溶胶—凝胶工艺制备二氧化钛自清洁薄膜的研究
摘要
近十几年来，光催化氧化应用于环境污染物的治理已经成为环境科学研究的热点。半导体TiO_2作为一种性能优异的光催化材料，可将许多化学法、生物法无法降解的有机物完全降解为CO_2、H_2O及相应无机酸，且成本低廉，不造成二次污染，使其在废水处理、空气净化、杀菌以及自清洁和太阳能转化等方面有着十分诱人的前景。本论文对半导体光催化和亲水性的工作原理，存在问题及发展前景进行了综述，同时对二氧化钛(TiO_2)光催化的改性的研究进行了介绍。
由于TiO_2的带隙较宽(约3.2eV)，半导体的光吸收波长范围窄(主要在紫外区)，故其太阳能的利用效率低，且还存在半导体载流子的复合率高，量子化效率低等缺陷。本论文对玻璃表面TiO_2光催化薄膜作为自清洁薄膜材料进行了一系列探讨。从进行TiO_2掺杂改性和结构修饰着手，针对TiO_2自清洁性能有待提高的问题，用溶胶—凝胶浸置提拉法在玻璃基板上制备了掺HPC、掺硅、掺钒薄膜和钒、硅共掺杂，钒、铁共掺杂TiO_2薄膜，对它们的光催化性能和亲水性能作了系统的研究。
对掺HPC薄膜进行光催化活性和亲水性测试结果表明：适量(3m最佳)的HPC加入可以使二氧化钛颗粒的团聚程度降低，颗粒均匀分布，TiO_2晶粒纳米化，粗糙度增加，使TiO_2拥有更大的比表面积，使其光催化性能和亲水性均得到改善。其中3m的HPC改性的TiO_2薄膜经过紫外光照3h后表现为超亲水性。
对掺硅薄膜进行光催化活性和亲水性测试结果表明：硅掺杂提高了TiO_2薄膜光催化活性。但硅的添加量过大时，薄膜光催化活性下降，原因是产生无催化作用的二氧化硅。硅的加入对二氧化钛薄膜的亲水性没有明显影响。
对掺钒薄膜进行光催化活性和亲水性测试结果表明：掺钒后薄膜光学带隙变小，扩大了可利用光的范围，提高了TiO_2薄膜光催化活性。同时钒掺入产生电子空穴俘获阱，降低电子空穴复合，对光催化活性的提高也有贡献。而钒掺杂使TiO_2薄膜亲水性能显著提高，甚至在太阳光照下就具有亲水性。
另外，钒、硅共掺杂进一步提高了Ti_2薄膜光催化活性。选择更为合适的
浙江大学硕士毕业论文
刘琴华:溶胶.凝胶工艺制备二城化钦自清洁薄膜的研究
双离子共掺杂可能会更有效地提高TIO:的光催化。实验中发现共掺杂薄膜的亲
水性能不佳。
综上所述，本研究用溶胶凝胶制备了一系列改性的TIO:薄膜，对它们的自
清洁(光催化性能和亲水性性能)作了系统研究。研究结果发现，对光催化性能
而言，掺HPC、掺钒、掺硅和钒、硅共掺杂都对Tio:薄膜光催化活性有所提高，
但不是所有的改良都带来更好的亲水性。其中，3mHPC掺杂薄膜样品和x二0.巧
的钒掺杂薄膜光催化性能和亲水性性能都比未掺杂Tio:薄膜样品好，可作为自
清洁薄膜。
In recent decades, studies on photocatalysis have attracted considerable attention. Titanium dioxide (TiO2), which is one of the most basic materials in our daily life, has emerged as an excellent photocatalyst material for environmental purification. In this thesis, the history, principle, problems and prospect of the photo induced super-hydropholicity and photocatalytic activity of TiO2 films are reviewed. At the same time, the modifying methods of TiO2 photocatalytic are introduced.
Because of the anatase's broad Eg (3.2eV), the absorption thresholds correspond to 380nm for the TiO2. Consequently, only the ultraviolet fraction of the solar irradiation can be active in the photoexcitation processes using pure TiO2 solid. The high recombination rate of Charge carrier and low efficiency of quantization are also the deficiencies of pure TiO2. This thesis is focused on TiO2 films as self-cleaning material. Using hydroxypro-pylcellulose (HPC) as additive TiO2 films, V-doped TiO2 films, Si-doped TiO2 films and co-doped TiO2 films by the sol-gel technique on glass substrates, the hydropholicity and photocatalytic activity were investigated.
As to the HPC-doped TiO2 film, it was found that TiO2 films with HPC are composed of smaller particles, and possess higher surface areas and surface roughness. TiO2 films with HPC show better light-induced hydropholicity and higher photocatalytic activity than the films without HPC.
The results show the optical absorption by Vanadium ions doped TiO2 films. The presence of Vanadium and Silica in TiO2 greatly enhanced their photo-activity. The reason of the increasing photo-activity was analyzed. It was found that the acidification of water could also improve the photocatalyst.
The photocatalyst of V and Si co-doped TiO2 films is improved and the hydropholicity of V and Si co-doped TiO2 films is reduced..
由于TiO_2的带隙较宽(约3.2eV)，半导体的光吸收波长范围窄(主要在紫外区)，故其太阳能的利用效率低，且还存在半导体载流子的复合率高，量子化效率低等缺陷。本论文对玻璃表面TiO_2光催化薄膜作为自清洁薄膜材料进行了一系列探讨。从进行TiO_2掺杂改性和结构修饰着手，针对TiO_2自清洁性能有待提高的问题，用溶胶—凝胶浸置提拉法在玻璃基板上制备了掺HPC、掺硅、掺钒薄膜和钒、硅共掺杂，钒、铁共掺杂TiO_2薄膜，对它们的光催化性能和亲水性能作了系统的研究。
对掺HPC薄膜进行光催化活性和亲水性测试结果表明：适量(3m最佳)的HPC加入可以使二氧化钛颗粒的团聚程度降低，颗粒均匀分布，TiO_2晶粒纳米化，粗糙度增加，使TiO_2拥有更大的比表面积，使其光催化性能和亲水性均得到改善。其中3m的HPC改性的TiO_2薄膜经过紫外光照3h后表现为超亲水性。
对掺硅薄膜进行光催化活性和亲水性测试结果表明：硅掺杂提高了TiO_2薄膜光催化活性。但硅的添加量过大时，薄膜光催化活性下降，原因是产生无催化作用的二氧化硅。硅的加入对二氧化钛薄膜的亲水性没有明显影响。
对掺钒薄膜进行光催化活性和亲水性测试结果表明：掺钒后薄膜光学带隙变小，扩大了可利用光的范围，提高了TiO_2薄膜光催化活性。同时钒掺入产生电子空穴俘获阱，降低电子空穴复合，对光催化活性的提高也有贡献。而钒掺杂使TiO_2薄膜亲水性能显著提高，甚至在太阳光照下就具有亲水性。
另外，钒、硅共掺杂进一步提高了Ti_2薄膜光催化活性。选择更为合适的
浙江大学硕士毕业论文
刘琴华:溶胶.凝胶工艺制备二城化钦自清洁薄膜的研究
双离子共掺杂可能会更有效地提高TIO:的光催化。实验中发现共掺杂薄膜的亲
水性能不佳。
综上所述，本研究用溶胶凝胶制备了一系列改性的TIO:薄膜，对它们的自
清洁(光催化性能和亲水性性能)作了系统研究。研究结果发现，对光催化性能
而言，掺HPC、掺钒、掺硅和钒、硅共掺杂都对Tio:薄膜光催化活性有所提高，
但不是所有的改良都带来更好的亲水性。其中，3mHPC掺杂薄膜样品和x二0.巧
的钒掺杂薄膜光催化性能和亲水性性能都比未掺杂Tio:薄膜样品好，可作为自
清洁薄膜。
In recent decades, studies on photocatalysis have attracted considerable attention. Titanium dioxide (TiO2), which is one of the most basic materials in our daily life, has emerged as an excellent photocatalyst material for environmental purification. In this thesis, the history, principle, problems and prospect of the photo induced super-hydropholicity and photocatalytic activity of TiO2 films are reviewed. At the same time, the modifying methods of TiO2 photocatalytic are introduced.
Because of the anatase's broad Eg (3.2eV), the absorption thresholds correspond to 380nm for the TiO2. Consequently, only the ultraviolet fraction of the solar irradiation can be active in the photoexcitation processes using pure TiO2 solid. The high recombination rate of Charge carrier and low efficiency of quantization are also the deficiencies of pure TiO2. This thesis is focused on TiO2 films as self-cleaning material. Using hydroxypro-pylcellulose (HPC) as additive TiO2 films, V-doped TiO2 films, Si-doped TiO2 films and co-doped TiO2 films by the sol-gel technique on glass substrates, the hydropholicity and photocatalytic activity were investigated.
As to the HPC-doped TiO2 film, it was found that TiO2 films with HPC are composed of smaller particles, and possess higher surface areas and surface roughness. TiO2 films with HPC show better light-induced hydropholicity and higher photocatalytic activity than the films without HPC.
The results show the optical absorption by Vanadium ions doped TiO2 films. The presence of Vanadium and Silica in TiO2 greatly enhanced their photo-activity. The reason of the increasing photo-activity was analyzed. It was found that the acidification of water could also improve the photocatalyst.
The photocatalyst of V and Si co-doped TiO2 films is improved and the hydropholicity of V and Si co-doped TiO2 films is reduced..
引文
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