【作者】 汪瑾徽；

【导师】 赵宗彬；

【作者基本信息】 大连理工大学 ， 功能材料化学与化工， 2009， 硕士

【摘要】 开发高比表、高活性、可见光响应的高效光催化材料是光催化领域的研究热点,人们对TiO₂光催化剂的掺杂、贵金属沉积、负载等改性方法进行了广泛研究。多孔空心球材料、核壳结构材料和大孔材料具有稳定性好、密度低、比表面积大等特性,在催化反应、光电子器件、环境保护等领域应用前景广阔。本论文结合水热、溶胶-凝胶、模板等合成技术,合成了以TiO₂为主的一系列半导体金属氧化物的多孔空心球、核壳和大孔结构光催化剂。研究了不同催化剂的的形貌、结构、组成及光催化性能,采用扫描电镜、透射电镜、X射线衍射、红外、热重-同步热差和紫外-可见吸收光谱等技术手段进行了表征。在紫外光照射条件下以亚甲基蓝溶液的光催化降解为探针反应,考察了产品的光催化活性。主要结果如下:1.设计了一种小巧智能型悬浮式光催化反应装置,具有光照强度均匀、光利用率高、传质速率快、反应时间自动控制、取样快捷方便和安全可靠等优点,能够较为科学准确地研究光催化剂的活性和光催化反应的影响因素。2.用葡萄糖为原料,水热合成了富含活性官能团的炭微球模板,利用沉积-表面反应法制备了锐钛矿型TiO₂、WO₃和W掺杂TiO₂空心球,考察了W掺杂量和煅烧温度对W-TiO₂空心球的光催化活性的影响;溶胶-凝胶法制备了TiO₂多孔光催化剂,研究了炭微球用量对其光催化活性的影响。3.用葡萄糖和AgNO₃为原料,水热合成了富含活性官能团的Ag@C核-壳微球模板,沉积-表面反应法制备了Ag/TiO₂、Ag/AgCl/TiO₂和Ag/WO₃空心球催化剂,溶胶-凝胶法制备了Ag/NiO、Ag/SnO₂和Ag/WO₃具有大孔结构的材料。4.利用分散聚合法制备出单分散PS微球,用浓硫酸改性得到磺化PS微球。以其为模板,在水热条件下合成了Fe-TiO₂-PS、Fe-TiO₂、α-FeO（OH）-PS和α-Fe₂O₃空心球催化剂,研究了Fe掺杂量对Fe-TiO₂空心球光催化活性的影响;结合模板法和溶胶凝胶法,制备了大孔TiO₂光催化剂,考察了煅烧温度其光催化活性的影响。5.用溶胶-凝胶法制备了SiO₂粒子和纳米Ag粒子修饰的Ag/SiO₂复合粒子,以葡萄糖为炭源通过水热反应对Ag/SiO₂进行炭包覆,得到表面富含活性官能团的Ag/SiO₂@C核壳结构粒子,以其为模板制备出了Ag/SiO₂@TiO₂核壳结构催化剂,并对其光催化活性进行了研究。更多还原

【Abstract】 Nowadays,the creation of effective photocatalytic materials with large specific surface area,high catalytic activity,visible-light-respond,become a hot topic in photo-catalytic research.The modifications of TiO₂ photocatalyst is studied widely,such as metallic or non-metallic doping,noble metal depositing as well as supported TiO₂.Porous hollow sphere materials,core-shell structure materials and macroporous materials with good stability,low density,large specific surface area and other characteristics,have promising applications in the catalytic reaction,optoelectronic devices,and environmental protection.In this paper,combined hydrothermal with so-gel and template methods,a series of TiO₂-based photocatalysts were successfully synthesized,including porous hollow spheres, core-shell structure and macroporous materials.The structures,morphologies and compositions of the samples were characterized by SEM,TEM,X-ray diffraction, TGA-SDTA,FT-IR spectrometer and UV-Vis spectrophotometer.The photo-catalytic activities of the products were evaluated via the photo-catalytic degradation of methyl blue under UV-light irradiation.The main results are summarized as follows:1.A smart and compact floating-type photocatalytic reactor was designed,with the advantages of uniform light intensity,high light utilization and high mass transfer rate,reaction time automatic controlling,sampling convenience,safety and reliability.It can be used to investigate photo-catalyst activities and photocatalytic reaction factors scientifically and accurately.2.Carbonaceous micro-sphere templates with rich oxygen-containing groups on their surface were synthesized under hydrothermal condition using glucose as starting materials. TiO₂,WO₃ and W doped TiO₂ porous hollow spheres were prepared through template-deposition-surface reaction method.The influence of W contents and calcination temperatures on the catalytic activites of W doped TiO₂ porous hollow spheres was systematically examined.TiO₂ macroporous catalyst was prepared by so-gel method,and the relationship between its photocatalytic activity and the amount of carbon microspheres used was also investigated.3.Ag@C core-shell micro-spheres with rich oxygen-containing groups on their surface were synthesized under hydrothermal condition using glucose and AgNO₃ as starting materials.With Ag@C as templates,deposition-surface reaction was used to prepare Ag/TiO₂, Ag/AgCl/TiO₂ and Ag/WO₃ porous hollow spheres,while so-gel method was used to prepare Ag/NiO,Ag/SnO₂ and Ag/WO₃ macroporous materials.4.Monodisperse polystyrene（PS） microspheres were synthesized through dispersion polymerization method,and their surface was modified by concentrated sulfuric acid.With the sulfonated PS microspheres as templates,Fe-TiO₂-PS,Fe-TiO₂,α-FeO（OH）-PS andα-Fe₂O₃ porous hollow microspheres were successfully prepared under hydrothermal condition.The influence of Fe-doped amount on the photocatalytic activity of Fe-TiO₂ porous hollow microspheres was also examined.5.Monodisperse SiO₂ microspheres were prepared by Stober method,then Ag nanoparticles were deposited on their surface by Ag⁺ reduction in aqueous solution, carbonaceous materials was sequentially encapsulated on Ag/SiO₂ microspheres with glucose as the carbon precursor during hydrothermal process to form Ag/SiO₂@C microspheres.With Ag/SiO₂@C microsphere as templates,Ag/SiO₂@TiO₂ composites were successfully fabricated with template-deposition-surface reaction method.The photo-catalytic activity of the obtained Ag/SiO₂@TiO₂ was investigated.更多还原