【作者】 张格红；

【导师】 关卫省；

【作者基本信息】 长安大学 ， 市政工程， 2014， 博士

【摘要】 水污染一直是人们关注最多的环境问题，伴随着医药工业的快速发展，抗生素被发现存在于很多水源中。当抗生素被释放到水体中，会影响水生生物的生长，诱导抗药细菌的产生，毒性大、成分复杂、难于处理；同时抗生素废水中残留的抗生素所带来的负面效应对人体的健康造成了威胁，从而引起人们越来越多的关注。目前抗生素废水处理的手段主要有物理法、化学法、生物化学法等，但这些传统的处理技术或存在运行成本高、或带有二次污染等缺点，使得处理效果不能令人满意。光催化氧化技术是一种高级光催化氧化技术，是一种最有可能利用自然界太阳光实现清洁去污的环境友好技术，目前已成为人们关注较多的废水处理方法。在众多光催化材料中氧化物类光催化剂具有低廉、无污染、抗光腐蚀等优点被誉为环境友好的污染处理材料，在环保和节能的应用前景受到广泛的关注。但是很多氧化物本身也存在局限性，如光量子效率比较低、光催化降解缺乏选择性等。因此，近年来开发具有可见光响应能力强、光催化活性高、有选择性降解能力的低价带光催化剂成为了研究的热点。因此制备氧化物类光催化剂，并对该类光催化剂实施表面修饰以提高光催化剂的光催化效率及对可见光的响应能力。本论文研究主要包括以下内容：（1）水热法制备三氧化钨纳米片光催化剂及性能研究a.采用水热技术，在低温条件下制备纳米片状WO3，以罗丹明B和四环素废水溶液为模拟废水进行光催化降解试验。研究结果表明：低温条件下制备的光催化剂WO3在可见光下具有一定的催化活性。b.通过在材料的表面负载一层贵金属Pt作为电子的接受体来有效地分离电子和空穴。对WO3和Pt/WO3进行了光催化性能的对比实验表明Pt/WO3纳米片比WO3纳米片有着很明显的光催化增强的活动，同时研究了Pt/WO3光催化机理，通过活性物种捕获试验表明在光催化过程中羟基自由基是光催化过程中最主要的活性物种。（2）三氧化二铟光催化剂的制备及性能研究通过微波辅助水热法合成三氧化二铟立方块形貌和微球形貌。通过光降解性能分析可知，三氧化二铟立方块形貌具有可见光下降解四环素的性质。（3）微波辅助水热法制备三氧化二铋纳米管光催化剂及性能研究a.采用微波辅助水热技术，在低温条件下制备Bi2O3。以四环素废水和环丙沙星废水为模拟废水进行光催化降解试验。研究显示：低温条件下合成的光Bi2O3催化剂在可见光下具有较强的吸收并且在可见光下具有催化活性。b.合成的Bi2O3纳米管在可见光下表现出对四环素和环丙沙星的光降解率。在可见光照射下1小时内降解10mg/L和20mg/L的四环素降解率为83.63%和61.04%，而降解20mg/L环丙沙星的降解率仅为34.90%。结果显示：Bi2O3纳米管在降解四环素比降解环丙沙星有着更好的光催化性能，而且Bi2O3在光降解抗生素的过程中具有一定的选择性。（4）溶剂热法制备固溶体InxBi(2-x)O3微米球光催化剂及性能研究a.通过溶剂热法制备了固溶体InxBi2-xO3微米球，方法简单经济，无需添加表面活性剂等模板。通过制备过程中通过适当地改变反应参数及条件来研究固溶体InxBi2-xO3微米球的最佳形成条件。b.该固溶体InxBi2-xO3微米球在可见光下显示对四环素的光降解率。该物质与三氧化二铟和三氧化二铋的光催化性能进行对比。研究结果表明：固溶体InxBi2-xO3微米球比三氧化二铟和三氧化二铋有着明显的光催化增强的活动。同时研究了固溶体InxBi2-xO3微米球的光催化机理。通过活性物种捕获试验表明在光催化过程中空穴是光催化过程中最主要的活性物种。（5）快速水热制备的铁掺杂二氧化钛大孔光催化剂的制备及性能研究具有3D大孔结构Fe/Ti-M (1%、5%、10%和50%)可见光催化剂。调整Fe的掺杂量对Fe/Ti-M的晶体结构具有很重要的影响。当Fe的量与Ti的相等时，得到Fe3Ti3O10相。而且，Fe/Ti-M随着Fe的掺杂出现了红移现象，并进一步研究了Fe/Ti-M对四环素的光催化性能。结合晶体结构和吸收光谱，Fe/Ti-M（10%）表现了最优的光催化性能。更多还原

【Abstract】 Water pollution as a primary issue of environmental pollution attracts most attention.With the continuous development of medical industry, various kinds of antibodies have beenwidely found in different aquatic environments. After released into the environment,antibiotics will affect aquatic organisms and induce bacterial resistance.Also, it is difficult totreat antibodies due to its high toxicity and complicated composition. At the same time thenegative impact of antibiotics residue in water pose the risk to the health of human.Therefore, more and more attented have been paid to this serious issue. The treated methodsof waste water mainly included physics methods, chemical methods, biochemical methods, etal. Unfortunately, the conventional physical and chemical treatments are always high cost orhave seconded pollution which lack of enough efficiency for antibodies removal.Photocatalytic oxidation technology, as one of the AOPs (Advanced Oxidation Processes),is most likely to take advantage of natural sunlight for decontamination environmentallyfriendly, which may be an ideally method to realize removal of pollutant. Among thephotocatalytic material, oxide photocatalyst, as one friendly materials, have attracted mostattention for environmental protection and energy saving due to its low price, none pollutionto environment and resistance light corrosion. However, oxide photocatalyst has limitation forpractical application, such as low photons efficiency and lack of selectivity. Thus, to developstrong respond to visible light irradiation, high photocatalytic activity and low-band gapphotocatalysts becomes a research hotspot.Herein, we prepared and modified oxide photocatalyst to improve the photocatalyticefficiency of photocatalyst and responsiveness of visible light.The work mainly included the following items:(1) Hydrothermal synthesis of WO3nanosheets photocatalyst and the study onphotocatalytic performancea. In our work, we have successfully synthesized WO3nanosheets via a hydrothermalmethod under the condition of low temperature preparation and conducted photocatalyticdegradation test with Rhodamine B and tetracycline waste water solution. The results showedthat WO3nanosheets in visible light had catalytic activity.b. Pt decorated WO3nanosheets favors electron transfer process to improve the separationof electrons and holes effectively. Significant enhancement of activity has been clearly foundon Pt/WO3nanosheets compared with WO3nanosheets. The photocatalytic mechanism ofPt/WO3are studied at the same time, and the active species captured test indicated the·OH radicals do exist in the process of the photocatalytic oxidation (PCO) ofTC.(2) The synthesis and application research of indium trioxide of two differentmorphologies photocatalystBy microwave hydrothermal method and solution heat method indium trioxide cube andmicrospheres are synthesized respectively. The photodegradation performance analysisshowed that indium trioxide cube and microspheres has properties to photodegrade TC undervisible light.(3) Rapid microwave-assisted synthesis of Bi2O3tubes and photocatalytic properties forantibioticsa. Bismuth oxide (Bi2O3) nanotubes have been successfully synthesised via a rapidmicrowave-assisted synthetic method for the first time. Moreover, the photocatalyticproperties of Bi2O3in the degeneration of antibiotics, especially tetracycline (TC) andciprofloxacin (CIP), were studied. Our research showed that the prepared Bi2O3sample at lowtemperatures has a strong absorbency and has a perfect photocatalytical activity under visiblelight.b. We study the time-dependent degradation of TC and CIP by the same amount of Bi2O3under the same photocatalytic degeneration condition. The photocatalytic degeneration rate of10mg/L TC and20mg/L TC is83.63%and61.04%, respectively，and that of20mg/L CIPis only34.90%. We have found that it has better photocatalytic effect in the degeneration ofTC compared with CIP which means that Bi2O3has certain selectivity in the photocatalyticdegradation process of antibiotics.(4) Solvent thermal synthesis and photocatalytic degradation of waste water ofInxBi(2-x)O3microspherea. InxBi(2-x)O3microspheres were synthesized by solvothermal solution, The method issimple, economical, without adding a surfactant template. Through the preparation byappropriate changes in reaction parameters and conditions to investigate the optimalformation conditions of solid solution InxBi(2-x)O3microspheres.b. InxBi2-xO3microspheres showed high photodegradation rate of tetracycline undervisible light. Significant enhancement of activity has been clearly found on InxBi2-xO3microspheres compared with In2O3and Bi2O3. The photocatalytic mechanism of InxBi2-xO3isstudied at the same time, and the active species captured test indicated the holes do exist inthe process of the photocatalytic oxidation (PCO) of TC. (5)Titanium dioxide macroporous materials doped with iron: synthesis andphoto-catalytic propertiesFe/Ti-M (1%,5%,10%, and50%) with a3D macroporous structure has beensuccessfully synthesized. Tuning the doping quantity of Fe can significantly affect the crystalstructure of the resulting Fe/Ti-M. The obtained samples exhibited the Fe3Ti3O10phase whenthe quantity of Fe was equal to Ti. Moreover, the Fe/Ti-M showed a significant red shift inresponse to the doping of Fe. The photo-catalytic properties of Fe–Ti–Oxide-M were studiedunder visible light in-depth. Taking into account the crystal structure and absorption spectra,the Fe/Ti-M (10%) showed the optimal catalytic activity among the samples with differentdoping quantities of Fe in this system.更多还原