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.     

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。     

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。     

钨酸铋光催化降解萘普生效果及其机理

以萘普生(NPX)为目标污染物,钨酸铋(Bi₂WO₆)为光催化剂,考察NPX浓度、Bi₂WO₆投加量、阴离子种类、溶液pH对Bi₂WO₆光催化降解NPX效果的影响并确定最佳反应条件。通过原位捕获实验、中间产物识别及反应体系化学需氧量(COD)去除效果,解析光催化过程产生的活性自由基种类及其作用、NPX降解路径及反应体系矿化度,揭示NPX降解机理。结果表明：经水热法制备的Bi₂WO₆为纯正交晶系,具有由2D纳米方片构成的3D花朵状结构,平均孔径为10.79 nm,比表面积为32.54 m²·g⁻¹,带隙能为2.54 eV;在500 W长弧氙灯照射下,当NPX浓度为10 mg·L⁻¹、Bi₂WO₆投加量0.4 g·L⁻¹、溶液pH值为4.6时,NPX降解率可达99.83%,光照180 min时矿化度为67.91%,光照反应时间延长至360 min时矿化度为82.14%;Bi₂WO₆价带电势(3.01 eV)高于OH⁻/·OH和H₂O/·OH的电势,因此,空穴(h⁺)能氧化OH⁻和H₂O生成羟基自由基(·OH);而Bi₂WO₆导带电势(0.47 eV)同样高于O₂/$ \cdot {\rm{O}}_2^ - $的电势,单电子(e⁻)还原O₂过程很难发生,只能经多e⁻还原O₂,生成超氧自由基($ \cdot {\rm{O}}_2^ - $)。同时还发现,h⁺和·OH在NPX降解过程中起主要氧化作用,$ \cdot {\rm{O}}_2^ - $起辅助作用。综合上述结果,NPX的降解机理是在活性自由基协同氧化下,NPX分子中的C—C、C—O、C=C键断裂发生脱羧反应和羟基化反应,生成结构简单的中间产物,中间产物继续氧化分解为小分子化合物并部分矿化成CO₂和H₂O。     

不同煅烧温度的N-TiO2制备、表征及可见光催化性能

以钛酸丁酯为钛源,氯化铵为氮源,采用溶胶-凝胶法,不同煅烧温度条件制备N掺杂TiO2纳米材料,采用X射线粉末衍射(XRD)、傅里叶变换红外(FT-IR)、扫描电镜(SEM)、紫外-可见漫反射(UV-Vis DRS)手段对其进行表征,并通过降解腐殖酸(HA)实验,探讨N-TiO2可见光催化性能。结果表明,制备的光催化纳米材料为锐钛矿相,TiO2光响应范围可拓宽到可见光区;煅烧温度是影响可见光催化活性的重要因素,350℃煅烧的N-TiO2可见光催化活性最佳,光反应140 min后,对初始浓度为5 mg/L的HA溶液降解率达80.32%,光催化反应过程符合准一级动力学,煅烧温度过高或过低,动力学反应速率常数呈现不同程度的减小,降解反应速率明显下降。     

水环境中微塑料的生态效应及去除研究进展

以微塑料对水环境的影响为切入点,综述了其在水环境中的迁移和转化途径,分析了其对水生生态系统的危害,并探讨了现行的水体微塑料去除技术及应用,为微塑料污染的防治提供一些建议和指导。     

ZJR型涂料的制备及特性研究

利用溶胶凝胶法制备TiO2光催化剂,使用磷酸氢二钠、十水合四硼酸钠和氢氧化镁等制备了阻燃体系料,复合后制成ZJR涂料。利用热分析仪分析纳米TiO2和阻燃体系复合的防火涂料的温度与热失率关系,并得到热重与微商热重曲线。550~650℃之间,失重率约为11%,ZJR涂料在400~600℃有较好的阻燃效果。该涂料对污染气体的光催化降解研究结果表明:光照60 m in后,对二氧化硫的降解率为90.40%,紫外光照40 m in后,甲醛气体降解率为68.98%。进一步添加聚乙二醇和银离子使涂料改性,使涂料光催化甲醛的活性分别提高了11%和14%,效果显著。     

炮采放顶煤采空区自然发火的数值模拟应用

针对炮采放顶煤开采采空区容易发生自燃问题，基于漏风渗流方程、气体渗流一扩散-氧消耗方程，建立了采空区自然发火非稳定数值模型，采空区按非均质考虑，耗氧汇按煤矸氧化和瓦斯涌出稀释两方面综合考虑，用有限元数值方法联立求解模型。结合羊草沟矿实例，通过该矿自然发火后来的测试区的现场实测结果，拟合反演得到采空区煤的耗氧速度、瓦斯涌出强度和渗透特征参数，用确定的模型分析了前段出现自然发火的原因；描绘了炮采放顶煤开采时采空区冷却带、自燃带和窒息带等三带的形状，指出冒落压实的不均衡的非均质采空区，自燃点在偏人风一侧。用三带划分理论讨论了工作面参数（风量、推进度、控顶距）同自燃的量化关系，提出了从根本上预防采空区自然发火的途径与方法。     

磷酸银/树脂复合物的制备及其对亚甲基蓝的光催化降解

以聚乙烯吡咯烷酮(PVP)为稳定剂,采用化学沉积法制备了磷酸银/树脂复合物,降解亚甲基蓝,研究其光催化活性,并对样品进行了XRD和SEM表征。探讨了不同的光源、催化剂投加量、PVP含量、p H值等因素对亚甲基蓝降解率的影响。结果表明,在太阳光(夏天早上9点到11点的阳光)下,偏酸介质中,催化剂用量为0.8 g/L,PVP质量分数为0.01%的磷酸银/树脂复合物,液面高度为15 cm的条件下对亚甲基蓝有最佳降解效果。