發(fā)布時(shí)間：2018-04-03 03:33

  本文選題：均相催化劑　切入點(diǎn)：氯球　出處：《浙江理工大學(xué)》2017年碩士論文

【摘要】：水是人類生活中不可或缺的一種物質(zhì),人體組織中的水份占體重的60%至70%,其他動(dòng)植物體內(nèi)的水份也占5%以上,這表明水是維持生命必不可少的物質(zhì)。此外,水也是關(guān)系到國家經(jīng)濟(jì)命脈的重要因素,因?yàn)闊o論是工業(yè)發(fā)展、商業(yè)活動(dòng)、農(nóng)業(yè)經(jīng)營、水產(chǎn)養(yǎng)殖等,都離不開水。但是目前水污染的問題越來越突出,主要是由于工業(yè)和農(nóng)業(yè)運(yùn)行過程中產(chǎn)生了一些有毒有機(jī)污染物,比如染料、抗生素以及農(nóng)藥等的使用就會(huì)對(duì)環(huán)境造成嚴(yán)重的危害。然而這些污染物化學(xué)需氧量高,成分復(fù)雜,傳統(tǒng)的生物技術(shù)和物理技術(shù)難以將其降解。高級(jí)氧化技術(shù)(AOPs)是通過產(chǎn)生強(qiáng)氧化活性種,將有機(jī)污染物氧化成易被生化的小分子物質(zhì)或者將其徹底礦化。而從原子經(jīng)濟(jì)和環(huán)境友好的角度考慮,使用過氧化氫作為綠色氧化劑和以廉價(jià)的金屬銅、鐵作為催化活性中心的催化氧化反應(yīng),在廉價(jià)大規(guī)模生產(chǎn)和合成領(lǐng)域具有重要的意義。本篇論文設(shè)計(jì)并合成了一系列體現(xiàn)高價(jià)金屬-氧活性種的配位化合物,對(duì)此催化體系高效高選擇性地催化雙氧水氧化染料、抗生素等有機(jī)污染物的反應(yīng)進(jìn)行了系統(tǒng)的研究。通過對(duì)各部分的實(shí)驗(yàn)結(jié)果進(jìn)行分析和比較,對(duì)比出不同金屬活性種的催化體系的活性差異,且驗(yàn)證了4-氨基吡啶取代基對(duì)其催化活性的影響。本論文共包括以下幾方面的內(nèi)容:合成均相的催化體系—亞氨基二乙酸/銅(Ⅱ)/4-氨基吡啶配合物(IDA/Cu(Ⅱ)/4-ampy),考察其催化活性及反應(yīng)機(jī)理;然而均相催化劑雖然具有非常高的催化活性,可被廣泛應(yīng)用于有機(jī)污染物的去除,但因其具有難回收,易造成二次污染的缺點(diǎn),故將其負(fù)載到載體上,從而可解決此問題。離子交換樹脂—氯球(PS)有優(yōu)異的化學(xué)穩(wěn)定性,改性后有很好的吸附性,可作為催化劑的載體,并且可以促進(jìn)溶液中的有機(jī)污染物富集,從而更好地催化降解有機(jī)污染物,因此將均相催化劑負(fù)載到PS上制備負(fù)載型催化劑,并考察負(fù)載后的催化活性;然后改變中心金屬,合成氯球負(fù)載亞氨基二乙酸/鐵(Ⅱ)/4-氨基吡啶配位化合物(PS-IDA/Fe(Ⅱ)/4-ampy)催化劑,考察其催化活性及反應(yīng)機(jī)理并對(duì)其進(jìn)行一系列表征實(shí)驗(yàn)。研究結(jié)果表明4-氨基吡啶取代基對(duì)其催化活性的影響較大,且各催化體系都表現(xiàn)出較高的催化性能,且不同催化體系均不受異丙醇的影響,再通過EPR測(cè)試,表明了各催化體系均為非·OH反應(yīng)機(jī)理,因此可以推測(cè)出的機(jī)理是催化體系在活化雙氧水過程中產(chǎn)生了高價(jià)金屬-氧活性種。
[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，

本文編號(hào)：1703462