Toxicity of nanoparticulate and bulk ZnO, Al2O3 and TiO2 to the nematode Caenorhabditis elegans

Limited information is available on the environmental behavior and associated potential risk of manufactured oxide nanoparticles (NPs). In this research, toxicity of nanoparticulate and bulk ZnO, Al₂O₃ and TiO₂ were examined to the nematode Caenorhabditis elegans with Escherichia coli as a food source. Parallel experiments with dissolved metal ions from NPs were also conducted. The 24-h median lethal concentration (LC₅₀) and sublethal endpoints were assessed. Both NPs and their bulk counterparts were toxic, inhibiting growth and especially the reproductive capability of the nematode. The 24-h LC₅₀ for ZnO NPs (2.3 mg L⁻¹) and bulk ZnO was not significantly different, but significantly different between Al₂O₃ NPs (82 mg L⁻¹) and bulk Al₂O₃ (153 mg L⁻¹), and between TiO₂ NPs (80 mg L⁻¹) and bulk TiO₂ (136 mg L⁻¹). Oxide solubility influenced the toxicity of ZnO and Al₂O₃ NPs, but nanoparticle-dependent toxicity was indeed observed for the investigated NPs.     

Fe_3O_4@SiO_2/TiO_2核壳结构纳米颗粒降解TNT溶液

针对TNT炸药废水具有成分复杂、排放量大、有毒等特点,立足于炸药废水在排放前的降解处理,研究开发一种基于核壳结构Fe3O4@SiO2/TiO2纳米颗粒的高效、可控回收、无二次污染且成本低的光催化降解方法。利用高温碳还原法和溶胶凝胶法制备了具有核壳结构的Fe3O4@SiO2/TiO2纳米颗粒。XRD分析表明,内核Fe3O4呈现磁铁矿特征,表面覆盖的纳米TiO2为锐钛矿型。磁滞回线测试结果显示,复合颗粒的饱和磁化强度为46.5 emu/g,N2吸附-解吸分析结果表明,该颗粒具有典型的介孔结构。使用Fe3O4@SiO2/TiO2纳米颗粒在紫外光下对含TNT废水进行降解,降解率达到81.9%,且颗粒的回收率达到88.4%,为实现高效、可控回收、无二次污染光催化-吸附降解TNT奠定了基础。     

CuO/TiO2-H2O2可见光催化亚甲基蓝脱色效果及影响因素研究

以水解法制备的锐钛矿型TiO2为载体,制备了CuO/TiO2型光催化剂.以亚甲基蓝为对象,在可见光照射下研究了H2O3加入量、pH值和催化剂投加量对脱色效果的影响,同时与改性前的TiO2催化剂进行了脱色效果的对比.结果表明亚甲基蓝在碱性条件下能较好脱色,H2O2用量和CuO/TiO2催化剂投加量分别为每1 000 mL反应液各加入10 mL和0.1 g时脱色最好;另外,TiO2催化剂也在碱性条件下能较好脱色,H2O2用量和催化剂投加量分别为每1 000 mL反应液各加入12.5 mL和0.1 g时脱色最好.最优条件下对比实验表明,CuO/TiO2型催化剂在可见光照射下具有很高的催化活性,亚甲基蓝2 h脱色率达到88%,远好于改性前的TiO2和Degussa P25催化剂.     

活性炭纤维负载TiO2光催化降解甲醛的影响因素

利用自制光催化气体反应器体系，以活性炭纤维负载TiO₂作催化剂，在紫外光照射下模拟降解室内污染气体甲醛，测试了活性炭纤维负载TiO₂催化剂的催化活性，探讨了紫外光光强、催化剂的酸度、反应器内湿度及反应时间等控制反应的主要因素对甲醛降解率的影响。结果表明，活性炭纤维与TiO₂的协同作用大大提高了对甲醛的降解效果；紫外光强增倍对甲醛降解率有一定提高，但提高幅度仅为11.71%；活性炭纤维用pH=5的TiO₂溶胶浸泡做催化剂对甲醛的降解效果最好，60 min内降解率达到68.37％；反应器内的湿度为81%甲醛降解率最高，反应60 min后达82.2%；随着反应时间的延长，甲醛降解率的上升幅度不断减小,最高只能达到94.59%。     

UV/H_2O_2/TiO_2联合水解酸化+MBR工艺处理亚砜废水

二甲基亚砜(DMSO)废水因其COD高、可生化性差的特性而较难处理。本实验以采用硫酸二甲酯法生产DMSO的某化工厂废水为研究对象,设计并建立了组合式光催化氧化装置联合水解酸化+MBR工艺的中试系统,探讨了组合式光催化氧化装置、氧化剂投加量、pH、反应时间和水力停留时间对系统处理效果的影响。结果表明,组合式光催化氧化装置可有效提高DMSO废水的可生化性。最优工艺参数为:按H2O2与原水COD质量浓度比为2∶1投加H2O2,在pH值为4、反应时间为6 h、水力停留时间为4 h的条件下,该系统对原水COD(5 000 mg/L)去除率大于98%,出水COD达到《污水综合排放标准》(GB 8978-1996)一级要求。     

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%。     

Comparative studies of the Fe–UV, H2O2–UV, TiO2–UV/vis systems for the decolorization of a textile dye X-3B in water

The degradation of a common textile dye, Reactive-brilliant red X-3B, by several advanced oxidation technologies was studied in an air-saturated aqueous solution. The dye was resistant to the UV illumination (wavelength λ  320 nm), but was decolorized when one of Fe³⁺, H₂O₂ and TiO₂ components was present. The decolorization rate was observed to be quite different for each system, and the relative order evaluated under comparable conditions followed the order of Fe²⁺–H₂O₂–UV  Fe²⁺–H₂O₂ > Fe³⁺–H₂O₂–UV > Fe³⁺–H₂O₂ > Fe³⁺–TiO₂–UV > TiO₂–UV > Fe³⁺–UV > TiO₂–visible light (λ  450 nm) > H₂O₂–UV > Fe²⁺–UV. The mechanism for each process is discussed, and linked together for understanding the observed differences in reactivity.     

碳纳米管/二氧化钛/壳聚糖催化薄膜光催化活性及苯降解机理

通过X-射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)和紫外可见光漫反射谱(UV-vis)对碳纳米管/二氧化钛/壳聚糖复合薄膜的晶体结构和形貌进行表征,以室内空气典型污染物气相苯为模型反应物,研究碳纳米管/二氧化钛/壳聚糖催化薄膜的光催化活性及其对苯的光降解机理。结果表明,制备的碳纳米管/二氧化钛/壳聚糖催化薄膜所具有的良好催化活性归功于碳纳米管、二氧化钛和壳聚糖三者的协调效应;气相苯光降解产生的主要中间产物是乙酸乙酯和十一烷,以及少量的丙烯醛、4-羰基-甲基-苯乙酮、十二烷烃、2,4,-二叔丁基苯酚、二十一烷烃。根据红外光谱分析与GC/MS分析结果,进一步提出了气相苯的降解机理过程。     

Phenol electrooxidation on Fe-Co3O4 thin film electrodes in alkaline medium

Fe-Co₃O₄ thin film with different amounts of Fe have been used for the electro-oxidation of phenol in alkaline medium at room temperature. The electrodes were prepared by coating stainless steel supports with successive layers of the oxides, obtained by thermal decomposition at 673 K. The electrolysis was carried out at constant potential and the phenol disappearance, during the electrolysis, was monitored by UV-Vis absorbance measurements between 250 and 500 nm. After 3 h of electrolysis, the intermediates were identified by comparing the HPLC data and UV-Vis spectra to those from pure standards. The results indicate that the same oxidation products are formed on the different prepared electrodes, namely the decomposition products of phenol such as benzoquinone, hydroquinone and cathecol in basic medium. Simulated results show clearly the decrease of the amount of phenolic species with the electrolysis time. An enhancement of the phenol removal is observed with the presence of iron in the oxide. Under the operating conditions, around 30% of the initial phenol has been removed at ca. 3 h and the complete degradation is obtained after 54 h of electrolysis, when Fe-Co₃O₄ thin film with 10% of Fe is used as anode.     

汉沙黄/TiO_2光催化剂的制备及其光催化活性

采用溶剂热合成法制备了一种新型的汉沙黄/TiO2复合物光催化剂,利用多种手段SEM、XRD、FT-IR对催化剂的样品形貌、结构进行表征。分别以罗丹明B、亚甲基蓝、中性红为目标降解物,考察了可见光下溶液pH值对催化剂的吸附性能和催化活性的影响。结果表明,敏化后的TiO2对光的响应由紫外区扩展到可见区,催化活性优于纯TiO2,对上述3种染料的吸附率分别为19.2%、29.2%和43.2%,降解率分别为98.6%、92.5%和97.8%。制备的汉沙黄/TiO2光催化剂稳定性好,重复使用率高,在印染废水处理中具有很好的应用前景。     

In vivo screening to determine hazards of nanoparticles: Nanosized TiO2

A single-species laboratory test with terrestrial invertebrates was used to identify the hazard of nanosized TiO₂. Feeding parameters, weight change, mortality, and the activities of catalase and glutathione-S-transferase were evaluated after 3 or 14 days of dietary exposure. The effects of nano-TiO₂ were dependent on exposure concentration and duration, total consumed quantity, size and pre-treatment of particles. The intensity of a response was ruled by duration of exposure and not by consumed quantity of nano-TiO₂ or exposure concentration as expected. The response to nano-TiO₂ is described as threshold-like. The exposure concentrations 10-1000 μg TiO₂/g dry food (1.35-1025 μg of total consumed quantity of TiO₂/g animal wet wt.) were identified as safe for tested species after tested exposure period. We conclude that the response to nanoparticles is different from that of soluble chemicals therefore these two types of data should be interpreted and processed differently.     

纳米Bi2O3/TiO2复合光催化剂的制备及性能研究

以光催化效果为评价标准，采用超声波作用下水解法制备Bi₂O₃/TiO₂复合光催化剂，考察了水解条件和Bi₂O₃掺入量等制备条件对复合光催化剂性能的影响。结果表明，与传统制备方法相比，该方法操作简单、快速；当水和乙醇的比例为4∶1时所得样品的光催化活性最好；Bi₂O₃的掺入拓宽了TiO₂对光的吸收范围，提高了TiO₂的光催化活性，掺入量(Bi₂O₃)为0.25%复合光催化剂催化活性最高；复合光催化剂对多种水溶性染料均具有较好的处理效果。     

纳米TiO2/活性炭复合光催化剂的制备及其对甲醛气体降解

研究了纳米TiO2/活性炭复合光催化剂对空气中典型污染气体甲醛的光催化降解特性。采用扫描电镜(SEM)表征复合催化剂的表面特征。结果显示,经改性后的纳米TiO2在复合催化剂表面分布均匀,呈球状。对甲醛气体的降解实验显示TiO2负载量为1%时对甲醛的去除效果最好,6 h去除率为61.7%。结果显示复合催化剂把甲醛气体分解成CO2,可以直接排空,无二次污染。     

TiO2/Ni PECO体系降解DMP的动力学和光电协同作用研究

以采用微波辅助法制备的TiO₂/Ni光电极为阳极，纤维状石墨毡材料(graphite felt,GF)为阴极，饱和甘汞电极(saturated calomel electrode, SCE)为参比电极建立TiO₂/Ni 光电催化氧化（PECO）体系。以邻苯二甲酸二甲酯（dimethy phthalate,DMP）为目标物，研究其光电催化降解反应动力学和光电协同作用。结果显示：DMP的降解符合拟一级动力学规律；当DMP初始浓度一定时，影响DMP光电催化降解速率的因素由强到弱依次为：催化剂有效面积，紫外光强度，曝氧速率，外加偏转电压等。实验证明本体系中光电之间具有协同作用。     

UV/H2O2/Fe-FeOxH2x-3和UV/H2O2工艺降解水中富里酸的研究

采用硼氢化钠还原法制备核-壳结构的Fe-FeO_xH_2x-3复合材料，研究了富里酸在UV/H₂O₂和UV/H₂O₂/Fe-FeO_xH_2x-3两种不同反应体系下的降解情况。结果表明，核-壳结构Fe-FeO_xH_2x-3的存在，提高了UV/H₂O₂降解富里酸的反应速率，TOC去除达到84%。采用XAD树脂吸附法对反应前后的富里酸进行化学分级表征，结果表明，富里酸经反应后憎水酸（HoA）、弱憎水酸（WHoA）和憎水中性物质（HoN）都有所减少，进而转化为亲水性物质（HiM）；用超滤膜法对富里酸进行物理分级表征，考察了富里酸在反应前后分子量分布的变化情况。同时，富里酸经过反应后生成的中间产物降低了三氯甲烷生成趋势。     

Cu/La共掺杂TiO2光催化氧化水中的氨氮

采用水解-沉淀法制备了Cu/La共掺杂纳米TiO2催化剂,利用XRD、XPS和BET技术对其进行表征,并考察了在紫外灯下,共掺杂TiO2对氨氮的光催化氧化工艺条件。物相结构和比表面积测试结果表明,共掺杂催化剂具有较好的锐钛矿晶型,孔径分布为4～8 nm,Cu/La共掺杂TiO2La以La3+,Cu是以Cu2+、Cu+的形式掺杂进入TiO2的晶格。光催化实验表明:所得改性光催化剂对氨氮的去除及焦化废水的处理均具有较高的催化活性。     

Synergistic increase in cell lethality by dieldrin and H2O2 in rat thymocytes: Effect of dieldrin on the cells exposed to oxidative stress

Dieldrin, one of persistent pesticides, is highly resistant to biotic and abiotic degradation. It is accumulated in organisms. Recent studies suggest that dieldrin exerts a potent cytotoxic action on cells exposed to oxidative stress. In this study, the effect of dieldrin on rat thymocytes exposed to hydrogen peroxide (H₂O₂)-induced oxidative stress was examined. Dieldrin at 5 μM and H₂O₂ at 300 μM slightly increased cell lethality from a control value of 5.4 ± 0.5% (mean ± standard deviation of four experiments) to 7.8 ± 1.3% and 9.0 ± 0.3%, respectively. Simultaneous application of dieldrin and H₂O₂ significantly increased cell lethality to 46.2 ± 1.8%. The synergistic increase in cell lethality was dependent on dieldrin concentration (0.3–5 μM) but not on H₂O₂ concentration (30–300 μM). Dieldrin accelerated H₂O₂-induced cell death, which was estimated with the help of annexin V-FITC and propidium iodide. Presence of either dieldrin or H₂O₂ decreased the cellular content of nonprotein thiol and increased intracellular Zn²⁺ concentration. The combination of dieldrin and H₂O₂ further pronounced these effects. TPEN, a chelator of intracellular Zn²⁺, significantly attenuated the synergistic increase in cell lethality induced by dieldrin and H₂O₂. It is, therefore, suggested that dieldrin augments the cytotoxicity of H₂O₂ in a Zn²⁺-dependent manner.     

TiO2膜降解水中污染物的稳定性考察与再生方法研究

针对实际水处理中对催化剂性能的要求，以光催化降解苯酚溶液作为探针反应，考察了玻璃纤维网上负载的TiO₂膜催化剂长期使用条件下的稳定性，研究了催化剂在自来水中使用失活后的再生方法。结果表明，经过50次使用之后，膜催化剂120 min反应对苯酚的降解率从100%下降至83%，总体上看，所制催化剂还是具有相当好的稳定性；在反应器中用蒸馏水浸泡配合光催化反应对TiO₂膜催化剂进行原位再生是一种可行的再生途径。     

Heterogeneous UV/Fenton degradation of bisphenol A catalyzed by synergistic effects of FeCo2O4/TiO2/GO

A new method for bisphenol A (BPA) degradation in aqueous solution was developed. The characteristics of BPA degradation in a heterogeneous ultraviolet (UV)/Fenton reaction catalyzed by FeCo₂O₄/TiO₂/graphite oxide (GO) were studied. The properties of the synthesized catalysts were characterized using scanning electron microscopy, X-ray diffraction, and vibrating sample magnetometry. FeCo₂O₄ and TiO₂ were grown as spherical shape, rough surface, and relatively uniform on the surface of GO (FeCo₂O₄/TiO₂/GO). Batch tests were conducted to evaluate the effects of the initial pH, FeCo₂O₄/TiO₂/GO dosage, and H₂O₂ concentration on BPA degradation. In a system with 0.5 g L⁻¹ of FeCo₂O₄/TiO₂/GO and 10 mmol L⁻¹ of H₂O₂, approximately 90 % of BPA (20 mg L⁻¹) was degraded within 240 min of UV irradiation at pH 6.0. The reused FeCo₂O₄/TiO₂/GO catalyst retained its activity after three cycles, which indicates that it is stable and reusable. The heterogeneous UV/Fenton reaction catalyzed by FeCo₂O₄/TiO₂/GO is a promising advanced oxidation technology for treating wastewater that contains BPA.

     

CNTs/TiO2/CS光降解苯的动力学

综合光催化氧化苯的动力学过程、光辐射场模型和质量守恒定律,采用平板型反应器建立了碳纳米管/二氧化钛/壳聚糖(CNTs/TiO2/CS)催化薄膜光催化氧化气相苯的数学模型;该模型考虑了光强、相对湿度、初始浓度与气体流速对气相苯光降解的影响。结果表明,建立的数学模型与实验结果吻合较好。