高价金属—氧活性种的生成及降解有机污染物的研究

发布时间：2018-04-03 03:33

  本文选题：均相催化剂　切入点：氯球　出处：《浙江理工大学》2017年硕士论文

【摘要】：水是人类生活中不可或缺的一种物质,人体组织中的水份占体重的60%至70%,其他动植物体内的水份也占5%以上,这表明水是维持生命必不可少的物质。此外,水也是关系到国家经济命脉的重要因素,因为无论是工业发展、商业活动、农业经营、水产养殖等,都离不开水。但是目前水污染的问题越来越突出,主要是由于工业和农业运行过程中产生了一些有毒有机污染物,比如染料、抗生素以及农药等的使用就会对环境造成严重的危害。然而这些污染物化学需氧量高,成分复杂,传统的生物技术和物理技术难以将其降解。高级氧化技术(AOPs)是通过产生强氧化活性种,将有机污染物氧化成易被生化的小分子物质或者将其彻底矿化。而从原子经济和环境友好的角度考虑,使用过氧化氢作为绿色氧化剂和以廉价的金属铜、铁作为催化活性中心的催化氧化反应,在廉价大规模生产和合成领域具有重要的意义。本篇论文设计并合成了一系列体现高价金属-氧活性种的配位化合物,对此催化体系高效高选择性地催化双氧水氧化染料、抗生素等有机污染物的反应进行了系统的研究。通过对各部分的实验结果进行分析和比较,对比出不同金属活性种的催化体系的活性差异,且验证了4-氨基吡啶取代基对其催化活性的影响。本论文共包括以下几方面的内容:合成均相的催化体系—亚氨基二乙酸/铜(Ⅱ)/4-氨基吡啶配合物(IDA/Cu(Ⅱ)/4-ampy),考察其催化活性及反应机理;然而均相催化剂虽然具有非常高的催化活性,可被广泛应用于有机污染物的去除,但因其具有难回收,易造成二次污染的缺点,故将其负载到载体上,从而可解决此问题。离子交换树脂—氯球(PS)有优异的化学稳定性,改性后有很好的吸附性,可作为催化剂的载体,并且可以促进溶液中的有机污染物富集,从而更好地催化降解有机污染物,因此将均相催化剂负载到PS上制备负载型催化剂,并考察负载后的催化活性;然后改变中心金属,合成氯球负载亚氨基二乙酸/铁(Ⅱ)/4-氨基吡啶配位化合物(PS-IDA/Fe(Ⅱ)/4-ampy)催化剂,考察其催化活性及反应机理并对其进行一系列表征实验。研究结果表明4-氨基吡啶取代基对其催化活性的影响较大,且各催化体系都表现出较高的催化性能,且不同催化体系均不受异丙醇的影响,再通过EPR测试,表明了各催化体系均为非·OH反应机理,因此可以推测出的机理是催化体系在活化双氧水过程中产生了高价金属-氧活性种。
[Abstract]:Water is an indispensable substance in human life. Water in human tissue accounts for 60% to 70% of body weight, and more than 5% in other animals and plants, which indicates that water is essential to life.In addition, water is also an important factor related to the national economic lifeline, because whether it is industrial development, commercial activities, agricultural operations, aquaculture and so on, can not do without water.However, the problem of water pollution is becoming more and more serious, mainly due to the production of some toxic organic pollutants, such as dyes, antibiotics and pesticides, which will cause serious harm to the environment.However, the chemical oxygen demand of these pollutants is high, the composition is complex, it is difficult to degrade them by traditional biotechnology and physical technology.Advanced oxidation technology (AOPs) is to oxidize organic pollutants into biodegradable small molecules or to mineralize them completely by producing highly oxidized active species.From the point of view of atomic economy and environmental friendliness, the use of hydrogen peroxide as a green oxidant and the use of cheap metal copper and iron as the catalytic active center is of great significance in the field of cheap large-scale production and synthesis.In this paper, a series of coordination compounds with high valence metal-oxygen activity have been designed and synthesized. The catalytic system has been used to catalyze the oxidation of organic pollutants such as hydrogen peroxide dyes and antibiotics with high efficiency and selectivity.Through the analysis and comparison of the experimental results of each part, the difference of catalytic activity of different metal active species was compared, and the effect of 4-aminopyridine substituents on their catalytic activity was verified.This thesis includes the following aspects: synthesis of homogeneous catalytic system-iminodiacetic acid / copper (鈪，

本文编号：1703462