【作者】 林婵；

【导师】 曹立新；

【作者基本信息】 中国海洋大学 ， 海洋化学工程与技术， 2014， 博士

【摘要】 近年来随着纺织工业的发展和个人护理用品、杀虫剂、表面活性剂、药物等的滥用，大量的废水被排放到河流中，对人类的生存造成了严重的威胁。通常废水的处理方法包括物理处理法、化学处理法、物理化学处理法和生物处理法。半导体光催化技术处理废水是近年来兴起的新的废水处理方法，其基本原理是用半导体作光催化材料,当用具有一定能量的光线照射时，光敏半导体材料被光激发出电子-空穴对，而吸附在半导体表面的水以及污染物的分子接受光生电子-空穴对，从而发生一系列的氧化还原反应，使有毒、有色的污染物降解为无毒或者毒性较小的物质的一种处理方法。在众多的催化剂中，TiO2因其化学稳定性高、耐光腐蚀、氧化能力强、光催化反应驱动力大、光催化活性高，可使一些吸热的化学反应在被光辐射的TiO2表面得到实现和加速，加之无毒、成本低，所以TiO2的光催化研究最为活跃。但TiO2较大的禁带宽度和较高电子空穴复合几率限制了其的光催化效率。要克服这些缺点需要对TiO2纳米材料进行改性。围绕该方向，我们的主要开展了以下工作：（1）采用阳极氧化法在水和丙三醇的混合电解液中制备出了排列有序的TiO2纳米管阵列，考察了不同的制备参数（电解液组成、阳极氧化时间和阳极氧化电压）对TiO2纳米管阵列形貌的影响。对于制备过程中形成的竹节状TiO2纳米管阵列，通过考察不同制备参数对竹节形貌的影响，提出了竹节状TiO2纳米管阵列的形成机理。对于在不同的阳极氧化时间和阳极氧化电压下制备出的不同管长和管径的TiO2纳米管阵列，通过光催化降解茜素红的实验考察了不同形貌TiO2纳米管阵列的光催化性能，并通过不同的热处理条件，考察了不同晶型TiO2纳米管阵列的光催化性能。（2）利用电化学沉积法制备出了Zr掺杂TiO2纳米管阵列。通过考察不同沉积电压和电解液浓度找出最优的沉积条件；通过UV-Vis漫反射光谱考察了Zr掺杂TiO2纳米管阵列的光吸收性能；通过在紫外光下光催化降解茜素红溶液考察了Zr掺杂TiO2纳米管阵列的光催化性能。（3）对TiO2纳米管阵列进行半导体复合，通过热处理法和连续化学沉积法制备出TiO2/ZnO/CdS纳米复合材料。通过考察不同沉积次数找出最优的复合层数；通过UV-Vis漫反射光谱考察了纳米复合材料的光吸收性能；通过在紫外光下光催化降解茜素红溶液考察了纳米复合材料的光催化性能。（4）通过两相水热合成法制备出直径在5nm左右、具有荧光性能的TiO2纳米颗粒。在此基础上，在C纳米颗粒的溶液中制备出碳杂化的TiO2纳米颗粒。通过UV-Vis吸收光谱考察了C-TiO2纳米颗粒的光吸收性能；通过荧光光谱考察了C-TiO2纳米颗粒的光致发光性能；通过X-射线光电子能谱考察了C-TiO2纳米颗粒的表面元素种类、化学状态和电荷分布；通过在紫外光下光催化降解亚甲基蓝溶液考察了C-TiO2纳米颗粒的光催化性能。C-TiO2的X-射线光电子能谱和荧光光谱表明，与TiO2纳米颗粒相比，碳与TiO2之间有电子相互作用，这一特性导致了C-TiO2纳米复合材料在光催化降解亚甲基蓝的过程中催化活性的显著提高。（5）将两种带不同配体的Ru纳米颗粒通过两相水热合成法与TiO2纳米颗粒反应，得到Ru-TiO2纳米颗粒。通过UV-Vis吸收光谱考察了Ru-TiO2纳米颗粒的光吸收性能；通过X-射线光电子能谱考察了Ru-TiO2纳米颗粒的表面元素种类、化学状态和电荷分布；通过在紫外光下光催化降解亚甲基蓝溶液考察了Ru-TiO2纳米颗粒的光催化性能。（6）将前面制备的TiO2纳米颗粒与HAuCl4进行水热合成反应，然后用抗坏血酸还原，得到Au-TiO2纳米复合材料。通过调节HAuCl4的量得到不同Au负载量的Au-TiO2纳米复合材料；通过X射线光电子能谱计算得到每个样品的Au含量；通过循环伏安法对Au-TiO2纳米复合材料在氧还原反应中的电催化活性进行了测试；通过在紫外光下光催化降解亚甲基蓝溶液考察了Au-TiO2纳米复合材料的光催化性能。（7）通过水热法制备出TiO2纳米薄片。将得到的纳米薄片用NaOH溶液进行清洗，通过清洗前后TiO2纳米薄片在紫外光下对甲基橙溶液、亚甲基蓝溶液、罗丹明溶液和甲基紫溶液的光催化降解情况，比较了表面含F与无F的TiO2纳米薄片对不同染料的光催化活性。更多还原

【Abstract】 To date, with the development of textile industry and the abuse of personal careproducts, pesticide, surface active agent and drugs, a large amount of wastewater hasbeen discharged into rivers, causing serious threat to human survival. The common usedmethods for wastewater treatment includs physical process, chemical treatment, physicaland chemical treatment and biological treatment. Semiconductor photocatalytictechnology is an emerging approach for wastewater treatmen in recent years. The basicprinciple is to use semiconductor photocatalytic materials, combined with certain energyof light, electron-hole pairs were inspired, and the water and pollutant moleculesadsorbed on the surface of semiconductor accept the electronic-hole pair inspired by thelight, causing a serious of oxidation-reduction reaction, degrading the toxic and coloredpollutants into non-toxic or low toxicity products. Among various catalysts, TiO2photocatalyst is the most active studied due to its high chemical stability, resistance tocorrosion, strong oxidation, light catalytic reaction driving force, high photocatalyticactivity, non-toxic and low cost, which can realize and accelerate the endothermicchemical reaction on the surface of TiO2under irradiation. Unfortunately, the largebandgap and high electron hole recombination limit the photocatalytic efficiency. Toovercome these shortcomings, the modification of TiO2nanomaterials is of greatimportant. Surrounding the direction, our mainly works are listed below:(1) Well-ordered TiO2nanotubes array was prepared by anodic oxidation method inthe mixture electrolyte of water and glycerol. The influence of synthesis parameters (suchas electrolyte composition, anodic oxidation time and voltage etc.) on the morphology ofTiO2nanotubes array was discussed. For the bamboo-type TiO2nanotubes array appearedin the experiment, we investigated the influence of synthesis parameters and proposed thepossible formation mechanism of bamboo-like TiO2nanotubes array. For the TiO2nanotubes array prepared under different anodic oxidation time and voltage with differentnanotube length and diameter, we investigated the photocatalytic performance of TiO2nanotubes array with different morphology by photocatalytic degradation of alizarin red. Besides, the influence of different crystal type on the photocatalytic performance of TiO2nanotubes array was also investigated by photocatalytic degradation of alizarin red.(2) Zr doped TiO2nanotubes array were prepared by electrochemical depositionmethod. The optimal deposition conditions were found out by investigating differentdeposition voltage and electrolyte concentration; the optical absorption property of Zrdoping TiO2nanotubes array was investigated by UV-vis diffuse reflectance spectrum;the photocatalytic performance was investigated by photocatalytic degradation of alizarinred under UV light irradiation.(3) TiO2/ZnO/CdS nanocomposite was prepared by heat treatment method andsuccession chemical deposition method. The optimal deposition layer was found out byinvestigating different deposition times; the optical absorption property was investigatedby UV-vis diffuse reflectance spectrum; the photocatalytic performance was investigatedby photocatalytic degradation of alizarin red under UV light irradiation.(4) TiO2nanoparticles with the diameter of5nm and also fluorescence propertywere prepared by two phase hydrothermal synthesis method. On this basis, carbonhybridization TiO2nanoparticles were prepared in carbon nanoparticle solution. The XPSand PL tests indicated that there are electrons interactions exist between C and TiO2in C-TiO2nanomaterial, causing the great improvement in photocatalytic activity.(5) Ru-TiO2nanoparticles were prepared with the reaction of Ru nanoparticles andTiO2nanoparticles by two phase hydrothermal synthesis method. The optical absorptionproperty of Ru-TiO2nanoparticles were investigated by UV-vis diffuse reflectancespectrum; the photocatalytic performance was investigated by photocatalytic degradationof methylene blue under UV light irradiation.(6) Au-TiO2nanocomposite was prepared by reacting TiO2nanoparticles withHAuCl4through hydrothermal synthesis method following by reduction with ascorbicacid. The loading amount of Au was adjusted by changing the amount of HAuCl4and theamount of Au loading was calculated by x-ray photoelectron spectroscopy; the electro-catalytic property during the oxygen reduction reaction was tested by cyclic voltammetrymethod; the photocatalytic performance was investigated by photocatalytic degradationof methylene blue under UV light irradiation. (7) TiO2nanosheets were prepared by hydrothermal method. The TiO2nanosheetswere washed with NaOH solution. The photocatalytic performance of TiO2nanosheetsbefore and after washed with NaOH solution was investigated by photocatalyticdegradation of methyl orange, methylene blue, rhodamine and methyl violet under UVlight irradiation. The photocatalytic activity of F on the TiO2nanosheets surface todifferent dyes was studied.更多还原