分类号: X5 10710-2010129016 硕 士 学 位 论 文 改良型 ZnO 光催化剂的制备及其光催化降 解抗生素废水的研究 宋优男 导师姓名职称 关卫省 教授 申请学位级别 工学硕士 学科专业名称 市政工程 论文提交日期 2013 年 6 月 5 日 论文答辩日期 2013 年 6 月 19 日 学位授予单位 长安大学 Preparation of Supported ZnO Photocatalysts and Study on Photocatalytic Degradation of Antibiotic Wastewater A Dissertation Submitted for the Degree of Master Candidate：：Song Younan Supervisor：：Prof. Guan Weisheng Chang’an University, Xi’an, China I 摘摘 要要 抗生素废水为难处理工业废水，排入水环境中会对生态平衡和人类健康造成危害 半导体光催化技术具有反应条件温和、净化彻底、绿色环保、经济高效的优点，适宜于 抗生素废水的处理。
ZnO 是一种光催化活性高，价格低廉的半导体光催化剂，在水污染 控制方面有较大的应用潜力本论文以改进传统 ZnO 纳米催化剂的光催化性能为目的， 分别制备了过渡金属离子掺杂 ZnO 光催化剂、多壁碳纳米管负载 ZnO 光催化剂、埃洛 石纳米管负载 ZnO 光催化剂、PVC 合金超滤膜负载 ZnO 光催化剂采用 X 射线衍射仪 （XRD） 、扫描电子显微镜（SEM） 、透射电子显微镜（TEM） 、紫外–可见漫反射吸收光 谱（UV–Vis）等手段对制得样品进行表征，探讨了过渡金属掺杂 ZnO 光催化剂和负载 型 ZnO 光催化剂的物理、化学特性和光催化性能 （1）利用水热合成法制备了 Fe、Co、Ni 单一掺杂和 Fe–Co、Fe–Ni 共掺杂的过渡 金属离子掺杂ZnO复合光催化剂 Fe离子掺杂的ZnO催化剂、 Fe–Co离子共掺杂与Fe–Ni 离子共掺杂的 ZnO 催化剂较纯 ZnO 光催化剂的催化效果有所提高表征结果表明，过 渡金属掺杂使 ZnO 光催化剂吸收光谱红移，纳米 ZnO 有了响应可见光的能力制得样 品中 3%Fe–1%Ni/ZnO 材料的光催化活性最好，在 300W 氙灯光源（250nm~800nm）下 反应 2h 对盐酸四环素的降解率达 87.95%。
（2）采用溶胶法合成了 ZnO/碳纳米管复合光催化材料通过溶胶法制得了在碳纳 米管（CNTs）表面均匀、致密包覆 ZnO 纳米颗粒的复合材料ZnO/CNTs 复合材料光 催化活性较纯 ZnO 有显著提高， 这主要归功于复合材料良好的吸附性能， 其在 300W 氙 灯光源（250nm~800nm）下反应 2h 对盐酸四环素的降解率达 82.38%由于碳纳米管良 好的化学稳定性，优异的电学性能及吸附性能，复合材料能提高 ZnO 在酸碱溶液中的 稳定性并能有效抑制 ZnO 的光腐蚀 （3）采用溶胶法合成了 ZnO/埃洛石纳米管复合光催化材料观察发现，ZnO 不能 附着在埃洛石纳米管（HNTs）管壁上生长，而是独立成核生长成纳米颗粒ZnO/HNTs 材料的光催化活性高于纯 ZnO，在 300W 氙灯光源（250nm~800nm）下反应 2h 对盐酸 四环素的降解率为 77.07%而且由于埃洛石纳米管优良的吸附性能，ZnO/HNTs 复合材 料能抑制 ZnO 的光腐蚀，在重复利用数次后仍保持良好的光催化活性 （4）利用硅烷偶联剂作为粘结剂，采用超声处理法制备了 PVC 超滤膜负载纳米 ZnO 颗粒的复合光催化材料。
SEM 图像显示在 PVC 超滤膜表面负载了一层 ZnO 颗粒， II 负载ZnO纳米颗粒后， 复合光催化材料有了利用紫外光进行光催化降解的能力 在300W 氙灯光源（250nm~800nm）下反应 2h 对盐酸四环素的降解率为 54.35%，ZnO/PVC 复合 材料对盐酸四环素的降解能力低于纯 ZnO 纳米颗粒但复合光催化材料有着良好的抵 御光腐蚀的能力，经过数次回收利用后，其光催化活性几乎不变，优于纯 ZnO 光催化 剂 本文制备了四种改良型 ZnO 光催化剂，所制备的材料对抗生素有较高的降解效率， 在实际抗生素废水处理领域有良好的应用前景 关键词：关键词：ZnO，，光催化降解光催化降解，，抗生素废水抗生素废水，，过渡金属过渡金属，，掺杂掺杂，，负载型光催负载型光催化剂化剂 III Abstract Antibiotic wastewater is a kind of untreatable wastewater, which was discharged into water environment will cause harm to the ecological balance and human health. Semiconductor photocatalytic oxidation process is deemed as an ideal treatment technology for antibiotic wastewater because it exhibits outstanding superiority such as mild reaction conditions, thorough purification, environmental protection, high economic efficieney, and etc. ZnO has great potential applications in the field of environmental pollution control due to its high photocatalytic activity and low cost. In this article, transition metal doped ZnO photocatalysts; ZnO nanoparticles coated on carbon nanotubes photocatalysts; ZnO nanosphere coated on halloysite nanotubes photocatalysts; ZnO nanoparticles coated on PVC alloy ultrafiltration membrane photocatalytic materials were prepared via different methods. The as-obtained products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM) and ultraviolet and visible diffuse reflectance spectra (UV–Vis DRS). Their main physical properties, chemical properties and photocatalytic activity were discussed. (1) Fe doped, Co doped, Ni doped and Fe–Co codoped, Fe–Ni codoped ZnO photocatalysts were prepared via a hydrothermal synthesis method. Fe doped ZnO samples, Fe–Co codoped and Fe–Ni codoped ZnO samples have shown greater photocatalytic performance than pure ZnO photocatalysts. The characterization results showed that absorbance spectra of ZnO had a red shift with doping of doping of transition metal, which give ZnO ability of using visible light. And photocatalytic activity of 3%Fe–1%Ni/ZnO is highest. The photocatalytic degradation of tetracycline hydrochloride reached 87.95% in 2 hours under the irradiation of xenon lamp light (λ=250nm~800nm). (2) ZnO/CNTs composite photocatalysts were prepared by a sol method. The characterization results showed that a dense layer of ZnO nanoparticles cover on carbon nanotubes. Attributed to the excellent adsorption ability, photocatalytic activity of ZnO/CNTs was higher than that of pure ZnO. The photocatalytic degradation of tetracycline hydrochloride reached 82.38% in 2 hours under the irradiation of xenon lamp light (λ=250nm~800nm). The ZnO/CNTs samples showed higher stability in extreme pH values IV solution, photocorrosion suppression of ZnO was also be suppressed. It benefited from the excellent chemical stabilities, electrical properties, and adsorption abilities of CNTs. (3) ZnO/HNTs composite photocatalysts were prepared via a sol method. The characterization results showed that ZnO crystal grown into nanoparticles without HNTs. The photocatalytic degradation of tetracycline hydrochloride reached 77.07% in 2 hours under the irradiation of xenon lamp light (λ=250nm~800nm). Attributed to the excellent adsorption ability, photocatalytic activity of ZnO/HNTs was higher than that of pure ZnO. ZnO/HNTs also showed a great photocatalytic activity after reused for multiple times. (4) ZnO n。