化氧化过程的研究表明，初始浓度在6.68-17.36mg/L的范围内，间二甲苯的光催化反应遵循表观一级反应动力学规律。反应的表观速率常数随溶液初始浓度的增大而减小，半衰期则随初始浓度的增大而增加，经1.5h反应后，溶液中间二甲苯的去除率从17.36mg/L的54.44%增加到6.68mg/L的75.90%。     

3种染料化合物在UV-TiO2/H2O2和UV-TiO2体系中的光催化降解研究

采用自制的TiO2膜和平板式固定床型光催化氧化反应装置,对甲基橙、茜素红和罗丹明B 3种含有不同生色基团的染料化合物进行了TiO2光催化氧化降解研究,通过对照测定降解过程中吸光度、电导率、pH的变化,分析了在加入和不加入H2O22种情况下降解过程的异同,比较了3种染料化合物脱色的难易程度,揭示了降解产物中无机离子的变化规律及某些可能的产物类型.     

H4SiW12O40/TiO2/beads光催化降解亚甲基蓝的研究

以钛酸四丁酯为原料,空心微珠为载体,采用溶胶-凝胶法制备TiO2/beads光催化剂载体,然后浸渍法制备出H4SiW12O40/TiO2/beads表面负载修饰型复合光催化剂,并运用SEM、XRD、FT-IR和DRS对催化剂进行表征和分析。研究了H4SiW12O40/TiO2/beads对亚甲基蓝降解的光催化活性,考察了光强度、pH值、曝气量、底物浓度和催化剂用量等对催化效率的影响。实验结果表明,在中性条件下,H4SiW12O40/TiO2/beads催化剂的投加量为0.25 g/L,浓度为7.5 mg/L的亚甲基蓝溶液在250 W的紫外灯和600 W的可见光灯下光照60 min降解率分别可达到94.5%和55%。     

TiO2/H2O2/UV和TiO2/O3/UV降解对氯苯甲酸和喹啉的试验研究

主要叙述TiO2/H2O2/UV和TiO2/O3/UV体系降解对氯苯甲酸(4-CBA)和喹啉的试验研究.研究表明,(1)在TiO2/H2O2/UV体系里目标物降解速度先随过氧化氢投加量的增加而提高,但超过一定浓度之后便开始下降;(2)在TiO2/O3/UV体系中,目标降解物的反应速度都非常快,且臭氧浓度高的时候降解速度更快;(3)二氧化钛催化剂在TiO2/O3/UV体系中作为积极因素有助于提高反应速率,而在TiO2/H2O2/UV体系是消极因素,会降低反应速率.     

Reaction pathways of dimethyl phthalate degradation in TiO2-UV-O2 and TiO2-UV-Fe(VI) systems

The photocatalytic degradation of dimethyl phthalate (DMP) in aqueous TiO₂ suspension under UV illumination has been investigated using oxygen (O₂) and ferrate (Fe(VI)) as electron acceptors. The experiments demonstrated that Fe(VI) was a more effective electron acceptor than O₂ for scavenging the conduction band electrons from the surface of the catalyst. Some major intermediate products from DMP degradation were identified by HPLC and GC/MS analyses. The analytical results identified dimethyl 3-hydroxyphthalate and dimethyl 2-hydroxyphthalate as the two main intermediate products from the DMP degradation in the TiO₂–UV–O₂ system, while in contrast phthalic acid was found to be the main intermediate product in the TiO₂–UV–Fe(VI) system. These findings indicate that DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) systems followed different reaction pathways. An electron spin resonance analysis confirmed that hydroxyl radicals existed in the TiO₂–UV–O₂ reaction system and an unknown radical species (most likely an iron–oxo species) is suspected to exist in the TiO₂–UV–Fe(VI) reaction system. Two pathway schemes of DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) reaction systems are proposed. It is believed that the radicals formed in the TiO₂–UV–O₂ reaction system preferably attack the aromatic ring of the DMP, while in contrast the radicals formed in the TiO₂–UV–Fe(VI) reaction systems attack the alkyl chain of DMP.     

TiO2光催化降解水中苯酚的试验研究

以悬浆态TiO2为光催化剂，在紫外光催化反应器中，进行了苯酚溶液的动态光催化降解性能的研究，考察了TiO2用量、TiO2焙烧温度、溶液pH值以及循环流量对苯酚光催化降解的影响。结果表明，TiO2用量1．0g／L，TiO2焙烧温度450℃，循环流量20L／h，紫外光照反应5h，苯酚去除率为71．2％。     

亚甲基蓝溶液的光催化脱色及降解

以高压汞灯为光源,在自ＴｉＯ２纳米粉末悬浮体系内,以在蓝溶液光催化降解脱色反应为模型,研究了其脱色降解动力学及其影响因素。研究表明,亚甲基蓝光催化反应动力学常数为４．５３μｍｏｌ／Ｌ．ｍｉｎ．吸附常数为３３．５５Ｌ／ｍｍｏｌ;随着ｐＨ值的上升以及Ｈ２Ｏ２的加入,其脱色降解速率加快。     

Photocatalytic degradation with immobilised TiO(2) of three selected neonicotinoid insecticides: imidacloprid, thiamethoxam and clothianidin

This research focused on photocatalytic degradation of imidacloprid, thiamethoxam and clothianidin employing a tailor-made photoreactor with six polychromatic fluorescent UVA (broad maximum at 355 nm) lamps and immobilised titanium dioxide (TiO₂) on glass slides. The disappearance was followed by high pressure liquid chromatography (HPLC-DAD) analyses, wherein the efficiency of mineralization was monitored by measurements of total organic carbon (TOC). Within 2 h of photocatalysis, all three neonicotinoids were degraded following first order kinetics with rate constants k = 0.035 ± 0.001 min⁻¹ for imidacloprid, k = 0.019 ± 0.001 min⁻¹ for thiamethoxam and k = 0.021 ± 0.000 min⁻¹ for clothianidin. However, the rate of mineralization was low, i.e. 19.1 ± 0.2% for imidacloprid, 14.4 ± 2.9% for thiamethoxam and 14.1 ± 0.4% for clothianidin. This indicates that several transformation products were formed instead. Some of them were observed within HPLC-DAD analyses and structures were proposed according to the liquid chromatography-electro spray ionization tandem mass spectrometry analyses (LC-ESI-MS/MS). The formation of clothianidin, as thiamethoxam transformation product, was reported for the first time.     

Photocatalytic degradation of the fungicide Fenhexamid in aqueous TiO(2) suspensions: identification of intermediates products and reaction pathways

Liquid-chromatography interfaced with time-of-flight mass spectrometry (LC-TOF/MS) was used to separate and characterize the transformation products arising from TiO₂-photocatalytic degradation of the fungicide Fenhexamid (FEX) in aqueous solution under simulated solar irradiation. Prior to identification, irradiated solutions of FEX (10 mg L⁻¹) were concentrated by solid-phase extraction. Assignments of the mass spectra ions were aided by elemental composition calculations, comparison of structural analogues and available literature, and acquired knowledge regarding mass spectrometry of related heterocyclic compounds. The primary transformation intermediates identified were hydroxyl and/or keto-derivatives. Several positional isomers are typically produced as a consequence of the non-selectivity of the OH radical attack. Moreover, products resulted from the cleavage of the amide and NHdichlorophenol bonds were formed. Finally, cyclic - benzo[d]oxazole intermediates are also formed through an intramolecular photocyclization process and cleavage of halogen - carbon bond. In the case of the hydroxy and/or keto-derivatives, the generic fragmentation scheme obtained from the interpretation of the ESI-TOF-MS data cannot be diagnostic to precisely localize the position of the entering substituent on the FEX molecule, and thus to characterize all its possible oxygenated derivatives by assigning a plausible structure with confidence. On the basis of identified products different pathways of photocatalytic degradation of FEX were proposed and discussed.     

Ecotoxic Effect of Photocatalytic Active Nanoparticles (TiO2) on Algae and Daphnids (8 pp)

Background, Aim and Scope Due to their large potential for manifold applications, the use of nanoparticles is of increasing importance. As large amounts of nanoparticles may reach the environment voluntarily or by accident, attention should be paid on the potential impacts on the environment. First studies on potential environmental effects of photocatalytic TiO2 nanoparticles have been performed on the basis of widely accepted, standardized test systems which originally had been developed for the characterization of chemicals. The methods were adapted to the special requirements of testing photocatalytic nanoparticles. Materials and Methods: Suspensions of two different nanoparticles were illuminated to induce their photocatalytic activity. For testing, the growth inhibition test with the green alga Desmodesmus subspicatus and the immobilization test with the daphnid Daphnia magna were selected and performed following the relevant guidelines (algae: ISO 8692, OECD 201, DIN 38412-33; daphnids: ISO 6341, OECD 202, DIN 38412-30). The guidelines were adapted to meet the special requirements for testing photocatalytic nanoparticles. Results: The results indicate that it is principally possible to determine the ecotoxicity of nanoparticles. It was shown that nanoparticles may have ecotoxicological effects which depend on the nature of the particles. Both products tested differ in their toxicity. Product 1 shows a clear concentration-effect curve in the test with algae (EC50: 44 mg/L). It could be proven that the observed toxicity was not caused by accompanying contaminants, since the toxic effect was comparable for the cleaned and the commercially available product. For product 2, no toxic effects were determined (maximum concentration: 50 mg/L). In the tests with daphnids, toxicity was observed for both products, although the concentration effect-curves were less pronounced. The two products differed in their toxicity; moreover, there was a difference in the toxicity of illuminated and non-illuminated products. Discussion: Both products differ in size and crystalline form, so that these parameters are assumed to contribute to the different toxicities. The concentration-effect curves for daphnids, which are less-pronounced than the curves obtained for algae, may be due to the different test organisms and/or the differing test designs. The increased toxicity of pre-illuminated particles in the tests with daphnids demonstrates that the photocatalytic activity of nanoparticles lasts for a period of time. Conclusions: The following conclusions can be drawn from the test results: (I) It is principally possible to determine the ecotoxicity of (photocatalytic) nanoparticles. Therefore, they can be assessed using methods comparable to the procedures applied for assessing soluble chemicals. - (II) Nanoparticles may exert ecotoxicological effects, which depend on the specific nanoparticle. - (III) Comparable to traditional chemicals, the ecotoxicity depends on the test organisms and their physiology. - (IV) The photocatalytic activity of nanoparticles lasts for a relevant period of time. Therefore, pre-illumination may be sufficient to detect a photocatalytic activity even by using test organisms which are not suitable for application in the pre-illumination-phase. Recommendations and Perspectives: First results are presented which indicate that the topic 'ecotoxicity and environmental effects of nanoparticles' should not be neglected. In testing photocatalytic nanoparticles, there are still many topics that need clarification or improvement, such as the cause for an observed toxicity, the improvement of the test design, the elaboration of a test battery and an assessment strategy. On the basis of optimized test systems, it will be possible to test nanoparticles systematically. If a potential risk by specific photocatalytic particles is known, a risk-benefit analysis can be performed and, if required, risk reducing measures can be taken.     

掺杂负载型纳米TiO2降解橙黄G的光催化活性及其动力学研究

采用溶胶-凝胶法和浸渍-焙烧法制备了掺杂Sn(Ⅳ)的TiO2/AC光催化剂,以偶氮染料橙黄G为目标降解物,对光催化反应条件进行了优化.结果表明:利用Sn(Ⅳ)掺杂量为2.5 at.%的TiO2/AC光催化剂,在进水浓度50 mg/L,催化剂的用量12.5 g/L,pH值2.0,H2O21.5 mL/L,主波长为365 nm的300W高压汞灯光照条件下,反应60 min,橙黄G的光催化去除率可达99.1%.该反应符合Langmuir-Hinshelwood动力学方程,其速控步为吸附反应.共存阴离子SO42-和H2PO4-,对橙黄G的光催化降解反应均有一定的抑制作用.     

Photocatalytic Degradation of an Organophosphorus Pesticide Phosalone in Aqueous Suspensions of Titanium Dioxide

Abstract

The present work deals with photocatalytic degradation of an organophosphorus pesticide, phosalone, in water in the presence of TiO₂ particles under UV light illumination (1000 W). The influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO₂, irradiation time, stirring rate, and distance from UV source, on the photodegradation efficiency of phosalone was investigated. The degradation rate of phosalone was not high when the photolysis was carried out in the absence of TiO₂ and it was negligible in the absence of UV light. The half-life (DT₅₀) of a 20 ppm aqueous solution of phosalone was 15 min in optimized conditions. The plot of lnC (phosalone) vs. time was linear, suggesting first order reaction (K = 0.0532 min^?1). The half-life time of photomineralization in the concentration range of 7.5–20 ppm was 13.02 min. The efficiency of the method was also determined by measuring the reduction of Chemical Oxygen Demand (COD). During the mineralization under optimized conditions, COD decreased by more than 45% at irradiation time of 15 min. The photodegradation of phosalone was enhanced by addition of proper amount of hydrogen peroxide (150 ppm).     

掺Ni2+的TiO2颗粒光催化性能的研究

通过溶胶-凝胶法制备掺杂Ni2 的纳米TiO2,并用XRD和TEM进行了表征,发现Ni2 的掺杂减小了TiO2颗粒的粒径,Ni2 /TiO2晶型为锐钛型.通过对目标物罗丹明B的光催化降解实验,发现Ni2 的掺杂提高了TiO2的光催化活性,其降解罗丹明B的反应遵从一级反应动力学方程,Ni2 惨杂量为1.2%时的光催化活性最高.