联噻唑类金属配合物制备与光催化水制氢研究

发布时间：2018-02-24 03:36

本文关键词： 光催化水制氢联噻唑金属配合物 C_(60) 纳米铜银量子点　出处：《华南理工大学》2016年博士论文　论文类型：学位论文

【摘要】：随着社会的不断发展,传统化石能源的消耗。由于化石能源储备有限,而且对环境造成的污染不断加剧,因此开发一种清洁、环保的可再生能源,代替传统化石能源,已经成为人们的目标。可再生能源主要包含太阳能、水能、地热能和氢能等。其中,氢能被认为是最理想的能源之一。可是快速高效地制备氢气,一直是氢能应用中的难题。迄今为止,光催化技术可以将太阳能转化为氢能,是制备氢气既环保又理想的方式。目前采用的光致产氢体系主要由催化剂和电子给体两种组分构成。然而在大多数光催化体系中,催化剂采用无机半导体材料,从而限制了它们的光响应范围。因此,探索金属配合物类催化剂更具有实际意义。本文通过溶剂热、掺杂等方法设计制备了一系列高性能的光催化剂,所取得的研究结果主要包括:(1)设计和研发新型联噻唑金属配合物,以此作为光催化剂,设计并合成三种联噻唑金属配合物,并借助于核磁共振、红外、高分辨质谱、紫外可见分光光度计、荧光光谱仪、瞬态荧光光谱仪对其结构、光学等能进行表征。同时,经过光催化水制氢测试,在可见光照射下,发现它们都有光致产氢活性。(2)在已合成述三种联噻唑类金属配合物的基础上,,采用溶剂热法加入C_(60)制备复合型光催化剂,探讨不同C_(60)的量对联噻唑类金属配合物的光催化性能影响,发现当C_(60)的量为2.0 wt%,该复合型材料的光催化效果最好(7.39 mmol*h~(-1)*g~(-1))。(3)以纳米铜和联噻唑类金属配合物为原料,制备等离子体光催化剂,该材料具有蓬松的球形介孔结构,比表面积较大,在紫外-可见光区域均有吸收。在可见光照射下,当纳米铜负载量为5.4 wt%时,Cu NPs/Cu-2TPABTz的光催化活性最高。不仅如此,它还呈现较好的催化稳定性,循环使用六次后依然保持活性不变。4、在已优化联噻唑类金属配合物的基础上,以CTAB和Ag NO_3为原料,通过沉淀沉积法结合光还原技术,制备了不同Ag QDs/Co-2TPABTz高效复合光催化剂,拓宽了催化剂对光的吸收范围(从紫外光拓展到可见光范围),实现了光催化水制氢,并依据反应条件给出了可见光辐射下催化剂的光催化机理。5、以纳米氧化锌为前驱体,采用溶胶-凝胶法,制备得到含钇、铝共掺杂的,规整的纳米氧化锌催化剂。该钇铝共掺杂纳米氧化锌催化剂具有良好的光催化水制氢性能,更加优异的光化学稳定性。通过研究不同钇含量的催化剂,我们发现,钇对于该光催化剂规整球形形貌及多孔结构的形成有着非常重要的作用,通过改变前驱体中的钇用量,可以调节催化剂的多孔结构及比表面积。对于特定的催化剂,当钇含量为5%时,其比表面积可高达118.5 m2*g~(-1)。
[Abstract]:With the continuous development of society, the consumption of traditional fossil energy. Because of the limited reserves of fossil energy and the increasing pollution to the environment, we develop a clean, environmentally friendly renewable energy instead of traditional fossil energy. Renewable energy mainly includes solar energy, water energy, geothermal energy and hydrogen energy. Among them, hydrogen energy is considered as one of the most ideal energy sources. So far, photocatalytic technology has been able to convert solar energy into hydrogen energy. It is an environmentally friendly and ideal way to produce hydrogen. The photogenic hydrogen production system is mainly composed of two components: catalyst and electron donor. However, in most photocatalytic systems, inorganic semiconductor materials are used as catalysts. Therefore, it is of practical significance to explore metal complex catalysts. In this paper, a series of high performance photocatalysts were designed and prepared by solvothermal, doping and other methods. The main results of the study include the design and development of novel bithiazolium metal complexes, which can be used as photocatalysts to design and synthesize three kinds of bithiazolium metal complexes. The complexes are characterized by NMR, IR and high resolution mass spectrometry. The structure and optical properties were characterized by UV-Vis spectrophotometer, fluorescence spectrometer and transient fluorescence spectrometer. It is found that all of them have photogenic activity. 2) on the basis of the three kinds of metal complexes of bithiazoles synthesized, the composite photocatalyst was prepared by solvothermal addition of Che 60). In this paper, we studied the effect of different amount of Che (60) on the photocatalytic properties of thiazolium metal complexes. It was found that when the amount of CSP 60) was 2.0 wt, the photocatalytic effect of the composite material was the best (7.39 mmol / L). Plasma photocatalyst was prepared. The material has a fluffy spherical mesoporous structure, large specific surface area and absorption in the UV-Vis region. The photocatalytic activity of Cu NPs/Cu-2TPABTz is the highest when the loading amount of nano-copper is 5.4 wt%. Not only this, but also the photocatalytic stability is good. After six cycles, the activity remains unchanged .4. on the basis of the optimized metal complexes of bithiazolium, Using CTAB and Ag NO_3 as raw materials, different Ag QDs/Co-2TPABTz composite photocatalysts were prepared by precipitation and deposition combined with photoreduction technology. The range of photoabsorption of the catalysts was broadened from ultraviolet to visible light, and the photocatalytic water production of hydrogen was realized. According to the reaction conditions, the photocatalytic mechanism of the catalyst under visible light radiation was given. Using nanometer zinc oxide as precursor, yttrium and aluminum co-doped were prepared by sol-gel method. This nanometer zinc oxide catalyst co-doped with yttrium and aluminum has good photocatalytic properties for hydrogen production from water and better photochemical stability. By studying the catalysts with different contents of yttrium, we find that, Yttrium plays an important role in the formation of spherical morphology and porous structure of the photocatalyst. By changing the amount of yttrium in the precursor, the porous structure and specific surface area of the catalyst can be adjusted. When the yttrium content is 5, its specific surface area can be as high as 118.5 m ~ (2) g ~ (-1) ~ (-1).
【学位授予单位】：华南理工大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：O643.36;TQ116.2

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