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.     

负载TiO2浮石对污水处理厂二沉池出水的矿化与灭菌研究

城市污水处理厂第二沉淀池出水的污染物浓度较低,经过矿化及灭菌等深度处理后可以回用,从而减轻对淡水资源的需求。本实验采用溶胶-凝胶法制备了负载TiO2的浮石光催化剂,对城市污水处理厂第二沉淀池出水进行了矿化及灭菌处理研究。采用低压汞灯对处理水样照射2h,有机物降解率可以达到50％,灭菌效率达到100％。处理后的水可以作为农作物灌溉、城市绿化和娱乐用水。负载在浮石表面的TiO2薄膜经过10次的光催化循环实验后,没有明显破损,可以再次循环使用。TiO2浮石具有质轻、机械性能好和价格低等优点,该方法处理废水的适用浓度低,可以广泛应用于微污染水和城市污水处理厂出水的深度处理。     

溶胶凝胶法制备磷钨酸掺杂TiO2薄膜及其光催化性能

以钛酸四丁酯为前驱物,采用溶胶凝胶法制备了磷钨酸掺杂的二氧化钛薄膜。通过XRD、FT-TR对该薄膜进行了表征,研究了薄膜在对氯苯酚光降解中的催化活性。结果表明,当磷钨酸与二氧化钛摩尔比为0.01∶1、薄膜烧结温度600℃、对氯苯酚溶液浓度30 mg/L（pH＝5）、光催化8 h的条件下,对氯苯酚的降解率超过90%,且薄膜可以重复使用。磷钨酸对二氧化钛的光催化活性具有明显的促进作用。     

Ce-ZnO/AC在真空紫外下催化降解对二甲苯废气

将Ce掺杂ZnO光催化剂通过负载活性炭 (AC)的方式制备Ce-ZnO/AC吸附-催化复合材料,并以对二甲苯为典型挥发性有机污染物(VOC),研究其在真空紫外体系中光催化转化性能。结果表明：活性炭的负载能有效提高臭氧的利用效率,强化对二甲苯的去除率和矿化率;当Ce-ZnO与活性炭的负载比例为1∶2时,复合材料的光催化性能达到最优,此时对二甲苯的转化率达到95%以上;活性炭的负载不仅可使污染物与催化剂充分接触,还可有效利用臭氧从而产生·OH等自由基,协同促进对二甲苯的降解,同时更多的中间产物被降解。复合催化材料显示了良好的稳定性,在利用5次后,仍可再生恢复其光催化性能至初始状态。相对于单独的真空紫外光解,Ce-ZnO/AC吸附-催化复合材料与真空紫外体系耦合降解二甲苯的能量利用率提高了2倍,经济性好。     

碘掺杂Ti02可见光光催化性能研究

在低于100℃温度条件下,采用溶胶一凝胶法以钛酸正丁酯为钛源,碘酸钾为碘源,制备了I掺杂纳米TiO2催化剂（I-TiO2）,运用x-射线衍射（XRD）、透射电镜（TEM）及x-射线光电子能谱（XPS）等对催化剂进行表征,结果表明,TiO2及I-TiO2催化剂均为锐钛矿,I吸附并包裹在TiO2表面或以间隙进入的形式存在,并未进入TiO2晶格。通过在可见光照射下（A〉420nm）以罗丹明B（RhodamineB,RhB）的光催化降解为探针反应研究了在不同条件下制备催化剂的催化性能,结果表明,掺杂比为n1：n^ti=0．05：l,焙烧温度为400℃,降解介质条件pH=7时,l-TiO2光催化活性明显优于未掺杂的TiO2。光催化降解过程通过红外光谱（IR）,总有机碳（TOC）跟踪测定,比较了TiO2掺杂前后降解RhB和对氯苯酚（4-CP）的光催化特性差异;同时采用苯甲酸荧光光度法跟踪测定体系中的氧化物种,表明在可见光下,I-TiO2光催化体系中产生·OH高活性氧化物种从而氧化降解目标化合物。     

TiO2光催化技术在有害气体净化中的应用

主要介绍了TiO2光催化技术在有害气体净化中的应用、提高TiO2光化效率的方法以及影响TiO2光催化效率的因素。     

钴掺杂二氧化钛的制备及光催化性能的研究

钴掺杂制备超细TiO2粒子,并进行了表征。CoO与TiO2形成固溶体抑制了TiO2晶粒的长大并促进相变。钴掺杂有利于提高TiO2光催化剂的寿命。     

氨基修饰增强的Fe/Cu-MOF对罗丹明B的光催化降解性能及相关机理

利用溶剂热合成法合成了氨基修饰的Fe/Cu-MOF-NH₂,分别采用XRD、SEM、N₂吸附-脱附、UV-vis、EA等检测方法进行了表征分析,并将其用于RhB的光催化降解,考察了RhB的初始质量浓度、催化剂质量浓度和pH对光催化降解的影响。结果表明,氨基的引入显著提升了催化剂的可见光响应性能;在合成Fe/Cu-MOF-NH₂时,当含氨基配体与不含氨基配体的摩尔比为1∶1、RhB初始质量浓度为300 mg·L⁻¹、催化剂质量浓度为1 mg·mL⁻¹、pH为4.2时,光照4 h后,催化剂对RhB的去除率达到99.53%。活性物种淬灭实验结果表明,·OH、h⁺分别是Fe/Cu-MOF-NH₂和Fe/Cu-MOF在催化降解过程中的主要活性物种。以上结果可为探究Fe/Cu-MOF-NH₂光催化降解RhB的机制提供参考。     

部分水溶性偶氮染料的光催化降解研究

本研究以高压汞灯为光源,系统地研究了１６种偶氮染料在水溶液中的ＴｉＯ２光催化降解。结果表明,这些偶氮染料的光解为一级动力学反应,采用ＴｉＯ２光催化降解方法处理所研究的偶氮染料是可行的,并初步探讨了染料的结构与光解反应表观速率常数之间的关系。     

高铁-光催化氧化协同去除藻毒素的研究

研究了高铁-光催化氧化体系去除水中藻毒素的效能.结果表明,通过投加10mg/L的高铁到光催化体系中,由于高铁的强氧化性及其还原产物可作为电子捕获剂的特点,可将光催化效率从63%提高到100%,实现快速完全去除藻毒素的目的.同时对照研究了高铁、光催化、Fe³⁺-光催化、高铁-光催化4种不同反应体系对藻毒素去除的效能.结果显示,单纯的高铁或光催化都可以降解一部分藻毒素,但去除率低,分别为54%和63%,且需大剂量的高铁投加或大大延长光照时间.而在Fe³⁺-光催化、高铁-光催化体系中,只需投加10mg/L的三价铁或高铁,就可以将藻毒素去除率提高到73%和100%,但采用高铁协同光催化体系比三价铁协同光催化体系更有效.也就是说在本体系中,高铁具有十分重要的作用,明显存在着高铁与TiO₂光催化的协同效应.