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.     

Enhanced activation of peroxymonosulfate by CNT-TiO2 under UV-light assistance for efficient degradation of organic pollutants

CNT-TiO₂ composite is used to activate PMS under UV-light assistance. Superior performance is due to the enhanced electron-transfer ability of CNT. SO₄•⁻, •OH and ¹O₂ play key roles in the degradation of organic pollutants. In this work, a UV-light assisted peroxymonosulfate (PMS) activation system was constructed with the composite catalyst of multi-walled carbon nanotubes (CNT) - titanium dioxide (TiO₂). Under the UV light irradiation, the photoinduced electrons generated from TiO₂ could be continuously transferred to CNT for the activation of PMS to improve the catalytic performance of organic pollutant degradation. Meanwhile, the separation of photoinduced electron-hole pairs could enhance the photocatalysis efficiency. The electron spin resonance spectroscopy (EPR) and quenching experiments confirmed the generation of sulfate radical (SO₄•⁻), hydroxyl radical (•OH) and singlet oxygen (¹O₂) in the UV/PMS/20%CNT-TiO₂ system. Almost 100% phenol degradation was observed within 20 min UV-light irradiation. The kinetic reaction rate constant of the UV/PMS/20%CNT-TiO₂ system (0.18 min⁻¹) was 23.7 times higher than that of the PMS/Co₃O₄ system (0.0076 min⁻¹). This higher catalytic performance was ascribed to the introduction of photoinduced electrons, which could enhance the activation of PMS by the transfer of electrons in the UV/PMS/CNT-TiO₂ system.     

聚苯乙烯/CdS/TiO_2双壳层核壳纳米颗粒可见光催化降解甲基橙

采用溶胶-凝胶法,在聚苯乙烯(PS)/CdS核壳纳米颗粒表面包覆致密TiO_2层,制备出具有双壳层结构的PS/CdS/TiO_2纳米复合颗粒,考察了制备条件对材料结构的影响,并利用甲基橙溶液对其光催化性能进行了评价。SEM、TEM、XRD和FTIR分析结果表明,制得的微球单分散性良好,壳层包覆完整,厚度均匀。PS/CdS/TiO_2制备的适宜反应时间为12~18 h,适宜反应pH为7~9。PS/CdS/TiO_2较PS/CdS具有更为优异的可见光催化性能。     

CePO4-TiO2固溶体的NH3-SCR活性

采用共沉淀法合成了不同Ce与Ti摩尔比的CePO₄-TiO₂复合材料,利用XRD、TEM、NH₃-TPD和H₂-TPR技术对其物理化学性质进行了表征,并对其NH₃-SCR活性进行了评价。实验结果表明：随着CePO₄含量的增加,催化剂的活性提高;当Ce与Ti的摩尔比为8:2时催化剂的活性最高,230 ℃的NO转化率达到100%,且具有更广的温度窗口,优于纯CePO₄。表征结果显示,CePO₄与TiO₂形成固溶体后,颗粒尺寸较为均匀,强酸位的数量增多,氧化还原性能提升,从而提高了催化剂的SCR反应活性,同时改善了其抗水抗硫性能。     

无机阴离子对TiO2/SiO2光催化降解酸性红B活性的影响

以酸性红B为模型化合物，分别考察了6种常见的无机阴离子对TiO2/SiO2复合光催化剂活性的影响，并考察了导致催化剂失活的无机阴离子的最低浓度。结果表明，除了HCO3^-能引起催化剂部分不可逆中毒外，其余5种离子并没有在催化剂形成占位。失活的催化剂通过简的HCl冲洗即可再生。另外，对催化剂的失活机制作了初步探讨。     

前驱物结晶体升华成膜法制备TiO2薄膜及其光催化性研究

采用“前驱物结晶体升华成膜法”工艺，使含钛前驱物结晶体草酸氧钛酸以升华的方式，均匀地在玻璃表面形成前驱物薄膜；经过热处理，制备出外观平整透明的玻璃基TiO2薄膜，其薄膜厚度为80-100nm，粒度≤50nm。初步研究了制备条件、薄膜性能和本工艺制备的玻璃基TiO2纳米薄膜对甲基对硫磷的光催化降解性能。     

吸附模式对有机物光催化降解的影响2.H-酸在TiO2表面的光催化降解途径

水溶液中H-酸通过磺酸基团吸附在TiO2表面,UV照射TiO2所产生的自由基首先进攻吸附在TiO2表面的磺酸基团,从而进一步导致萘环开环.pH 2.5条件下,虽然饱和吸附量较大,但由于H-酸仅通过一个磺酸基团吸附在TiO2表面,过程中产生的硫酸根速率较慢,最终的光降解速率也较慢.pH 5.0条件下,虽然饱和吸附量较小,但由于吸附在TiO2表面的两个磺酸基团同时受到来自TiO2表面自由基的进攻,过程中产生的硫酸根速率较快,最终的光降解速率也较快.吸附模式的差异是导致H-酸在不同pH值条件下光催化降解途径和速率差异的关键因素.     

偏电压对Ti/TiO2光电催化氧化富里酸的影响

采用光电催化反应器对水中天然有机物富里酸(FA)进行降解试验,考察了外加阳极偏电压对光电催化反应器降解富里酸的影响.结果表明,当外加电压为1.2V时,具有最佳的UV254和有机碳TOC去除率,当反应时间为2h时,富里酸的UV254和总有机碳TOC的去除率分别为77.4%和45.4%.另外,在反应初期(前1h内)富里酸光电催化反应动力学常数主要受外加偏电压的影响.     

玻璃弹簧负载镶嵌纳米粒子TiO2膜光催化降解活性深蓝K-R

以玻璃弹簧负载镶嵌纳米粒子的TiO2膜降解活性深蓝K-R模拟废水,考察了pH值和温度对脱色率的影响以及CODCr去除率与脱色率之间的关系,并用XRD和SEM对催化剂进行了表征.结果表明,pH值和温度对脱色率均有显著影响,CODCr去除率与脱色率的比值约为70%左右;XRD表明,TiO2矿相主要为锐钛型,SEM表明,镶嵌TiO2粒子均匀,粒径约50nm.     

纳米TiO2光催化氧化异丙醇和丙酮反应的研究

分别研究了纳米TiO2 在主波长为 364nm的汞灯光照下催化氧化i C3H7OH和CH3COCH3水溶液的反应速率 .通过XRD ,TEM ,BET和FT IR PAS对催化剂进行表征 ,粉末的晶型主要为锐钛矿型 .平均粒径在 1 5nm左右 ,比表面积为 1 0 1 0± 0 2m2 ·g- 1 ,FT IR PAS的检测结果表明 ,CH3COCH3是i C3H7OH光催化氧化的中间产物 ,其光催化氧化反应为 :i C3H7OH [O]CH3COCH3[O]CH3COOH[O]…[O]CO2 H2 O