摘要
光催化技术是近年来兴起的一种新型环境治理技术,得到人们的广泛关注。发展高效的可见光催化剂是实现该技术实用化的关键。针对非金属离子掺杂TiO_2制备工艺条件复杂和普适性差以及BiVO_4粒径尺寸大、活性差的问题,本论文分别开展了发展非金属离子掺杂TiO_2和小粒子BiVO_4光催化剂新方法的研究。
在结合水解法和溶剂热法优点的基础上,通过发展相分离的水解‐溶剂热法,可控合成氮、硫、硅等非金属离子掺杂的TiO_2,重点研究合成过程中各合成条件对样品可见光催化活性的影响。研究结果表明:与传统的溶胶‐水热法相比,本方法合成的TiO_2样品表现出了高的光催化活性,这主要是由于其具备了高的晶化度和好的分散性。通过在水相中引入氨水等物质,可控的实现了对TiO_2的氮等非金属离子的掺杂,显著拓宽了样品的光响应范围,样品表现出了高的可见光催化活性,明显要高于高温氮化法制得的样品。此外,通过在有机相中引入正硅酸乙酯也简单的实现了紫外光活性超过P25的高热稳定性硅掺杂TiO_2的合成。
针对BiVO_4在生成过程中晶核生长速度快、粒子易生长过大的问题,通过发展EDTA调制的水热法方法可控合成了纳米BiVO_4,重点研究了反应温度等因素对样品粒径尺寸的影响。研究结果表明,降低反应温度、缩短反应时间和增大EDTA的用量,有利于获得小尺寸的BiVO_4,可以得到粒径尺寸为20nm的BiVO_4粒子。基于红外分析的结果,反应过程中EDTA与Bi~(3+)反应形成稳定的螯合物,降低了Bi~(3+)的浓度,从而抑制了BiVO_4粒子的生长。所获得小粒子BiVO_4表现出了高的可见光催化活性,这主要与其具有小的粒径尺寸和大的比表面积有关。
Photocatalytic technology which is developed in recent years is a new environmental control technology, and has caught people's attention widely. Preparing the visible-light photocatalyst is the key for making this technology practical. To the problems of complicated technology and poor wide suitability in preparing nonmetal doped TiO_2 and large particle size and poor photocatalytic activity of BiVO_4 samples prepared by normal methods, we carried out the study of developing new methods to prepare non-metal doped TiO_2 and nano-sized BiVO_4 photocatalysts.
O_n the basis of combining the advantages of hydrolysis process and solvothermal process, we developed the phase-separated hydrolysis-solvothermal process, and through it we prepared the TiO_2 which doped with N, S, Si et al controllable, the effects of reaction temperature et al on the photocatalytic activity of samples were mainly investigated. The results show that, comparing to the TiO_2 prepared by hydrolysis-hydrothermal process, the TiO_2 we prepared has better UV-photocataltic activity due to the higher crystalline degree and dispersibility. By introducing the ammonia et al into the water phase, we obtain the N et al non-metal doped TiO_2 simply. The non-metal doping enhances the visible light absorption of TiO_2 effectively, and the sample exhibits a good Vis-photocatalytic activity, it is worth noting to that the N-doped TiO_2 exhibits better photocatalysis activity than the sample prepared by high-temperature nitriding. In addition, the Si-doped TiO_2 with high thermal stability and photocatalytic activity which is better than the photocatalytic activity of P25 also can be obtained by introducing the C8H20O_4Si into the organic phase.
To the problems the BiVO_4 particle is easy to grow too large in synthesis process, we developed a new method to prepare nano-sized BiVO_4 by introducing EDTA. And the effects of reaction temperature et al on the particle size of samples were mainly investigated. The results show that reducing the reaction temperature and time and increasing the addition of EDTA are benign to the controlling the particle size of BiVO_4, the BiVO_4 samples with an average particle size of 20 nm can be obtained. Based on the IR spectra, it is confirmed that the introduction of EDTA can be coordinate with Bi~(3+) to form a stable compound, consequently keeping a low-content free Bi~(3+) in the reaction system and then inhibiting the growth of BiVO_4 crystallites during the hydrothermal processes. The nano-sized BiVO_4 particles show a high Vis-photocatalytic activity, that is mainly due to its small particle size and large surface area.
引文
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