【作者】 陈世界；

【导师】 王鹏； 李英杰；

【作者基本信息】 哈尔滨工业大学 ， 环境科学与工程， 2014， 博士

【摘要】 新兴污染物的环境问题已经日益显现，开发对该类污染物的检测和处理技术具有重要的学术价值和实际意义。氟喹诺酮类抗生素(Fluoroquinolone antibiotics, FQs)是一类典型的新兴污染物，在不同环境水体中均有检出。本论文研究建立了诺氟沙星（NOR）和环丙沙星（CIP）二种FQs的荧光检测方法；制备出对可见光和Fenton反应具有良好响应的新型光催化剂C/Fe-BiVO4和C/Fe-Bi2WO6，建立光催化氧化处理NOR和CIP二种FQs的水处理方法和工艺，并探讨了其光催化作用机制。采用荧光猝灭法检测水中NOR。以中性红为探针分子，羟丙基-β-环糊精(HP-β-CD)与中性红形成包合物，从而使中性红的荧光强度大大增加，而NOR加入能够使NR-HP-β-CD体系的荧光猝灭，以此建立荧光猝灭法测定NOR的新方法。在优化条件下，NOR在0.02～0.4mg/L浓度范围内与荧光猝ΔF呈良好的线性关系，相关系数为: R2=0.9993；检出限为：6.1μg/L (S/N=3)，同时试验了常见金属离子与有机物对其测定的干扰，进行在胶囊和环境水样中NOR回收率试验以及含量测定。采用荧光探针法检测水中CIP。通过水热法合成L-半胱氨酸包覆ZnS微球，建立以L-半胱氨酸包覆ZnS微球荧光探针法测定CIP的新方法。在优化条件下，CIP在0.10～870μg·L-1浓度范围内与体系的荧光强度增加值ΔF呈良好的线性关系，相关系数为:线性方程为R2=0.9997，检出限为0.06μg·L-1(S/N=3)，同时试验了常见金属离子与有机物对其测定的干扰，进行在环境水样中CIP回收率试验以及含量测定。采用树脂碳化和水热两步法制备C/Fe-BiVO4光催化剂。对光催化剂的制备工艺进行优化，获得最佳制备参数为：水热反应温度180℃,水热反应时间24h,水热前驱物pH3,煅烧温度500℃,升温速率10℃/min,煅烧时间2h。利用EDX, XPS, XRD, SEM, BET, DRS, FT-IR, PL, Zeta电位等分析技术对催化剂的结构和化学性质等进行表征，并对其光催化性能进行评价。结果表明：制备的C/Fe-BiVO4催化剂为纳米级片状结构，具有良好的晶型，比表面积分别为17.76m2·g1，催化剂具有大孔和介孔的双孔结构。该催化剂具有良好的可见光吸收能力。以C/Fe-BiVO4光催化剂，以H2O2为氧化剂，对CIP具有良好的降解效果，且降解历程符合Landmuir-Hinshelwood(L-H)拟一级反应动力学模型，其反应动力学常数为0.1061min-1。采用树脂碳化和水热两步法制备C/Fe-Bi2WO6光催化剂，对光催化剂的制备工艺进行优化，获得最佳制备参数为：水热反应温度180℃,水热反应时间24h,水热前驱物pH11,煅烧温度500℃,升温速率10℃/min,煅烧时间2h。利用XRD, SEM, BET, EDX, XPS, DRS, FT-IR, PL, Zeta电位等分析技术对催化剂的结构和化学性质等进行表征，并对其光催化性能进行评价。结果表明：制备的C/Fe-Bi2WO6催化剂为纳米级片状结构，具有良好的晶型，比表面积分别为12.30m2·g1，催化剂具有大孔和介孔的双孔结构。该催化剂进一步提高了可见光吸收能力和Fenton技术在处理FQs污染物中pH值的使用范围。以C/Fe-Bi2WO6光催化剂，以H2O2为氧化剂，对NOR具有良好的降解效果，且降解历程也符合L-H拟一级反应动力学模型，其反应动力学常数为0.0751min-1。本文应用制备的C/Fe-BiVO4对CIP进行光催化氧化，通过单因素实验考察C/Fe-BiVO4去除CIP的影响因素。结果表明：C/Fe-BiVO4对CIP的去除率为96.18%;应用制备的C/Fe-Bi2WO6对NOR进行光催化氧化，通过单因素和中心复合实验设计的多因素实验对C/Fe-Bi2WO6去除NOR反应条件进行优化。结果表明：在最佳优化条件下，C/Fe-Bi2WO6对NOR的去除率达到了91.66%，TOC去除率也能达到60%。采用加入抑制剂的方法和分子荧光光谱法从定性和定量两个角度研究C/Fe-Bi2WO6光催化氧化去除NOR体系中羟基自由基的产生情况，通过不同工艺的对比证明C/Fe-Bi2WO6催化剂的加入对·OH自由基的生成量影响明显，其·OH自由基生成量远大于其它工艺，说明C/Fe-Bi2WO6光催化剂和Fenton技术二者存在协同效应，可大大提高H2O2氧化体系内·OH的生成量，从而增强对NOR的去除效率。结合LC-MS的分析结果，推测了NOR可能的降解路径和中间产物。更多还原

【Abstract】 Environmental problems of emerging contaminants have been increasingly obvious, developing corresponding detection and treatment technology are of great importance for academic research as well as for practical applications. Fluoroquinolone antibiotics (FQs) is a kind of typical emerging contaminants, having been detected in a variety of water bodies around the world. Herein, fluorescence detection methods of norfloxacin (NOR) and ciprofloxacin (CIP) were firstly established in the thesis. Novel photocatalysts of C/Fe-BiVO4and C/Fe-Bi2WO6were synthesized, with effective response to visible lights and Fenton reaction. The wastewater treatment method and process of those two FQs were established as well. In the end, the thesis discussed the photocatalysis mechanism.First, the fluorescence quenching method was used to test norfloxacin in water. With neutral red acted, as probe molecules, hydroxypropyl-beta-cyclodextrin (HP-β-CD) formed inclusion compound and thus fluorescence intensity of neutral red has greatly increased. On the other hand, addition of norfloxacin induced to the fluorescence quenching of NR-HP-β-CD system. A new detection method, with fluorescence quenching technique, of norfloxacin was invented accordingly. Under the optimal conditions, fluorescence intensity of the system presented good linear relationship with the concentration of NOR in the range of0.02～0.4mg/L, with correlation coefficient R20.9993, and the detection limit reached6.1μg/L (S/N=3). At the same time, the interferences from common metal ions and some organic matters were analyized. The recovery test and content determination of NOR were also carried out in environmental water samples.Second, the fluorescence probe method was used to test ciprofloxacin in water. L-cysteine coated ZnS microspheres was synthesized by hydrothermal method and a new approach of determining CIP is created based on fluorescent probe method of L-cysteine coated ZnS microspheres. Under the optimal comditions, fluorescence intensity of the system presented a good linear relationship with the concentration of CIP in the range of0.10～870μg·L-1, with the correlation coefficient R20.9997, and the detection limit reached0.06μg·L-1(S/N=3). The interferences from common metal ions and some organic matter were analyized as former. The recovery test and content determination of CIP were also carried out in environmental water samples.Moreover, the C/Fe-BiVO4photocatalyst was prepared by a two-step approach, involving resin carbonization and hydrothermal reaction process. Meantime, the preparation processes were optimized, which obtainted a set of best preparation parameters: the temperature of hydrothermal reaction is180℃, time of hydrothermal reaction is24h, pH value of hydrothermal precursors is3, calcining temperature is500℃, calcination velocity is10℃/min, calcining time is2h. The structure and chemical properties of the catalysts were characterized by EDX, XPS, XRD, SEM, BET, DRS, FT-IR, PL and Zeta potential analysis technology. Results showed the synthesized C/Fe-BiVO4catalysts have slice-shape nanostructures and good crystal structure, specific surface area17.76m2·g-1. The samples have macroporous and mesoporous structure. The catalyst has good visible light absorption ability. C/Fe-BiVO4acted and H2O2, as photocatalyst and oxidant respectively, performed good degradation effect for CIP. The degradation process complied with Landmuir-Hinshelwood (L-H) pseudo-first-order kinetics model, with the reaction kinetic constants0.1061min-1.Besides, the C/Fe-Bi2WO6photocatalyst was prepared by a two-step method, involving resin carbonization and hydrothermal reaction process. Meantime,the preparation processes were optimized, which obtainted a set of best preparation parameters: the temperature of hydrothermal reaction is180℃, time of hydrothermal reaction is24h, pH of hydrothermal precursors is11, calcining temperature is500℃, calcination velocity is10℃/min, calcining time is2h. The structure and chemical properties of the catalysts were characterized by XRD, SEM, BET, EDX, XPS, DRS, FT-IR, PL and Zeta potential analysis technology. The synthesized C/Fe-Bi2WO6catalysts are slice-shape nanostructures, good crystal structure, specific surface area12.30m2·g-1. The samples have macroporous and mesoporous structure. The catalyst can furtherly improve to absorb visible lights, and widen avaible pH range for Fenton treatment of FQs. The C/Fe-Bi2WO6and H2O2oxidant, as photocatalyst and oxidant respectively, performed good degradation effect for NOR. The degradation process comply with L-H pseudo-first-order kinetics model, with the reaction kinetic constants0.0751min-1.In the end, the prepared C/Fe-BiVO4as photocatalyst were conducted to the photocatalytic oxidation of CIP, some factors with respect to CIP removal were examined through the single factor experiment. The results show that the removal efficiency of CIP is96.18%; the prepared C/Fe-Bi2WO6as photocatalyst, were conducted to the photocatalytic oxidation of NOR, some factors about the removol of NOR were examined through the single factor experiment and the multivariate experimental design. The results show that the removal efficiency of NOR is91.66%, and the TOC removal efficiency is also able to reach more than60%under the optimum processing condition. Adopting the method of adding inhibitor and molecular fluorescence spectrometry from two aspects of qualitative and quantitative, we determined the production of hydroxyl radicals in the C/Fe-Bi2WO6photocatalytic oxidation to remove NOR system. The addition of C/Fe-Bi2WO6 catalyst have significant effect on the generation amount of·OH radical through comparing different process, proves that the generation amount of·OH radical is much larger than that of other processes, and further illustrated that there was a synergistic effect between the two photocatalyst and Fenton technology, and can greatly improve the·OH generation in H2O2oxidation system, thereby enhancing the removal efficiency of NOR. Combined with the analysis results of LC-MS, possible degradation paths and intermediate products of NOR were speculated.更多还原