Effect of crystalline structure on terbuthylazine degradation by H2O2-assisted TiO2 photocatalysis under visible irradiation

Various methods for shifting the optical response of TiO₂ into the visible (Vis) range have been reported. Herein, we reported the application of a TiO₂/H₂O₂/Vis process and the effects of TiO2 crystalline structure on the degradation of terbuthylazine. The results indicated that TiO₂ crystalline structure and H₂O₂ addition had significant effects on terbuthylazine degradation: its degradation rate could be increased from 7% to 70% with H₂O₂ addition after 180?min of reaction, the synergistic degradation of terbuthylazine by TiO₂-Fe^{3 +} was substantially accelerated, with the degradation rate reaching up to 100% after 20?min of reaction, and rutile TiO₂ showed better photocatalytic activity and a more obvious synergistic effect than anatase TiO₂. The addition of free-radical scavengers (tert-butyl alcohol or methanol) inhibited the degradation efficiency of rutile TiO₂, but had a relatively minor effect on anatase TiO₂. Fluorescence spectrophotometry analysis indicated that hydroxyl free radicals could be continuously produced when using rutile TiO₂ as the photocatalyst. Degradation of terbuthylazine catalyzed by rutile TiO₂ occurred mainly in solution, but occurred on the particle surface of the photocatalyst when catalyzed by anatase TiO₂. This study provides new insight into the role of TiO₂ crystalline structure on the degradation of terbuthylazine and its photocatalytic degradation mechanism.     

Effects of elevated CO_2 on sensitivity of six species of algae and interspecific competition of three species of alga

Introduction The atm ospheric C O 2 concentration increases at a rate of 1.5 滋 m ol/(m ol·a) and w ill double com pared to pre-industrial levels around the year 2050 (W atson et al., 1990). Its effects and m echanism by elevated CO 2 on global clim ate,…     

焦化废水外排水的TiO2光催化氧化深度处理及有机物组分分析

采用TiO₂光催化氧化法对焦化废水外排水进行深度处理,考察反应时间,TiO₂投加量及废水初始pH对TOC降解的影响,通过GC/MS技术对处理前后废水中的有机物组分进行定性分析,解析废水在TiO₂光催化氧化过程中有机物的降解规律. 结果表明:在反应时间为3 h,TiO₂投加量为4 g/L,以及不调节废水pH的条件下,焦化废水外排水经TiO₂光催化氧化深度处理后TOC的去除率为53.40%,有机物种类由66种降为23种;TiO₂光催化氧化法对除多环芳烃外的其他有机物均有较好的去除效果;不同种类有机物在TiO₂光催化氧化过程中的降解速率为石油烃>醇、酸、醛等有机物>酚>苯系物>含氮杂环有机物>多环芳烃.      

离子对氧化铁纳米颗粒水中聚集作用的影响

研究了不同电解质(NaCl、CaCl2、KCl、K2SO4和K2CrO4)对氧化铁纳米颗粒(Fe2O3NP)聚集作用的影响,并用聚集效率来衡量聚集作用变化,用DLVO理论对各因素的影响进行解释.实验表明:浓度和价态的升高会显著增强NP的聚集作用;阴离子对NP聚集作用的影响强于阳离子(以KCl为对照,K2SO4引起了比CaCl2更显著的变化);K2CrO4的影响显著大于其他离子(0.5mmol/L的K2CrO4即可引起剧烈的聚集).通过DLVO理论发现:离子在较低浓度增长或价态的上升,会同时降低ζ电位和双电层厚度以促进聚集作用;阴离子和K2CrO4较阳离子,会更显著地降低ζ电位,从而加速聚集作用;浓度在较高区间变化时ζ电位相对稳定,此时双电层的压缩是促进聚集作用的主要原因.     

TiO2光催化剂的改性研究

采用浸渍法制备了掺杂Fe3+ ,用NH4 Cl提高单分散性并且用稀H2 SO4 表面修饰的TiO2 粉体光催化剂 ,考察了它与TiO2 在紫外光和日光作用下对直接耐晒黑G的降解效果。结果表明 ,以TiO2 干凝胶为母体 ,依次浸渍Fe3+ 、NH+ 4以及SO2 - 4所制备的粉体光催化剂Fe3+ /SO2 - 4/TiO2 在紫外光作用下降解效果比纯TiO2 高 2 .1倍 ,在日光作用下比TiO2 高 1 .9倍。X射线衍射分析表明 ,该法制备的TiO2 粉体中锐钛矿相占 1 0 0 % ,没有金红石相 ,平均晶粒粒径为 4nm ;红外吸收光谱分析表明 ,无论是纯TiO2 还是经过掺杂Fe3+ 、用H2 SO4 进行表面修饰后的TiO2 ,红外吸收光谱图基本相似 ,说明掺杂和表面修饰并没有极大地改变TiO2 的化学结构 ,光催化性能的提高归属于杂质能级的电子捕获陷阱作用、有效光成分增加和光生电子向反应物的迅速转移     

ZnFe_2O_4/TiO_2光催化剂制备及乙酰甲胺磷降解性能研究

分别采用共沉淀法和溶胶-凝胶法制备了ZnFe2O4和掺杂ZnFe2O4的纳米级TiO2光催化剂,进行了XRD、TEM和UV visDRS表征,以卤素灯为光源对纳米TiO2降解水溶液中乙酰甲胺磷农药进行了研究。考察了反应液初始pH值、催化剂用量、H2O2用量对降解率的影响。实验结果表明,焙烧温度为400℃、掺杂量为0.5%的ZnFe2O4/TiO2纳米粉体降解效果最佳,在相同条件下,反应2h后农药降解率可比纯TiO2提高20%左右。正交实验优化了降解反应条件,在常温常压下,起始pH值为12、H2O2浓度为12mmol/L、催化剂浓度为0.5g/L、反应3h后,初始浓度为1.0×10-4mol/L的乙酰甲胺磷农药降解率可达61.2%。     

纳米TiO2/硅藻土光催化降解蒽醌染料废水的研究

为提高光催化剂的稳定性,选取硅藻土为载体,以钛酸四异丙酯为前驱物,采用溶胶-凝胶法制备了TiO2/硅藻土光催化剂,并利用XRD、SEM、FT-IR等技术对其进行表征.以蒽醌染料弱酸性艳蓝RAW为目标降解物,考察了TiO2/硅藻土的光催化活性、最佳pH值范围及催化剂重复使用对光催化活性的影响.结果表明,所制备的TiO2为锐钛矿和金红石混晶型,平均粒径11nm,通过控制硅藻土加入量可以得到负载均匀的光催化剂.所制备的TiO2/硅藻土具有较强的光催化活性,对弱酸性艳蓝RAW的降解效果好于商品Degussa P25型TiO2,最佳pH值为4.0.该催化剂性质稳定,重复使用15次后,催化活性仅降低12.4%.     

Comparative toxicity of silver nanoparticles and silver ions to Escherichia coli

With the increase in silver(Ag)-based products in our lives, it is essential to test the potential toxicity of silver nanoparticles(Ag NPs) and silver ions(Ag ions) on living organisms under various conditions. Here, we investigated the toxicity of Ag NPs with Ag ions to Escherichia coli K-12 strain under various conditions. We observed that both Ag NPs and Ag ions display antibacterial activities, and that Ag ions had higher toxicity to E. coli K-12 strain than Ag NPs under the same concentrations. To understand the toxicity of Ag NPs at a cellular level, reactive oxygen species(ROS) enzymes were detected for use as antioxidant enzymatic biomarkers. We have also studied the toxicity of Ag NPs and Ag ions under various coexistence conditions including: fixed total concentration, with a varied the ratio of Ag NPs to Ag ions; fixed the Ag NPs concentration and then increased the Ag ions concentration; fixed Ag ions concentration and then increasing the Ag NPs concentration.Exposure to Ag NPs and Ag ions clearly had synergistic toxicity; however, decreased toxicity(for a fixed Ag NPs concentration of 5 mg/L, after increasing the Ag ions concentration) to E. coli K-12 strain. Ag NPs and Ag ions in the presence of L-cysteine accelerated the bacterial cell growth rate, thereby reducing the bioavailability of Ag ions released from Ag NPs under the single and coexistence conditions. Further works are needed to consider this potential for Ag NPs and Ag ions toxicity across a range of environmental conditions.Environmental Significance Statement: As silver nanoparticles(Ag NPs)-based products are being broadly used in commercial industries, an ecotoxicological understanding of the Ag NPs being released into the environment should be further considered. Here, we investigate the comparative toxicity of Ag NPs and silver ions(Ag ions) to Escherichia coli K-12 strain, a representative ecotoxicological bioreporter. This study showed that toxicities of Ag NPs and Ag ions to E. coli K-12 strain display different relationships when existing individually or when coexisting, and in the presence of L-cysteine materials. These findings suggest that the toxicology research of nanomaterials should consider conditions when NPs coexist with and without their bioavailable ions.     

CdS/TiO2复合半导体薄膜的制备及其光催化性能

以微弧氧化法制备出锐钛矿型TiO₂,进而以化学水浴法沉积CdS,通过调控时间,制备CdS/TiO₂复合半导体薄膜. X射线检测表明,微弧氧化所制备的TiO₂为锐钛矿结构, 化学水浴法制备的CdS主要以离子离子的方式沉积在TiO₂薄膜上. SEM及可见光催化降解亚甲基蓝的试验表明,沉积时间为15 min的复合半导体薄膜上的CdS粒子呈圆球形、单层孤立、均匀地分散在TiO₂表面,绝大多数粒子的粒径在nm级别,分布比较均匀,对亚甲基蓝有着较好的光催化性能,与TiO₂薄膜相比,复合半导体薄膜的光催化性能有很大的提高. 结合光催化评价结果,对复合半导体薄膜的光催化剂机制进行了讨论.      

UV/TiO_2/H_2O_2法对高浓度有机废水降解的应用研究

用UV TiO2 H2 O2 法对高浓度有机废水降解的实验表明 ,当TiO2 、H2 O2 的投加量分别为 2 0g与 1% ,反应时间为3h时 ,CODCr、Oil、Ar OH、NH3 N、S2 - 的平均去除率分别达到 73 %、83 %、86%、5 0 %、10 0 %。此处理工艺具有除臭、除色、快速高效、不产生污泥等优势。实验过程探索了TiO2 、H2 O2 的用量对各污染物降解率的影响 ,并设计了有实用意义的反应器     

Fe3+、Ce3+掺杂TiO2光催化降解气相二苯并呋喃

以气相二苯并呋喃为研究对象,考察了在TiO2、Ce3+/TiO2和Fe3+/TiO2 3种不同光催化剂作用下,反应物初始浓度、湿度、气体循环速率和光强等因素对间歇式光催化反应速率的影响,并建立了估算和测定二苯并呋喃光催化反应常数和Langmuir吸附常数的数学模型和方法.结果表明,Fe3+和Ce3+掺杂修饰TiO2光催化剂后,提高了对二苯并呋喃的光催化降解活性,其中Fe3+/TiO2光催化活性最高;随着二苯并呋喃初始浓度的增大,其光催化降解速率也随之增大;适量的水蒸气存在可以促进二苯并呋喃的降解,但当水蒸气过量后,反而阻碍二苯并呋喃光催化降解;随着气体循环速率加快和光强的增大,二苯并呋喃光催化降解初始速率也随之增大;TiO2、Ce3+/TiO2和Fe3+/TiO2光催化降解二苯并呋喃反应速率常数k分别为34.54×10-5、36.23×10-5和37.95×10-4mg.(min.m2)-1.     

漂珠为载体TiO_2/SiO_2膜的制备及性能研究

以漂珠为载体,探索采用液相沉积法制备TiO2/SiO2膜最佳条件。在自制的光催化反应器中,在相同的条件下,以酸性嫩黄和难处理的焦化废水为目标降解物,做了TiO2/SiO2和TiO2两种膜的光催化氧化对比试验。结果表明,与单一TiO2膜比较,以漂珠为载体,采用液相沉积法制备的TiO2/SiO2改性膜具有较高的光催化氧化性能。     

光/电/化学催化降解水中二甲基甲酰胺的反应特性

设计了以负载型TiO₂薄膜电极为阳极,以高纯多孔石墨为阴极,以饱和甘汞电极为参比电极的光/电/化学催化反应器,对二甲基甲酰胺(DMF)溶液进行降解. TiO₂/Ti薄膜电极能对阳极槽中的DMF进行降解;同时,阴极槽中产生的过氧化氢(H₂O₂)可与亚铁离子形成Fenton催化体系,对DMF溶液也具有良好的降解作用. 结果表明,在以0.02 mol/L的Na₂SO₄和0.01 mol/L的FeSO₄混合溶液作为支持电解质,初始pH为3.5,阴极电位(-E_c)为0.66 V,曝气强度为1.5 L/min和反应时间为60 min等的条件下,阳极槽和阴极槽中DMF的去除率分别达到85.10%和82.95%.      

Preparation of TiO_2/Ti mesh photoelectrode and properties

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Fulvic acid removal by nanoparticle TiO2 using a submerged membrane photocatalysis reactor

The degradation of fulvic acid（FA） by nanoparticle TiO2 in a submerged membrane photocatalysis（SMPC） reactor was studied. In this reactor, photocatalytic oxidation and membrane separation co-occured. The continuous air supplier provided O2 for the photocatalytical reaction and mixed the solution through an airflow controller. The particle TiO2 could automatically settle due to gravity without particle agglomeration so it could be easily separated by microfiltration（MF） membrane. It was efficient to maintain high flux of membranes. The effects of operational parameters on the photocatalytic oxidation rate of FA were investigated. Results indicated that photocatalyst at 0.5 g/L and airflow at 0.06 m^3/h were the optimum condition for the removal of fulvic acid, the removal efficiency was higher in acid media than that in alkaline media. The effects of different filtration duration on permeate flux rate of MF with P25 powder and with nanoparticle TiO2 were compared. Experimental results indicated that the permeate flux rate of MF was improved and the membrane fouling phenomenon was reduced with the addition of nanoparticle TiO2 catalyst compared with conventional P25 powder. Therefore, this submerged membrane photocatalysis reactor can faciliate potential application of photocatalytic oxidation process in drinking water treatment.     

长期暴露下纳米TiO2对厌氧颗粒污泥体系稳定性的影响

以厌氧颗粒污泥为研究对象,通过静态试验和连续流厌氧反应器,重点研究了长期暴露下纳米TiO_2在对厌氧产甲烷体系的影响及其在颗粒污泥中的归趋.结果表明,短期急性暴露于150 mg·g-1(以VSS计)的纳米TiO_2尽管会暂时减缓产甲烷速率,但产酸阶段及产甲烷阶段代谢产物总量不会明显受到影响,纳米TiO_2对厌氧颗粒污泥具有较低的急性毒性.反应器运行结果表明,纳米TiO_2的长期暴露可导致挥发性脂肪酸(VFAs)积累及生物气产量降低,产酸菌比产甲烷菌对纳米TiO_2的累积效应更加敏感,纳米TiO_2抑制机制可归因于"物理遮蔽"作用.出水中TiO_2的平均含量只有0.632 mg·L~(-1),绝大多数纳米TiO_2都被截留在了反应器中.FISH检测表明,厌氧颗粒污泥微生物的菌群结构有所变化,纳米TiO_2在反应器内的积累使得甲烷八叠球菌的丰度大幅增加了115.6%,其优势地位明显增强.长短期暴露试验的结果对比也说明,用短期暴露试验来说明纳米颗粒对厌氧体系的长期累积效应具有一定局限性,纳米TiO_2对厌氧颗粒污泥中微生物的负面影响需要较长时间的积累才会显现.本研究结果可为厌氧污水处理体系中纳米颗粒的潜在生态风险评价提供理论支持和参考依据.     

Co-adsorption of gaseous benzene, toluene, ethylbenzene, m-xylene (BTEX) and SO2 on recyclable Fe3O4 nanoparticles at 0-101% relative humidities

We herein used Fe3O4 nanoparticles(NPs) as an adsorption interface for the concurrent removal of gaseous benzene, toluene, ethylbenzene and m-xylene(BTEX) and sulfur dioxide(SO2), at different relative humidities(RH). X-ray diffraction, Brunauer–Emmett–Teller, and transmission electron microscopy were deployed for nanoparticle surface characterization.Mono-dispersed Fe3O4(Fe2O3·Fe O) NPs synthesized with oleic acid(OA) as surfactant, and uncoated poly-dispersed Fe3O4 NPs demonstrated comparable removal efficiencies.Adsorption experiments of BTEX on NPs were measured using gas chromatography equipped with flame ionization detection, which indicated high removal efficiencies(up to(95 ± 2)%) under dry conditions. The humidity effect and competitive adsorption were investigated using toluene as a model compound. It was observed that the removal efficiencies decreased as a function of the increase in RH, yet, under our experimental conditions, we observed(40 ± 4)% toluene removal at supersaturation for Fe3O4 NPs, and toluene removal of(83 ± 4)% to(59 ± 6)%, for OA-Fe3O4 NPs. In the presence of SO2, the toluene uptake was reduced under dry conditions to(89 ± 2)% and(75 ± 1)% for the uncoated and coated NPs, respectively, depicting competitive adsorption. At RH 100%,competitive adsorption reduced the removal efficiency to(27 ± 1)% for uncoated NPs whereas OA-Fe3O4 NPs exhibited moderate efficiency loss of(55 ± 2)% at supersaturation.Results point to heterogeneous water coverage on the NP surface. The magnetic property of magnetite facilitated the recovery of both types of NPs, without the loss in efficiency when recycled and reused.     

Ag/TiO2光催化降解H酸的研究

采用光化学沉积法制备了Ag TiO2 光催化剂 ,并对典型难生物降解的有机污染物H酸进行了光催化降解研究。结果表明 ,质量分数 1 0 %担载量的Ag能显著提高TiO2 光催化活性 ,可在较短时间内实现对H酸较高的降解效率     

典型纳米金属氧化物对氨氧化菌Nitrosomonas europaea的生物胁迫影响

对比研究了3种典型纳米金属氧化物颗粒(NPs,包括纳米TiO2(n-TiO2),纳米CeO2(n-CeO2)和纳米ZnO(n-ZnO))在不同作用浓度下(0,0.1,1,10,50mg/L)对污水生物脱氮系统中代表性氨氧化菌─ Nitrosomonas europaea连续作用6h的毒性效应及作用规律.结果表明,3种NPs对N.europaea的生物胁迫效应与其投加浓度均呈正相关.其中,50mg/L的n-CeO2, n-ZnO与对照组相比,可显著降低N.europaea细菌浓度,破坏细胞膜完整性,抑制氨氧化速率.相同浓度条件下, n-ZnO对N.europaea的毒性影响最大, n-TiO2影响最小.虽然n-ZnO释放的Zn2+对N.europaea具有明显的毒性效应,但n-ZnO及其产生的尺寸效应仍是其生物胁迫产生的重要来源.     

寒区水体中溶藻铜绿假单胞菌的分离和性质研究

我国北方,尤其是东北地区的一些水体由于富营养化导致的水华现象呈增加趋势,成为急需解决的水环境问题.溶藻菌可从生态调控的角度来控制水华的爆发,因此,在富营养化水体治理方面逐渐得到重视.本文从寒区水华爆发水体中分离获得了一株溶藻细菌JM1,系统发育分析表明,菌株JM1与铜绿假单胞菌的同源性最高.VITEK系统鉴定表明,菌株JM1与铜绿假单胞菌的相似度为98%.菌株JM1在不同的碳源和氮源培养基中可产生不同颜色和p H值的代谢产物,而以葡萄糖和蛋白胨分别为碳源和氮源时发酵液的溶藻效果明显好于其它培养基.菌株JM1的溶藻效果随藻细胞初始密度的降低而增强,随发酵液添加量的增加而增加;当菌体细胞的密度达到1011CFU·m L-1时,可单一抑制藻细胞的生长;当菌体细胞的密度大于105CFU·m L-1时,菌体细胞可促进发酵液的溶藻作用.发酵液作用于藻细胞6 h时可明显影响其恢复能力,当暴露时间达18 h时,藻细胞彻底丧失了恢复能力.菌株JM1发酵液在中性和偏碱性的藻液中的溶藻效果最强,并且经过酸化、碱化和高温处理后,仍然保持较高的溶藻活性.本研究可为基于微生物作用过程的水华控制提供优势的土著菌种及其应用上的技术支持.