本文選題：PPCPs　切入點：高級氧化技術　出處：《山東大學》2017年博士論文

【摘要】：藥品和個人護理用品(PPCPs)是一種公認的新興污染物,近年來在環(huán)境中不斷被檢出,成為污水處理系統(tǒng)的一大挑戰(zhàn)。因此,本論文選取布洛芬、酮洛芬和阿司匹林作為PPCPs的典型代表物,通過量子化學中的密度泛函理論(DFT)方法,系統(tǒng)地研究了水環(huán)境中PPCPs的降解及遷移轉化問題,為水環(huán)境中PPCPs的有效降解提供技術和理論依據,主要研究內容及結果如下:1.本文基于高精度量子化學計算方法和密度泛函數理論,揭示了布洛芬降解轉化的微觀機制,在M06-2x/6-311++G(2dp)//M06-2x/6-31+G(d,p)水平上研究了由OH自由基引發(fā)的布洛芬在高級氧化過程中降解機理。首先,對前線電子密度和鍵離解能進行計算和分析,指出最可能反應的位置。此外,構造了反應勢能剖面,并在此基礎上對所有可能的反應途徑進行探討和研究,從而發(fā)現氫抽提是最重要的反應機理。反應的主要產物為對異丁基苯乙酮(IBPA), 2-[4-(1-羥基異丁基)苯基]丙酸和1-(4-異丁基苯基)-1-乙醇。計算結果與實驗數據進行了比較,兩者具有很高的一致性。2.結合密度泛函理論計算和實驗方法探究了 OH自由基引發(fā)的酮洛芬的轉化降解機理。在密度泛函計算反面,分析了前線電子密度和鍵離解,構建了所有可能反應途徑的反應勢能剖面。此外,采用過渡態(tài)理論計算了每條反應途徑的速率常數。同時討論了次級反應中的脫羧基反應和雙苯環(huán)結構解離反應。實驗方面,進行了酮洛芬的Fenton降解實驗并采用UPLC-MSn方法鑒定了主要的轉化降解產物。3.采用密度泛函理論方法和實驗探究了阿司匹林在高級氧化技術體系中氧化轉化和水解的機理。在計算層面上分析了前線電子密度和鍵離解,構建了所有可能反應途徑的反應勢能剖面并計算了每條反應途徑的速率常數。進行了UV/H2O2降解實驗并采用UPLC-MS-MS方法鑒定了反應中的中間體和降解產物。得到了與之前報道不同的結論:甲基官能團上的氫抽提反應和苯環(huán)結構上的氫抽提反應在高級氧化技術降級阿司匹林時是最容易發(fā)生的。實驗檢測到羥基化阿司匹林為最主要的中間產物。更重要的是,這是首次采用密度泛函方法來探究芳香族酯類有機物的水解機理。
[Abstract]:Drugs and personal care products (PPCPs) are recognized as emerging pollutants, which have been continuously detected in the environment in recent years, and have become a major challenge in sewage treatment systems.Therefore, ibuprofen, ketoprofen and aspirin were selected as the typical representative of PPCPs, and the degradation and migration of PPCPs in water environment were systematically studied by using density functional theory (DFT) method in quantum chemistry.To provide technical and theoretical basis for the effective degradation of PPCPs in water environment, the main research contents and results are as follows: 1.Based on the high precision quantum chemistry calculation method and density universal function theory, the microcosmic mechanism of ibuprofen degradation and transformation was revealed. The degradation mechanism of ibuprofen initiated by OH radical during the advanced oxidation process was studied at the M06-2x/6-311 G(2dp)//M06-2x/6-31 Gudp level.First, the electron density and bond dissociation energy in the front line are calculated and analyzed, and the position of the most likely reaction is pointed out.In addition, the reaction potential energy profile was constructed, and all possible reaction pathways were discussed and studied on the basis of which, it was found that hydrogen extraction is the most important reaction mechanism.The main products of the reaction are p-isobutylacetophenone, 2-[ 4-butane-1-hydroxyisobutyl) phenyl] propionic acid and 1-mono-4-isobutyl phenyl -1-ethanol. the main products of the reaction are p-isobutyl acetophenone (p-isobutyl acetophenone), 2- [4-hydroxyisobutyl) phenyl] propionic acid.The calculated results are compared with the experimental data.The conversion and degradation mechanism of ketoprofen initiated by OH radical was investigated by density functional theory (DFT) and experimental method.On the contrary of density functional calculation, the forward electron density and bond dissociation are analyzed, and the potential energy profiles of all possible reaction pathways are constructed.In addition, the transition state theory is used to calculate the rate constants of each reaction pathway.At the same time, the decarboxylation reaction and the structure dissociation reaction of diphenyl ring in the secondary reaction were discussed.In addition, the Fenton degradation of ketoprofen was carried out and the main transformation degradation product. 3. 3 was identified by UPLC-MSn method.The mechanism of oxidation conversion and hydrolysis of aspirin in advanced oxidation system was investigated by density functional theory (DFT) and experiments.The electron density and bond dissociation at the front line were analyzed at the computational level. The potential energy profiles of all possible reaction pathways were constructed and the rate constants of each reaction pathway were calculated.UV/H2O2 degradation experiments were carried out and the intermediates and degradation products were identified by UPLC-MS-MS method.Different from previous reports, hydrogen extraction reaction on methyl functional group and hydrogen extraction reaction on benzene ring structure are most likely to occur when aspirin is degraded by advanced oxidation technology.Hydroxylated aspirin was identified as the most important intermediate product.More importantly, it is the first time that the density functional method is used to study the hydrolysis mechanism of aromatic esters.
【學位授予單位】：山東大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：X703

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